KR20110053981A - Phthalocyanine compound - Google Patents

Abstract

[화학식 2]
-X-A₁
[화학식 3]

[화학식 2']

It is an object of the present invention to provide a phthalocyanine compound having a maximum absorption wavelength in a shorter wavelength region, particularly 640 to 750 nm, and excellent in heat resistance. The above object is the following formula (1): wherein, Z ₁ to Z ₁₆ are each independently a hydrogen atom, a halogen atom, a group represented by the following formula 2: or the following formula 3: or the following formula 2 ': 4 to 10 of Z ₁ to Z ₁₆ are groups represented by Formula 2 or 2 ′, at least one of which is a group represented by Formula 2, 3 to 12 are hydrogen atoms, and Z ₁ to Z _16. In the case of 12 heavy hydrogen atoms, 4 are groups represented by the formula (2) or (2 '), and 1 to 3 of Z ₁ , Z ₄ , Z ₅ , Z ₈ , Z ₉ , Z ₁₂ , Z _13, and Z ₁₆ are A group represented by the formula (2) or (2 '), and 3 to 1 of Z ₂ , Z ₃ , Z ₆ , Z ₇ , Z ₁₀ , Z ₁₁ , Z _14, and Z ₁₅ are groups represented by the formula (2) or (2). In the case of 3 to 11 hydrogen atoms in Z ₁ to Z ₁₆ , at least one is a halogen atom, and M represents a nonmetal, a metal, a metal oxide, or a metal halide: All:

(2)
-XA ₁
(3)

[Formula 2 ']

Description

Phthalocyanine compound

The present invention relates to a phthalocyanine compound and a filter for a flat panel display. In detail, this invention relates to the phthalocyanine compound which has the maximum absorption wavelength in the wavelength range of 640-750 nm, and the filter for flat panel displays containing the same.

In recent years, a flat panel display is attracting attention as a display that can be thin and large screen. Among them, a plasma display panel (PDP) and a liquid crystal display (LCD) are widely attracting attention in the market. However, PDP generates near-infrared light at the time of plasma discharge, and this near-infrared light may cause malfunctions of peripheral electronic devices such as remote control such as home televisions, coolers, video decks, and transmission system optical communication, thereby cutting out the near-infrared light. It is necessary to install an infrared absorption filter in the front.

For this purpose, a phthalocyanine-based system having high visible light transmittance and capable of efficiently cutting near-infrared light of a relatively long wavelength range of 800 to 1000 nm from the display, i.e., having excellent selective absorption ability in the near-infrared wavelength range of the wavelength range. Various studies have been made on pigments (see, eg, US Patent Application Publication No. 2001/005278).

However, in recent years, the flow of increasing information volume has become very fast, and shorter recording wavelengths are required, for example, as CD-R is transformed into DVD ± R as a large capacity optical disk. Therefore, it is considered that the optical communication system currently used in the same manner at the wavelength of 800 to 900 nm used in mobile phones, game machines, etc., can be shortened in the wavelength of around 700 nm in the future. However, current PDPs have extra light emission at wavelengths of 700 to 750 nm, but filters for cutting wavelengths of 700 to 750 nm are not provided, which may cause malfunction of transmission system optical communication. I think it is necessary to install the filter in front.

At the same time, although light of 640-700 nm wavelength is used for some LCD which is weak in red color development, since it is a color tone called "magenta" unlike pure red of 610-635 nm wavelength range, flat panel display In the field of a liquid crystal display, it is not necessarily preferable to use light of a hue, and especially the PDP which has strong red light emission requires the filter which cuts the light of this wavelength range in order to reproduce pure red.

By the way, in addition to having a maximum absorption wavelength in the wavelength range of 640-750 nm, various characteristics, such as heat resistance, are calculated | required by the near-infrared absorbing dye added to the filter for plasma displays.

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 640 to 750 nm, and excellent in heat resistance.

That is, the said objective is following formula (1):

In the formula, Z ₁ to Z ₁₆ are each independently a hydrogen atom, a halogen atom, the following formula 2:

[Formula 2]

-XA ₁

In the formula, X is an oxygen atom or a sulfur atom, A ₁ is a phenyl group, a phenyl group having 1 to 5 substituents R or a naphthyl group having 1 to 7 substituents R, and the substituents R are each independently a nitro group or a COOR ₁ , OR ₂ (R ₂ is an alkyl group having 1 to 8 carbon atoms), a halogen atom, an aryl group, a cyano group or an alkyl group having 1 to 8 carbon atoms that may be substituted with a halogen atom, wherein R ₁ is an alkyl group having 1 to 8 carbon atoms (In this case, the alkyl group may be substituted with an alkyloxy group having 1 to 8 carbon atoms, a halogen atom or an aryl group) or the following general formula 3:

(3)

In the formula, R ₃ is an alkylene group having 1 to 3 carbon atoms, R ₄ is an alkyl group having 1 to 8 carbon atoms, n is an integer of 1 to 4;

[Formula 2 ']

In the formula, R 'is an alkylene group having 1 to 3 carbon atoms, R "is an alkyl group having 1 to 8 carbon atoms, l is an integer of 0 to 4;

In this case, 4 to 10 of Z ₁ to Z ₁₆ are a group represented by the formula (2) or (2 '), at least one of them is a group represented by the formula (2), 3 to 12 is a hydrogen atom,

When four of Z ₁ to Z ₁₆ are a group represented by the formula (2) or (2 '), and the rest are hydrogen atoms, Z ₁ , Z ₄ , Z ₅ , Z ₈ , Z ₉ , Z ₁₂ , Z ₁₃ and Z ₁₆ 1 to 3 are groups represented by Formula 2 or 2 ', and 1 to 3 of Z ₂ , Z ₃ , Z ₆ , Z ₇ , Z ₁₀ , Z ₁₁ , Z _14, and Z ₁₅ are represented by Formula 2 or Formula 2 'is a group

In the case of 3 to 11 hydrogen atoms in Z ₁ to Z ₁₆ , at least one is a halogen atom,

M represents a nonmetal, metal, metal oxide or metal halide:

It is achieved by the phthalocyanine compound represented by. In this specification, the phthalocyanine compound of the said Formula (1) is also only called "phthalocyanine compound (1)."

Since the phthalocyanine compound of this invention shows the maximum absorption wavelength especially in the vicinity of 640-750 nm, the light of the useless near-infrared (700-750 nm) emitted by a flat panel display, especially a PDP and LCD, or what is called crimson red By cutting the light having a wavelength of 640 to 700 nm, it is possible to prevent the malfunction of the optical communication system, for example, and to attain the effect of reproducing vivid red color at the same time.

Still other objects, features and characteristics of the present invention will become apparent by considering preferred embodiments illustrated in the following description and the annexed drawings.

EMBODIMENT OF THE INVENTION Hereinafter, embodiment of this invention is described in detail.

The present invention is the following formula (1):

In the formula, Z ₁ to Z ₁₆ are each independently a hydrogen atom, a halogen atom, the following formula 2:

[Formula 2]

-XA ₁

In the formula, X is an oxygen atom or a sulfur atom, A ₁ is a phenyl group, a phenyl group having 1 to 5 substituents R or a naphthyl group having 1 to 7 substituents R, and the substituents R are each independently a nitro group or a COOR ₁ , OR ₂ (R ₂ is an alkyl group having 1 to 8 carbon atoms), a halogen atom, an aryl group, a cyano group or an alkyl group having 1 to 8 carbon atoms that may be substituted with a halogen atom, wherein R ₁ is an alkyl group having 1 to 8 carbon atoms (In this case, the alkyl group may be substituted with an alkyloxy group having 1 to 8 carbon atoms, a halogen atom or an aryl group) or the following general formula (3);

(3)

In the formula, R ₃ is an alkylene group having 1 to 3 carbon atoms, R ₄ is an alkyl group having 1 to 8 carbon atoms, n is an integer of 1 to 4;

[Formula 2 ']

In the formula, R 'is an alkylene group having 1 to 3 carbon atoms, R "is an alkyl group having 1 to 8 carbon atoms, l is an integer of 0 to 4;

In this case, 4 to 10 of Z ₁ to Z ₁₆ are a group represented by the formula (2) or (2 '), at least one of them is a group represented by the formula (2), 3 to 12 is a hydrogen atom,

When four of Z ₁ to Z ₁₆ are a group represented by the formula (2) or (2 '), and the rest are hydrogen atoms, Z ₁ , Z ₄ , Z ₅ , Z ₈ , Z ₉ , Z ₁₂ , Z ₁₃ and Z ₁₆ 1 to 3 are groups represented by Formula 2 or 2 ', and 1 to 3 of Z ₂ , Z ₃ , Z ₆ , Z ₇ , Z ₁₀ , Z ₁₁ , Z _14, and Z ₁₅ are represented by Formula 2 or Formula 2 'is a group

In the case of 3 to 11 hydrogen atoms in Z ₁ to Z ₁₆ , at least one is a halogen atom,

M represents a nonmetal, metal, metal oxide or metal halide:

It relates to a phthalocyanine compound represented by.

In this specification, the phthalocyanine compound of the said Formula (1) is also only called "phthalocyanine compound (1)." In addition, in this specification, Z <_1> , Z <_4> , Z <_5> , Z <_8> , Z <_9> , Z <_12> , Z <_13> and Z <_16> in Formula (1) substitute the substituent which substitutes in eight alpha positions of the phthalocyanine nucleus. For the sake of illustration, these substituents are also called substituents at the α position. In the same manner, in the formula (1), Z ₂ , Z ₃ , Z ₆ , Z ₇ , Z ₁₀ , Z ₁₁ , Z _14, and Z ₁₅ represent substituents substituted at eight β-positions of the phthalocyanine nucleus. These substituents are also called substituents at the β-position.

Since the phthalocyanine compound (1) shows the maximum absorption wavelength in a specific wavelength range of 640 to 750 nm, it is possible to selectively cut light in these regions. For this reason, the filter for flat panel displays using the phthalocyanine compound of this invention is useful in preventing the malfunction of the optical communication system corresponding to the flow of information volume increase, for example, and simultaneously reproducing vivid red. In addition, the phthalocyanine compound (1) efficiently cuts light having a wavelength of 640 to 700 nm, which is not necessarily light of a desired color tone in the field of flat panel displays or liquid crystal displays, where red light is strong. The filter used can be used suitably for flat panel displays or liquid crystal displays that reproduce pure red color.

In the formula (1), Z ₁ ~ Z ₁₆ is a hydrogen atom, a halogen atom, the following formula 2:

[Formula 2]

-XA ₁

Or the following Formula 2 ':

[Formula 2 ']

Indicates. In this case, Z ₁ ~ Z ₁₆ are be the same, even if it is different.

As a halogen atom in Z <_1> -Z <_16> , there exist a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom, Among these, Preferably it is a fluorine atom and a chlorine atom, More preferably, it is a chlorine atom.

In the formula (2), X represents an oxygen atom or a sulfur atom. Preferably it is an oxygen atom. When X is an oxygen atom, since the maximum absorption wavelength of the phthalocyanine compound obtained can be shifted to the short wavelength side, the maximum absorption wavelength ((lambda) _max ) of the obtained phthalocyanine compound can be easily adjusted to the wavelength range of 640-750 nm among near-infrared regions. .

In Formula (2), A ₁ represents a phenyl group, a phenyl group having 1 to 5 substituents R, or a naphthyl group having 1 to 7 substituents R. Preferably, it is a phenyl group which has 1-5 substituents R, or a naphthyl group which has 1-7 substituents R, More preferably, it is a phenyl group which has 1-5 substituents R.

Although the number of substituents of a phenyl group is 1-5, More preferably, the integer of 1-3 is represented from a viewpoint of a gram extinction coefficient, and when a substituent is a halogen atom, the integer of 1-5 is all preferable. Although the number of substituents of a naphthyl group is 1-7, it is preferable that it is 1-5 from a viewpoint of a gram extinction coefficient (absorbance per gram), It is more preferable that it is 1-3, It is more preferable that it is 1 or 2.

The bonding position of a naphthyl group and X is not specifically limited, Any of the following 1-position (1-naphthyl group) or 2-position (2-naphthyl group) may be sufficient.

Likewise, the position of the bond in the naphthalene ring of the substituent is not particularly limited. For example, in the case where the naphthyl group and the X linking position are 1-position (1-naphthyl group), the bonding position in the naphthalene ring ring of the substituent is 2, 3, 4, 5, 6, 7 Although any of position or 8 position may be sufficient, in consideration of heat resistance, solvent solubility, etc., a 2nd-position and a 3-position position are preferable, and a 2nd position is more preferable. In the case where the naphthyl group is bonded to X at the 2-position position (2-naphthyl group), the position at which the substituent is bonded to the naphthalene ring is 1 position, 3 position, 4 position, 5 position, 6 position, 7 position or Although any of the 8-position site may be sufficient, 3-position and 6-position are preferable, and a 3-position is more preferable in consideration of heat resistance, solvent solubility, etc.

The substituent of the phenyl group or the naphthyl group (hereinafter also referred to as R) is a nitro group, COOR ₁ , OR ₂ (R ₂ is an alkyl group having 1 to 8 carbon atoms), a halogen atom, an aryl group, a cyano group, or an alkyl group having 1 to 8 carbon atoms. (In this case, the alkyl group may be substituted with a halogen atom). In this case, R ₁ is an alkyl group having 1 to 8 carbon atoms (wherein the alkyl group may be substituted with an alkyloxy group having 1 to 8 carbon atoms, a halogen atom or an aryl group) or a group represented by the following formula (3). When two or more substituents R exist in a phenyl group or a naphthyl group, some R may be same or different.

(3)

In general formula (3), R <_3> is a C1-C3 alkylene group, R <_4> is a C1-C8 alkyl group, n is an integer of 1-4.

When R is a COOR _1, R ₁ of the COOR ₁ indicates a group represented by formula (3) or an alkyl group having 1 to 8 carbon atoms which may be substituted.

When R <_1> is a C1-C8 alkyl group, a C1-C8 alkyl group is a C1-C3 alkyl group from a solvent solubility point. Examples of the alkyl group having 1 to 8 carbon atoms include methyl group, ethyl group, n-propyl group, iso-propyl group, n-butyl group, iso-butyl group, sec-butyl group, t-butyl group, n-pentyl group and n-hexyl group And linear, branched or cyclic alkyl groups such as cyclohexyl group, n-heptyl group, n-octyl group and 2-ethylhexyl group. Substituents which are optionally present in a C1-C8 alkyl group are a C1-C8 alkyloxy group, a halogen atom, or an aryl group. Examples of the alkyloxy group having 1 to 8 carbon atoms which are optionally substituted alkyl groups include methoxy group, ethoxy group, n-propyloxy group, iso-propyloxy group, n-butyloxy group, iso-butyloxy group, sec- Linear, branched, such as butyloxy group, t-butyloxy group, n-pentyloxy group, n-hexyloxy group, cyclohexyloxy group, n-heptyloxy group, n-octyloxy group, 2-ethylhexyloxy group Or a cyclic alkyloxy group. Among these, a C1-C4 alkyloxy group is preferable. As a halogen atom which is a substituent of the alkyl group which exists in some cases, a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom are mentioned. Among these, a fluorine atom or a chlorine atom is preferable. As an aryl group which is a substituent of the alkyl group which exists in some cases, a phenyl group, p-methoxyphenyl group, pt-butylphenyl group, p-chlorophenyl group etc. are mentioned. Among these, a phenyl group is preferable. A plurality of these substituents may be present, and in the case where a plurality of substituents are present, any one of the same kind or different kinds may be used, and even in the case of the same kind, they may be the same or different. Although the number of substituents of an alkyl group is not specifically limited, It is preferable that it is 1-3, and it is preferable that it is one or two.

When the R ₁ of the COOR ₁ group represented by the formula (3), R ₃ is a perspective alkyl of one to three groups from the effect of the ether solvent solubility in group represented by the following general formula (3). Examples of the alkylene group having 1 to 3 carbon atoms include methylene group, ethylene group, n-propylene group, and iso-propylene group. Preferably, they are ethylene group and a propylene group. In addition, R <_4> in group represented by General formula (3) is an alkyl group of 1-8 from a molecular weight viewpoint, More preferably, it is an alkyl group of 1-4. Examples of the alkyl group having 1 to 8 carbon atoms include those described above for R ₁ . N in group represented by General formula (3) is an integer of 1-4 from a viewpoint of molecular weight, and it is preferable that it is an integer of 1-3.

If R is an OR _2, OR _2, R ₂ represents an alkyl group of from 1 to 8 carbon atoms in the alkyl group, preferably having 1 to 3 carbon atoms in the crystallinity, better handling properties that the pigment of. Examples of the alkyl group having 1 to 8 carbon atoms represented by R ₂ include the substituents described in the above R ₁ .

When R is a halogen atom, a halogen atom includes a fluorine atom, a chlorine atom, a bromine atom and an iodine atom, and it is preferable that they are a fluorine atom, a chlorine atom or an iodine atom. Especially, since the molecular weight of a pigment | dye becomes small and a gram absorption coefficient becomes high, a chlorine atom and a fluorine atom are preferable, and a fluorine atom is more preferable.

When R is an aryl group, aryl groups, such as a phenyl group, p-methoxyphenyl group, p-t- butylphenyl group, and p-chlorophenyl group, are mentioned as an aryl group. Especially, since the molecular weight of a pigment | dye becomes small and a gram extinction coefficient becomes high, a phenyl group is preferable.

When R is an alkyl group, the alkyl group illustrated when R <_1> is a C1-C8 alkyl group as a C1-C8 alkyl group which may be substituted is mentioned. Preferably, it is a C1-C3 alkyl group from the point of the crystallinity and handleability of a pigment | dye being good. As a halogen atom which is a substituent of the alkyl group which exists in some cases, a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom are mentioned. Among these, a fluorine atom or a chlorine atom is preferable and a fluorine atom is more preferable. Two or more halogen atoms which are substituents of an alkyl group may exist, and when two or more exist, they may be same or different. Although the number of substituents of an alkyl group is not specifically limited, It is preferable that it is 1-3.

In general formula (2 '), R' is a C1-C3 alkylene group from an effect of ether solubility, and a molecular weight. Examples of the alkylene group having 1 to 3 carbon atoms include those exemplified for the above R ₃ . Preferably, they are ethylene group and a propylene group. R "is a C1-C8 alkyl group from the point of the effect of ether solubility, and a molecular weight, Preferably it is an alkyl group of 1-2. As an alkyl group of 1-8, the thing illustrated about said R <_1> is mentioned. It is an integer of 0-4 from a viewpoint of the effect of ether solubility, and molecular weight, and it is more preferable that it is an integer of 1-2.

In said Formula (1), M represents a nonmetal, a metal, a metal oxide, or a metal halide. Here, a nonmetal 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, tin, and the like. Examples of the metal oxides include titanyl and vanadil. Examples of the metal halides include aluminum chloride, indium chloride, germanium chloride, tin chloride (II), tin chloride (IV), and silicon chloride. Preferably, it is a metal, a metal oxide, or a metal halide, specifically, copper, zinc, cobalt, nickel, iron, vanadil, titanyl, indium chloride, tin (II) chloride, More preferably, copper, vana Dill and zinc, more preferably zinc, copper and most preferably zinc. If the center metal is zinc or copper, the heat resistance is high, so it is preferable. Moreover, when a center metal is zinc, it is especially preferable because solvent solubility with respect to general-purpose solvents, such as acetone, methanol, and methyl cellosolve, is high and also solubility with respect to resin is high.

As an absorption wavelength of the phthalocyanine compound (1) of this invention, it is preferable to have a maximum absorption wavelength ((lambda) max) in the wavelength region of 640-750 nm among near-infrared regions. In addition, in this specification, the maximum absorption wavelength employ | adopts the value measured by the measuring method in the following Example. Since the phthalocyanine compound of this invention shows the maximum absorption wavelength in the vicinity of 640-750 nm, the light of the useless near-infrared (700-750 nm) emitted by a flat panel display, especially a PDP and LCD, or the so-called crimson By cutting the light of the wavelength (640-700 nm), it can exhibit the effect which prevents the malfunction of an optical communication system, for example, and reproduces a clear red at the same time.

In the phthalocyanine compound (1), 4 to 10 of Z ₁ to Z ₁₆ are groups represented by the formula (2) or (2 '), at least one of which is a group represented by the formula (2), and 3 to 12 are hydrogen atoms. Z ₁ to Z ₁₆ are halogen atoms, except for the groups and hydrogen atoms represented by the formula (2) or (2 ').

Examples of suitable form of the phthalocyanine compound (1), (1) Z 1 ~ Z is a group represented by the formula (2) or (2), 4 out of ₁₆ dogs, and the others are hydrogen atoms, Z _1, Z _4, Z _5, Z _8, 1 to 3 of Z ₉ , Z ₁₂ , Z _13, and Z ₁₆ are groups represented by Formula 2 or Formula 2 ′, and Z ₂ , Z ₃ , Z ₆ , Z ₇ , Z ₁₀ , Z ₁₁ , Z _14, and Z ₁₅ 3 ~ 1 of the resulting phthalocyanine compound represented by the following formula (2) or formula (2) '(1-2), (2) Z ₁ and Z ~ 3 to 11 hydrogen atoms in the dog _16, the phthalocyanine compound, at least one is the halogen atom ( 1-3). Hereinafter, the phthalocyanine compound (1-2) and the phthalocyanine compound (1-3) are demonstrated.

(1) phthalocyanine compound (1-2)

A phthalocyanine compound (1-2) is a following formula (1-2):

In the formula, Z ₁ to Z ₁₆ are each independently a hydrogen atom, the following formula:

[Formula 2]

-XA ₁

In the formula, X is an oxygen atom or a sulfur atom, A ₁ is a phenyl group, a phenyl group having 1 to 5 substituents R or a naphthyl group having 1 to 7 substituents R, and the substituents R are each independently a nitro group or a COOR ₁ , OR ₂ (R ₂ is an alkyl group having 1 to 8 carbon atoms), a halogen atom, an aryl group, a cyano group or an alkyl group having 1 to 8 carbon atoms that may be substituted with a halogen atom, wherein R ₁ is an alkyl group having 1 to 8 carbon atoms (In this case, the alkyl group may be substituted with an alkyloxy group having 1 to 8 carbon atoms, a halogen atom or an aryl group) or the following general formula (3);

(3)

In the formula, R ₃ is an alkylene group having 1 to 3 carbon atoms, R ₄ is an alkyl group having 1 to 8 carbon atoms, n is an integer of 1 to 4;

[Formula 2 ']

In formula, R 'is a C1-C3 alkylene group, R "is a C1-C8 alkyl group, l is an integer of 0-4;

Which is represented by

In this case, 1 to 3 of Z ₁ , Z ₄ , Z ₅ , Z ₈ , Z ₉ , Z ₁₂ , Z _13, and Z ₁₆ are groups represented by Formula 2 or Formula 2 ′, and Z ₂ , Z ₃ , Z 3 to 1 of ₆ , Z ₇ , Z ₁₀ , Z ₁₁ , Z _14, and Z ₁₅ are groups represented by Formula 2 or 2 ′, and a total of 4 of Z ₁ to Z ₁₆ are represented by Formula 2 or Formula 2 ′. Is a group shown, at least one of Z ₁ to Z ₁₆ is a group represented by the formula (2),

M represents a nonmetal, metal, metal oxide or metal halide:

Indicates. Hereinafter, the phthalocyanine compound represented by Formula (1-2) is also called only a phthalocyanine compound (1-2).

The phthalocyanine compound (1-2) has a substituent represented by at least one formula (2) or formula (2 ') at each of the α and β positions. Conventionally known phthalocyanines include β- (nitrophenoxy) 4-substituted Zn phthalocyanines (2005), 9 (4), 268-274, or Makromoleculare, which are compounds having four nitrophenoxy groups at the β-position. Chemie (1988), 189 (5), 1001-1011. Also known are phthalocyanines (Chinese Patent Application Publication No. 101023945 and Chinese Patent Application Publication No. 101012234) having four phenoxy groups having an ester group (-COOR) at the α position. As a result of examination by the present inventors, it turned out that the phthalocyanine which has a substituent represented by Formula (2) or (2 ') only in (alpha) position is excellent in the solubility to an organic solvent, but it is inferior to heat resistance and light resistance. On the other hand, phthalocyanine having a substituent represented by the formula (2) or (2 ') only at the β-position improves heat resistance, but results in stacking of the spectrum (absorption of the absorption spectrum transversely) and a sharp peak at the maximum absorption wavelength. It was found that the gram extinction coefficient was lowered. Since the phthalocyanine compound (1-2) has at least one substituent represented by the general formula (2) or the general formula (2 ') at the α-position and the β-position, the phthalocyanine compound (1-2) has an excellent balance between the gram absorbance coefficient and the heat resistance, and is flat. Efficiently cut light with a wavelength of 640 to 700 nm for panel display applications.

In the formula (1-2), Z ₁ ~ Z ₁₆ is a hydrogen atom, the following formula 2:

[Formula 2]

-XA ₁

; Or the following Formula 2 ':

[Formula 2 ']

Indicates. At this time, Z ₁ to Z ₁₆ may be the same or different. Among these, in view of solvent solubility, in the formula _{(1-2), Z 1 ~ Z} 16 is preferably a hydrogen atom or (2).

The groups represented by the formulas (2) and (2 ') are the same as those described above for the phthalocyanine compound (1), and thus description thereof is omitted here.

When two or more Formula (2) exists, the kind of Formula (2) may be the same and may differ. When at least one of Z ₁ to Z ₁₆ is a phenoxy group or a phenoxy group (A ₁ is a phenol group), a group represented by the formula (2) other than the phenoxy group or phenoxy group is preferably present.

In terms of gram absorptivity, it is preferred that at least one of the groups represented by Formula 2 is A ₁ is a nitro group, a COOR _1, a halogen atom or a cyano group, a phenyl group or a naphthyl group substituted with ₁ -XA. Since the nitro group, COOR ₁ , halogen atom or cyano group is electron-absorbing, the gram extinction coefficient is considered to be improved.

In addition, a form of the formula (2) in which at least one of the groups represented by the formula (2) is a substituent of the phenyl group is present at the 2-position, or a substituent of the 2-naphthyl group is present in the 3-position. That is, at least one of Z ₁ to Z ₁₆ is preferably represented by the following Chemical Formula 5 or the following Chemical Formula 5 '. Especially, it is preferable that at least 1 substituent represented by General formula (5 ') exists.

[Chemical Formula 5]

[Formula 5 ']

In Chemical Formula 5, X is as defined in Chemical Formula 2, R corresponds to the substituent R in Chemical Formula 2, and m is an integer of 1 to 5. In addition, when m is 1, the substituent of Formula 3 means that R is present only at the 2 position. When m is 2, it is preferable that R exists in 2, 6 position, and 2, 5 position, and it is more preferable to exist in 2, 6 position. When R is present in at least 2, preferably 2, 2,6, 2,5, more preferably 2 or 2,6 positions, steric hindrance can occur to prevent the overlap of phthalocyanine molecules. Therefore, a sharp absorption spectrum can be obtained and the gram extinction coefficient becomes high. Moreover, it becomes what is excellent in the solubility with respect to the organic solvent.

In Chemical Formula 5 ', X is as defined in Chemical Formula 2, R corresponds to the substituent R in Chemical Formula 2, and m' 'is an integer of 1 to 7. When m "is 1, the substituent of Chemical Formula 5' Means that R exists only in 3 positions. When m "is 2, R is preferably present at positions 1, 3 and 3, 4. Since R is present at least at position 3, steric hindrance can occur and prevent phthalocyanine molecules from overlapping. A sharp absorption spectrum can be obtained, the gram absorption coefficient becomes high, and it becomes the thing excellent in the solubility with respect to the organic solvent.

In the above formula (5 '), a substituent R other than the X in the 2 position and the R in the 3 position may be substituted with any hydrogen atom of the naphthalene ring. That is, in Formula 5 ', the substituent "R" is present in the naphthalene ring on the side where X is present in the two naphthalene rings, but this substituent does not mean that it exists at the corresponding position, and the other benzene ring It may be present in. That is, Formula 5 'includes both of the following substituents (5'-1) and (5'-2).

Substituent (5'-1)

Substituent (5'-2)

In view of solubility in organic solvents, in particular, in ether solvents, at least one of the groups represented by Formula 2 is represented by the following Formula 4:

[Formula 4]

In formula (4), X and R ₁ are the same as defined in formula (2), R corresponds to the substituent R of the phenyl group, m and m ₁ are integers of 1 to 5 (wherein m ₁ ≦ m): Formula 4 '

[Formula 4 ']

In formula (4 '), X is as defined in formula (2), R corresponds to substituent R of the phenyl group, m' is an integer from 2 to 5: a group represented by or a naphthyloxy group wherein at least one substituent is COOR ₁ or It is preferable that it is a naphthylthio group. When an ester group exists as a substituent or a substituent exists in at least 2, 6 position, solubility to an ether type solvent further improves. m ₁ becomes like this. Preferably it represents the integer of 1-3, More preferably, it is 1 or 2. In the general formula (4 '), R is not particularly limited, but is preferably a halogen atom and more preferably a chlorine atom or a fluorine atom in view of electron attraction and steric effect. In addition, in Formula 4 ', when m' is 2, R exists in the 2,6 position. m ', Preferably it represents the integer of 2-3, More preferably, it is 2. When COOR ₁ exists as a substituent of a naphthalene ring in a naphthyloxy group or a naphthylthio group, it is preferable that the number of COOR ₁ is 1-3, More preferably, it is 1 or 2. Groups represented by the Formula 4, Z is preferably ₁ ~ Z dog 2-7 exist in view of the solubility of the ether _16. In addition, one group, Z ₁ Z 2 ~ ~ 7 in terms of the solubility of the ether ₁₆ represented by the formula (4) ', it is preferable that more preferably, 2-4 exists. Both the group represented by the formula (4) and the group represented by the formula (4 ') may be present, or only one of them may be present.

In the formula (1-2), 1 to 3 of Z ₁ , Z ₄ , Z ₅ , Z ₈ , Z ₉ , Z ₁₂ , Z ₁₃ and Z ₁₆ are groups represented by the formula (2) or the formula (2 ′), 3 to 1 of Z ₂ , Z ₃ , Z ₆ , Z ₇ , Z ₁₀ , Z ₁₁ , Z ₁₄ and Z ₁₅ are groups represented by Formula 2 or Formula 2 ′, and 4 of Z ₁ to Z ₁₆ in total Group represented by the formula (2) or (2 '). At least one of Z ₁ to Z ₁₆ is a group represented by the formula (2). That is, when there are three groups represented by the formula (2) or (2 ') at the α position of the phthalocyanine nucleus, there is one group represented by the formula (2) or (2') at the β position of the phthalocyanine nucleus. And other than that, it is a hydrogen atom. Similarly, when two groups represented by the formula (2) or (2 ') are present at the α position, two groups represented by the formula (2) or (2') are present at the β-position, and others are hydrogen atoms. When one group represented by the formula (2) or the formula (2 ') is present at the α position, three groups represented by the formula (2) or the formula (2') are present at the β position, and others are hydrogen atoms. Since the heat resistance of the phthalocyanine compound can be improved and a sharp absorption spectrum can be obtained, there are two groups represented by the formula (2) or (2 ') at the α position and two groups represented by the formula (2) or (2') at the β position. It is desirable to. Z ₁ ~ Z group represented by the formula 2 out of ₁₆₎ or (2 'Z ~ Z ₁ is other than _16, it is possible to increase the small and gram extinction coefficient of the molecular weight of the phthalocyanine, represent a hydrogen atom. The groups represented by the formula (2) or the formula (2 ') present in four of Z ₁ to Z ₁₆ may be the same or different. The group represented by the formula (2) or the formula (2 ') present in the α position and the group represented by the formula (2) or (2') present in the β position may be the same or different.

Since M in Formula (1-2) is as having demonstrated about the said phthalocyanine compound (1), description is abbreviate | omitted here.

In the phthalocyanine compound (1-2), four of Z ₁ to Z ₁₆ are substituents represented by the formula (2) or (2 ') so that each substituent is homogeneous to each benzene ring of the phthalocyanine skeleton (an almost equal number of benzene rings). Preferably a substituent). Especially, the phthalocyanine compound of this invention is a phthalocyanine compound represented by following formula (I) which has one substituent represented by Formula (2) or (2 ') in each benzene ring (henceforth only called "phthalocyanine compound (I)"). Is preferable.

In the above formula, B is a group represented by the formula (2) or (2 '), and M is the same as that used in the formula (1). The kind of substituent B which exists in each benzene ring may be the same, and may differ. Suitably, the kind of substituent B which exists in the (alpha) position is the same, and it is preferable that the kind of substituent B which exists in the (beta) position is the same. In addition, 1-3 substituents represented by the general formula (2) or (2 ') are present in the α position and 3 to 1 in the β position.

The following are mentioned as a preferable example of a phthalocyanine compound (1-2). In addition, the phthalocyanine compound of this invention is not limited to these. In the abbreviation of the following compound, Pc represents a phthalocyanine nucleus, Zn, Cu, VO represents a center metal, shows the substituent substituted by the alpha position immediately after Pc, and β after the substituent substituted by the alpha position The substituent substituted by a position is shown. For example, [ZnPc- {α- (2-NO ₂ ) C ₆ H ₄ O} ₂ , {β- (2-COOC ₃ H ₇ ) C ₆ H ₄ O} ₂ H ₁₂ ] is Zn , two of the α-positions are substituted with (2-NO ₂ ) C ₆ H ₄ O-, two of the β-positions are substituted with (2-COOC ₃ H ₇ ) C ₆ H ₄ O- and the remainder are hydrogen atoms Phthalocyanine compound is shown.

In addition, the number of substituents being optionally substituted with a substituent and can be substituted with a β position of the compound, where α is not an integer, for example, [ZnPc- {α- (2-NO 2) C 6 H 4 O} 0.5, { β- (2-COOCH ₃ ) C ₆ H ₄ O} _3.5 H ₁₂ ], [ZnPc- {α- (2-NO ₂ ) C ₆ H ₄ O} _3.5 , {β- (2-COOCH ₃ ) C ₆ H ₄ O} _0.5 H ₁₂ ] [ZnPc- {α- (2-NO ₂ ) C ₆ H ₄ O} _2.5 , {β- (2-COOCH ₃ ) C ₆ H ₄ O} _1.5 H ₁₂ ] and the like, It means that a plurality of compounds are present in the form of a mixture. The plural kinds of compounds referred to herein include three substituents represented by the formula (2) or (2 ') at the α position, and one substituent represented by the formula (2) or (2') at the β-position: 2 substituents shown, 2 substituents represented by formula (2) or (2 ') at the β position: 1 substituent represented by formula (2) or (2') at the α-position, 1 substituent represented by formula 2 or formula (2 ') at the β-position Is a compound such as three. That is, the phthalocyanine compound (1-2) includes what exists in the form of a mixture in addition to the case of one type of compound. For this reason, in this case, the number of substituents represented by the formula (2) or (2 ') in the substituent at the α position in the formula (1-2) is the average of the number of substituents represented by the formula (2) or the formula (2') in each phthalocyanine compound. Since it is shown as, it does not necessarily become an integer. Similarly, since the number of substituents represented by the formula (2) or (2 ') in the substituent at the β-position in the formula (1-2) is represented as an average of the number of substituents represented by the formula (2) or the formula (2') in each phthalocyanine compound, It is not necessarily an integer. Moreover, the sum total of the substituent represented by Formula (2) or Formula (2) which is a substituent of the (alpha) position, and the substituent represented by Formula (2) or (2 ') which is a substituent of the (beta) position is four. Such a phthalocyanine compound (1-2) is manufactured by the method of carrying out the cyclization reaction of this and a metal salt using what mixed the phthalonitrile compound A and phthalonitrile compound B which are raw materials in a predetermined | prescribed mixing ratio, although it mentions in detail below. can do.

Although it does not restrict | limit especially as a lower limit of the gram extinction coefficient of a phthalocyanine compound (1-2), Considering the use as mentioned above, especially the filter for flat panel displays, Preferably it is 50 or more, More preferably, 60 Above, more preferably 70 or more. In addition, the higher the gram extinction coefficient of the phthalocyanine compound of the present invention is preferable, and therefore, the upper limit of the gram extinction coefficient is not particularly limited, but the gram extinction coefficient is usually 500 or less. In addition, in this specification, the gram extinction coefficient employ | adopts the value measured by the measuring method in the following Example. The phthalocyanine compound (1-2) has a suitable number of substituents and types of substituents at the α and β positions to be introduced in order to adjust the absorption wavelength to a desired range, and because the molecular weight of the dye is not large and the absorption coefficient is also high, gram absorption It is thought that the coefficient becomes high.

(2) phthalocyanine compound (1-3)

A phthalocyanine compound (1-3) is a following formula (1-3):

In the formula, Z ₁ to Z ₁₆ are each independently a hydrogen atom, a halogen atom, the following formula 2:

[Formula 2]

-XA ₁

In the formula, X is an oxygen atom or a sulfur atom, A ₁ is a phenyl group, a phenyl group having 1 to 5 substituents R or a naphthyl group having 1 to 7 substituents R, and the substituents R are each independently a nitro group or a COOR ₁ , OR ₂ (R ₂ is an alkyl group having 1 to 8 carbon atoms), a halogen atom, an aryl group, a cyano group or an alkyl group having 1 to 8 carbon atoms that may be substituted with a halogen atom, wherein R ₁ is an alkyl group having 1 to 8 carbon atoms (In this case, the alkyl group may be substituted with an alkyloxy group having 1 to 8 carbon atoms, a halogen atom or an aryl group) or the following general formula (3);

(3)

Wherein R ₃ is an alkylene group having 1 to 3 carbon atoms, R ₄ is an alkyl group having 1 to 8 carbon atoms, and n is an integer of 1 to 4;

Or a group represented by the following formula (2 '):

[Formula 2 ']

In the formula, R 'is an alkylene group having 1 to 3 carbon atoms, R "is an alkyl group having 1 to 8 carbon atoms, l is an integer of 0 to 4;

In this case, 4 to 10 of Z ₁ to Z ₁₆ are a group represented by the formula (2) or (2), at least one of them is a group represented by the formula (2), 3 to 11 is a hydrogen atom, at least one Is a halogen atom,

M represents a nonmetal, metal, metal oxide or metal halide:

Indicates. Hereinafter, the phthalocyanine compound represented by Formula (1-3) is also called only a phthalocyanine compound (1-3).

In recent years, since the phthalocyanine-based compound is stable and excellent in light, heat, temperature, etc., near-infrared light used in optical recording media such as compact disks, laser disks, optical memory disks, optical cards, etc. using semiconductor lasers as light sources. It is used as an absorbent pigment. In addition, PDP (Plasma Display Panel), which can be applied to large screens in recent years, is attracting attention, and PDP generates near-infrared light during plasma discharge, and this near-infrared light is applied to electric appliances such as televisions, coolers, and video decks for home appliances. In order to solve this problem, there is a problem, and in order to solve such a problem, a phthalocyanine compound having high visible light transmittance, high near-infrared light cut efficiency, excellent absorption ability of near-infrared light, and excellent heat resistance, light resistance, and weather resistance Development has been done.

As described above, various phthalocyanine compounds have been studied and developed in the past, but conventional phthalocyanine compounds include methanol, alcohols such as ethanol and propanol, cellosolves such as ethyl cellosolve, glycols such as monoethylene glycol and diethylene glycol, acetone, It is known that it is soluble in organic solvents, such as ketones, such as methyl ethyl ketone, chloroform, and toluene, for example (refer JP-A-6-107663). However, the conventional phthalocyanine compound did not have sufficient solubility in an ether solvent. For this reason, even if it is a suitable use to use an ether solvent, a sufficient amount of a phthalocyanine compound cannot be mix | blended, and there existed a problem that the selection of the solvent to be used and the kind of resin to mix | blend is limited.

The phthalocyanine compound (1-3) is ether-based, while maintaining high visible light transmittance, high near-infrared cut efficiency (especially 640 to 750 nm), and near-infrared selective absorption in addition to excellent resin compatibility, heat resistance, light resistance, and weather resistance. Can be dissolved in a solvent. Therefore, even if it is resin which melt | dissolves in a ether solvent relatively selectively can be used. Moreover, when solvent other than an ether solvent is used, it can be used also for the use of applying a phthalocyanine pigment | dye on the plastic which may melt | dissolve.

In particular, color toner, inkjet ink, household inkjet ink, anti-counterfeiting ink, in particular, anti-counterfeiting barcode ink or anti-counterfeiting offset ink, lenses and shielding plates of goggles, dyeing agents for plastic recycling, optical recording media, Preheating aids in the shaping and processing of photosensitive pigments and PET bottles for laser treatment, thermal heat transfer agents such as thermal transfer, thermal stencils, optical heat exchangers for thermally rewritable recording, anti-counterfeiting of ID cards, laser permeation welding of plastics (LTW: Laser Transmission Welding) There is a limited selection of solvents for use in applications such as optical heat exchangers, heat shields, near-infrared absorbing filters, and the like. Therefore, there is a high demand for a phthalocyanine compound which has high solubility in an ether solvent and is useful for applications not conventionally applicable.

The phthalocyanine compound (1-3) is a group in which 4 to 10 of Z ₁ to Z ₁₆ are represented by the formula (2) and / or the formula (2 '). The present inventors have a plurality of groups represented by the formula (2) or (2 ') and at least one group represented by the formula (2), so that the solubility in the ether solvent is improved, and COOR ₁ is present as the substituent R in the formula (2) Or when R exists in 4 or 2, 6 positions, it was discovered that the solubility of the phthalocyanine compound (1-3) to an ether solvent is further improved. Since the phthalocyanine compound (1-3) has high solubility in an ether solvent, it can be used combining resin and pigment | dye with high solubility in an ether solvent, and using the plastic which melt | dissolves in solvents other than an ether solvent. Even in a case, a pigment | dye can be apply | coated on this plastic.

In addition, a phthalocyanine compound (1-3) is Z <_2> , Z <_3> , Z <_6> , Z <_7> , Z <_10> , Z <_11> , Z <_14> and Z <_15> after that, only the substituent of the (beta) position It is excellent in heat resistance by having a substituent). _{Also, Z 1, Z 4, Z} 5, Z 8, Z 9, Z 12, Z ₁₃ and Z ₁₆ by having a substituent on (also called later, only substituent in position α), is excellent in solubility. A phthalocyanine compound (1-3) selects the number of substituents and a type of substituent suitably, and aims at the balance of heat resistance and solubility.

In addition, the phthalocyanine compound (1-3) absorbs 710 nm of light and has a high transmittance of visible light such as 520 nm. Therefore, especially in PDP, since extra large light emission is seen in the vicinity of 710 nm, the phthalocyanine compound (1-3) is useful.

In the formula (1-3), Z ₁ ~ Z ₁₆ is a hydrogen atom, a halogen atom, the following formula 2:

[Formula 2]

-XA ₁

Or Formula 2 '

[Formula 2 ']

Indicates. At this time, Z ₁ to Z ₁₆ may be the same or different. X represents an oxygen atom or a sulfur atom.

The groups and halogen atoms represented by the formulas (2) and (2 ') in Z ₁ to Z ₁₆ are the same as those described above for the phthalocyanine compound (1), and thus description thereof is omitted here.

4-10 of Z ₁ ~ Z ₁₆ is more in view of the general formula (2) and / or the formula a group represented by the 2 ', ether solubility and molecular weight will be less desirable in the preferred point 4-8 pieces, an ether solvent solubility Preferably it is 6-8 pieces.

If the groups represented by the general formula (2) or the general formula (2 ') in Z ₁ to Z ₁₆ are less than 4, solubility in an ether solvent is lowered, which is not preferable. Moreover, since the molecular weight becomes large, when there are more than 10 groups represented by General formula (2), it is unpreferable. It is preferable that at least one substituent represented by the formula (2) or (2 ') is present in each benzene ring of the phthalocyanine skeleton.

Also, Z ₁ - Z 3 to 11 out of ₁₆ is a hydrogen atom, more preferably a 3 to 9, more preferably from three to six. When the phthalocyanine compound (1) has a hydrogen atom, the absorbance per gram is higher than that of the compound composed of only halogen atoms other than the groups represented by the formulas (2) and (2 '). For this reason, the effect of a phthalocyanine compound can be exhibited with a small amount of compounding.

Z ₁ ~ Z group represented by the formula (2) of _16, a group and a halogen atom other than a hydrogen atom represented by general formula (2). At least one halogen atom is present. Here, as a halogen atom, there exist a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom, Among these, Preferably it is a fluorine atom and a chlorine atom, More preferably, it is a chlorine atom.

When there are four groups represented by the formula (2) or (2 ') in Z ₁ to Z ₁₆ , the hydrogen atom is preferably 6 to 9, more preferably 6, when there are five groups represented by the formula (2) or (2), The number of hydrogen atoms is preferably 6 to 9, more preferably 9, and when the group represented by the formula (2) or (2 ') is 6, the hydrogen atoms are preferably 4 to 8, more preferably 6, When there are 7 groups represented by 2 or formula 2 ', it is preferable that they are 3-6 hydrogen atoms, It is more preferable that they are 3, When 8 groups represented by formula 2 or 2' are preferable, it is preferable that they are 4-6 hydrogen atoms. It is more preferable that it is six pieces.

In the case where a plurality of groups represented by the formula (2), a group represented by the formula (2 ') and a halogen atom are present, the substituents may be the same kind or different kinds.

In the phthalocyanine compound (1-3), A ₁ in the general formula (2) is preferably a phenyl group having a substituent R of 1 to 5 or a naphthyl group having a substituent R of 1 to 7, and more preferably of 1 to 5 It is a phenyl group which has a substituent R.

In the phthalocyanine compound (1-3), at least one of the groups represented by the formula (2) is the following formula 4:

[Formula 4]

In formula (4), X and R ₁ are the same as defined in formula (2), R corresponds to the substituent R of the phenyl group, m and m ₁ are integers of 1 to 5 (wherein m ₁ ? M): Formula 4 '

[Formula 4 ']

In formula (4 '), X is as defined in formula (2), R corresponds to substituent R of phenyl group, m' is an integer from 2 to 5: a naphthyloxy group or naph with the group represented by or at least one substituent is COOR ₁ It is preferable that it is a thiothio group. When an ester group exists as a substituent or a substituent exists in at least 2, 6 position, solubility to an ether type solvent further improves. m ₁ preferably represents an integer of 1 to 3, and more preferably 1 or 2. In the general formula (4 '), R is not particularly limited, but is preferably a halogen atom and more preferably a chlorine atom or a fluorine atom in view of electron attraction and steric effect. In addition, in Formula 4 ', when m' is 2, R exists in the 2,6 position. m 'becomes like this. Preferably it represents the integer of 2-3, More preferably, it is 2. When COOR ₁ exists as a substituent of a naphthalene ring in a naphthyloxy group or a naphthylthio group, it is preferable that the number of COOR ₁ is 1-3, More preferably, it is 1 or 2. Groups represented by the Formula 4, Z is preferably ₁ ~ Z dog 2-7 exist in view of the solubility of the ether _16. In addition, one group, Z ₁ Z 2 ~ ~ 7 in terms of the solubility of the ether ₁₆ represented by the formula (4) ', it is preferable that more preferably, 2-4 exists. Both the group represented by the formula (4) and the group represented by the formula (4 ') may be present, or only one of them may be present.

When four or eight groups represented by the general formula (4) in Z ₁ to Z ₁₆ are present, it is preferable that a group represented by the general formula (2) or a group represented by the general formula (2 ') other than the group represented by the general formula (4) is present. In the case where four groups represented by the formula (4) exist, it is preferable that two to four groups represented by the formula (2) or the group represented by the formula (2 ') exist other than the group represented by the formula (4).

In the phthalocyanine compound (1-3), ether solubility is further improved in a form in which at least one of the groups represented by the formula (2) in which R, which is a substituent of a phenyl group or a thiophenol group, is present at the 4th position, is present in Z ₁ to Z ₁₆ . Preferred at That is, at least one of Formula 2 is preferably represented by the following Formula 5a.

[Formula 5a]

In Chemical Formula 5a, X and R are as defined above, and m is an integer of 1 to 5. In addition, when m is 1, the substituent of Formula 5 means that R is present only at the 4 position. When m is 2, it is preferable that R exists in 2, 4 position, 3, 4 position, and it is more preferable to exist in 2, 4 position.

In the phthalocyanine compound (1-3), substituents other than the halogen atom and the hydrogen atom in Z ₁ to Z ₁₆ are preferably the substituents of the following (1) to (12).

In the above (1) to (12), X, R ₁ , R, m ', R' and R '' are as defined above, and in (4), (5) and (6), E is The halogen atom may be the same kind or different kinds.

Since M in said Formula (1-3) is as having demonstrated about the said phthalocyanine compound (1), description is abbreviate | omitted here.

In the phthalocyanine compound (1-3), when Z ₁ to Z ₄ , Z ₅ to Z ₈ , Z ₉ to Z ₁₂ , and Z ₁₃ to Z ₁₆ are each set to units A, B, C, and D, then A Of the four units of ˜D, there are two groups represented by formula (2) or formula (2 ′), two halogen atoms, three groups represented by formula (2) or formula (2 ′), one unit having one halogen atom, or a group represented by formula (2) or formula (2 ′) Unit (I) of one unit having three halogen atoms and unit (II) of one group represented by formula (2) or formula (2 ') with three hydrogen atoms include unit (I): unit (II) = 1: 3-3: It is preferable that it is 1. Here, being present as unit (I): unit (II) = 1: 3 among four units of A to D means that any one of A to D is a unit (I) and the remaining three are units (II). . More suitably, a unit (I) having two groups represented by the formula (2) and two halogen atoms, three groups represented by the formula (2) and one halogen atom, or a unit represented by formula (2) and one group and three halogen atoms; It is preferable that unit (II) which has one group represented by Formula (2) or Formula (2 ') and three hydrogen atoms is unit (I): unit (II) = 1: 3-3: 1.

Thus, by including in the phthalocyanine compound a unit having different configurations of substituents, such as unit (I) and unit (II), the group represented by the formula (2) or the group represented by the formula (2 '), the halogen atom and the hydrogen atom are represented by Z of the phthalocyanine compound. It is a suitable phthalocyanine compound that contains a number of ₁ ~ Z _16. Thus, it is preferable to mix three types of substituents from the point of balance of solubility, wavelength control, durability (light resistance, heat resistance), and absorbance per gram. Although the detailed mechanism is unclear, the ether solubility is improved by the proper number of the group represented by the formula (2) or the group represented by the formula (2 '), and the appropriate number of halogen atoms can increase the absorption wavelength, and also the durability (light resistance, heat resistance) It is thought that the absorbance per gram is improved by the presence of a suitable number of hydrogen atoms.

Since M in Formula (1-3) is the same as that of the said phthalocyanine compound (1), description is abbreviate | omitted here.

Since the substituent at the β-position is effective in improving the heat resistance, and the substituent at the α-position is effective in improving the solubility, it is preferable to mix them in a balanced manner. Therefore, in the present invention, it is preferable that the group represented by the formula (2) or the formula (2 ') exists in at least one of both the α and β positions, rather than the group represented by the formula (2) or (2') only in the α position or the β position. Do.

The phthalocyanine compound (1-3) has high solubility in an ether solvent. This is due to the presence of the group represented by the formula (2) and the group represented by the formula (2 ') and the number of substitution thereof substituted in the phthalocyanine nucleus. When applying a phthalocyanine compound, since the board | substrate used by a device does not melt | dissolve by a solvent and also the solubility to resin is needed, solubility to a solvent of a phthalocyanine compound is important. And the phthalocyanine compound of various absorption wavelengths can be obtained by selection of the kind, number, and center metal of a substituent. As the ether solvent, branched or linear ethers and cyclic ethers are effectively used. Specifically, tetrahydrofuran, 1,4-dioxane, 1,3-dioxolane, diethyl ether, diisopropyl ether, 1,2-dimethoxyethane, cyclopentylmethyl ether, propylene glycol monomethyl ether Acetate (PGMEA), ethylene glycol monoethyl ether acetate, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether and the like. In flat panel display applications, PGMEA is often used. It is preferable that the solubility to PGMEA which is an ether solvent is 10 mass% or more, and, as for the phthalocyanine compound of this invention, it is more preferable that it is 20 mass% or more. Although the upper limit of solubility is not specifically limited, Usually, it is about 50 mass% or less.

(Method for producing phthalocyanine compound (1))

Although the manufacturing method of the phthalocyanine compound (1) of this invention is not specifically limited, A conventionally well-known method can be used suitably, Preferably, the method of carrying out cyclization reaction of a phthalonitrile compound and a metal salt in a molten state or an organic solvent is preferable. This can be used preferably. Hereinafter, especially preferable embodiment of a manufacturing method is described about the phthalocyanine compound (1) of this invention. However, the present invention is not limited to the following preferred embodiment.

That is, the following formula (I):

Phtharonitrile compound (1) represented by the following formula (II):

Phtharonitrile compound (2) represented by the following formula (III):

Phtharonitrile compound (3) represented by the following formula (IV):

One type and ring selected from the group consisting of metal, metal oxides, metal carbonyls, metal halides, and organic acid metals (collectively referred to herein as "metal compounds") in the phthalonitrile compound (4) By the reaction, the phthalocyanine compound of the present invention can be produced.

Further, In the formula (I) ~ (IV), Z ₁ ~ Z ₁₆ is defined by the structure of the desired phthalocyanine compound (1). Specifically, in the formulas (I) to (IV), since Z ₁ to Z ₁₆ are the same as the definitions of Z ₁ to Z ₁₆ in the formula (1), the description is omitted here.

Cyclization reaction can be synthesize | combined by conventionally well-known methods, such as the method of Unexamined-Japanese-Patent No. 64-45474.

In the above aspect, the cyclization reaction is a molten state or a kind selected from the group consisting of phthalonitrile compounds of formulas (I) to (IV) and metals, metal oxides, metal carbonyls, metal halides and organic acid metals. It is preferable to make it react in an organic solvent. The metal, metal oxide, metal carbonyl, metal halide and organic acid metal which can be used at this time are not particularly limited as long as those corresponding to M of the phthalocyanine compound (1) of the formula (1) obtained after the reaction are obtained. For example, metals, such as iron, copper, zinc, vanadium, titanium, indium, and tin, which are listed in the term of M in Formula (1), metal halide compounds, such as chloride, bromide, and iodide of this metal, Metal oxides, such as metal oxides, such as vanadium oxide, a titanyl oxide, and copper oxide, complex compounds, such as organic acid metals, such as acetate, and acetylacetonato, metal carbonyl, such as carbonyl iron, etc. are mentioned. Specifically, metals, such as iron, copper, zinc, vanadium, titanium, indium, magnesium, and tin; Metal halide compounds such as chlorides, bromide, and iodides of the metals, for example vanadium chloride, titanium chloride, copper chloride, zinc chloride, cobalt chloride, nickel chloride, iron chloride, indium chloride, aluminum chloride, tin chloride, chloride Gallium, germanium chloride, magnesium chloride, copper iodide, zinc iodide, cobalt iodide, indium iodide, aluminum iodide, gallium iodide, copper bromide, zinc bromide, cobalt bromide, aluminum bromide, gallium bromide; Vanadium monoxide, vanadium trioxide, vanadium tetraoxide, vanadium pentoxide, titanium dioxide, iron monoxide, iron trioxide, iron trioxide, manganese oxide, nickel monoxide, cobalt monoxide, cobalt trioxide, cobalt dioxide, cuprous oxide, cuprous oxide Metal oxides such as copper trioxide, vanadium oxide, zinc oxide, germanium monoxide and germanium dioxide; Organic acid metals such as copper acetate, zinc acetate, cobalt acetate, copper benzoate and zinc benzoate; And complex compounds such as acetylacetonato and metal carbonyl such as cobalt carbonyl, iron carbonyl, nickel carbonyl, and the like. Among these, metal, metal oxides and metal halides are preferred, metal halides are more preferred, vanadium iodide, copper iodide and zinc iodide, and particularly preferably copper iodide and zinc iodide, most preferably Preferably zinc iodide. In the case of using zinc iodide, the center metal is made zinc. The reason for using iodide among metal halides is because it is excellent in solubility in a solvent and a resin, the spectrum of the phthalocyanine compound obtained is sharp, and it is easy to enter into 640-750 nm which is a desired wavelength. The detailed mechanism of sharpening the spectrum when using iodide in the cyclization reaction is unclear.However, when using iodide, iodine remaining in the phthalocyanine compound interacts with the phthalocyanine compound after the reaction, causing the phthalocyanine compound to intercalate. It is assumed that iodine is present. However, it is not limited to the above mechanism. In order to obtain the same effect as when metal iodide is used for the cyclization reaction, the obtained phthalocyanine compound may be treated with iodine.

In addition, in the said aspect, although the cyclization reaction can be performed even in absence of a solvent, it is preferable to carry out using an organic solvent. The organic solvent may be any inert solvent having low reactivity with the phthalonitrile compound as the starting material, and preferably no reactivity. For example, benzene, toluene, xylene, nitrobenzene, monochlorobenzene, o- Inert solvents such as chlorotoluene, dichlorobenzene, trichlorobenzene, 1-chloronaphthalene, 1-methylnaphthalene, ethylene glycol and benzonitrile; Alcohols such as methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 1-hexanol, 1-pentanol, 1-octanol; And pyridine, N, N-dimethylformamide, N, N-dimethylacetamide, N-methyl-2-pyrrolidinone, N, N-dimethylacetophenone, triethylamine, tri-n-butylamine, dimethylsulfoxide Aprotic polar solvents, such as a seed and a sulfolane, etc. are mentioned. Of these, preferably 1-chloronaphthalene, 1-methylnaphthalene, 1-octanol, dichlorobenzene and benzonitrile, more preferably 1-octanol, dichlorobenzene and benzonitrile are used. These solvents may be used alone or in combination of two or more thereof.

The reaction conditions of the phthalonitrile compound and the metal compound of formulas (I) to (IV) in the above aspect are not particularly limited as long as the reaction proceeds. For example, based on 100 parts by mass of the organic solvent, The total amount of the phthalonitrile compound (1) to (4) in the range of 1 to 500 parts by mass, preferably 10 to 350 parts by mass, and the metal compound with respect to 4 moles of the phthalonitrile compound, preferably 0.8 to 2.0 mol, More preferably, it is put in the range of 0.8-1.5 mol. Although it does not specifically limit at the time of a ring, Preferably it is made to react in 30-250 degreeC of reaction temperature, More preferably, it is 80-200 degreeC. Although reaction time is not specifically limited, Preferably it is 3 to 20 hours. After the reaction, the phthalocyanine derivative which can be used in the next step can be efficiently and highly purified by filtration, washing and drying in accordance with a conventionally known method for synthesizing a phthalocyanine compound.

In the said aspect, the phthalonitrile compound of Formula (I)-(IV) which is a starting raw material can be synthesize | combined by a conventionally well-known method, and can also use a commercial item.

Hereinafter, the phthalonitrile compound represented by following formula (A) which is a starting material of the phthalocyanine compound (I) which is a preferable aspect of a phthalocyanine compound (1-2) (henceforth only called "phthalonitrile compound A"), or a formula ( The synthesis example of the phthalonitrile compound represented by B) (henceforth only a "phthalonitrile compound B") is demonstrated. In addition, since B in Formula (A) and (B) is the same as B in the said Formula (I), description is abbreviate | omitted here.

A phthalonitrile compound A or a phthalonitrile compound B can be obtained by a conventionally well-known manufacturing method. Suitably, nitrophthalonitrile and the following formula (C);

Represented by the compound (hereinafter also referred to simply as "Compound C") or the following formula (C ');

It is obtained by reacting the compound (hereinafter, also referred to simply as "compound C '"). The nitro group in nitrophthalonitrile is substituted with a substituent represented by formula (2) derived from compound C or a substituent represented by formula (2 ') derived from compound C'. Formula A ₁ and X in (C) is omitted, here, explanation is the same as A _1, and X 2 in the general formula. In addition, since R ', R "and l in Formula (C') are the same as R ', R" and l in the said Formula (2'), description is abbreviate | omitted here. The phthalonitrile compound A can be obtained by reacting 3-nitrophthalonitrile with compound C or compound C ', and the phthalonitrile compound of formula (B) is 4-nitrophthalonitrile with compound C or compound C. It can be obtained by reacting.

Although the reaction of nitrophthalonitrile, the compound C, and the compound C 'may be performed in a non-solvent or in an organic solvent, Preferably it is performed in an organic solvent. As an organic solvent which can be used at this time, Nitriles, such as acetonitrile and benzonitrile; Polar solvents such as acetone and 2-butanone; Alcohol solvents, such as compound C, when methanol, ethanol, and X are oxygen atoms, etc. are mentioned. Among these, acetonitrile, benzonitrile and acetone are preferable. These solvents may be used alone or in combination of two or more thereof. The amount of the organic solvent used when the solvent is used is such that the concentration of nitrophthalonitrile is usually 1 to 50 (w / v)%, preferably 10 to 30 (w / v)%.

The use ratio of nitrophthalonitrile, compound C, and compound C 'is appropriately selected depending on the structure of the desired phthalonitrile compound, and is not particularly limited, but is usually used for compound C and 1 mole of nitrophthalonitrile. Compound C 'is used in an amount of 1.0 to 2.0 moles, preferably 1.1 to 1.5 moles.

The reaction between nitrophthalonitrile, compound C, and compound C 'is 1,8-diazabicyclo [5.4.0] -7-undecene (DBU), potassium fluoride (KF), potassium carbonate (K ₂ CO ₃ ) It is preferable to carry out in presence of catalysts, such as these. Moreover, you may add a phase transfer catalyst separately. By adding a phase transfer catalyst, the rate of the nucleophilic substitution reaction of nitrophthalonitrile and compound C or compound C 'is increased. The phase transfer catalyst is not particularly limited, but quaternary ammonium salts are preferred. Specifically, tetramethylammonium chloride, tetramethylammonium bromide, tetrabutylammonium chloride, tetrabutylammonium bromide, benzyltriethylammonium chloride, benzyltriethylammonium bromide, benzyltributylammonium chloride, benzyltributylammonium bromide and the like Can be mentioned. At this time, the amount of the catalyst containing the phase transfer catalyst is not particularly limited as long as the reaction proceeds satisfactorily. Specifically, the catalyst is preferably added in an amount of usually 1.0 to 2.0 mol, more preferably 1.1 to 1.5 mol, with respect to 1 mol of nitrophthalonitrile.

The reaction conditions of the nitrophthalonitrile, the compound C and the compound C 'are not particularly limited as long as the reaction proceeds satisfactorily. Specifically, at the time of reaction of nitrophthalonitrile with compound C and compound C ', Preferably it is 30-150 degreeC, More preferably, it is the temperature of 60-90 degreeC, Preferably it is 1-50 hours, More preferably, React for 3 to 20 hours.

The phthalocyanine compound (I) can be manufactured by carrying out the cyclization reaction of the obtained phthalonitrile compound A and the phthalonitrile compound B with 1 type chosen from the group which consists of a metal compound as a raw material. Under the present circumstances, the mixing molar ratio of the phthalonitrile compound A and the phthalonitrile compound B may be adjusted suitably so that the number of substituents of a desired phthalocyanine compound may be sufficient. For example, in the case of [ZnPc- {α- (2-NO ₂ ) C ₆ H ₄ O} _0.5 , {β- (2-COOCH ₃ ) C ₆ H ₄ O} _3.5 H ₁₂ ], a phthalonitrile compound What is necessary is just to mix and manufacture A and a phthalonitrile compound B in a molar ratio of 0.5: 3.5.

Next, when manufacturing the phthalocyanine compound (1-3) which is a suitable aspect of this invention, the phthalonitrile shown by following formula (G) as (1) as a phthalonitrile compound of Formula (I)-(IV) which is a starting raw material It is preferable to use a compound (hereinafter only referred to as "phthalonitrile compound G") and (2) a phthalonitrile compound represented by the following general formula (H) (hereinafter also referred to simply as "phthalonitrile compound H"). .

Because of formula (G) and (H) of the X and A ₁ is the same as X, A ₁ in the second formula, R ', R ", and l is the general formula (2)" of R', R "and l the same, in which Omit the description.

In addition, p 'and q' in phthalonitrile compound G are 0 or 1, and p '+ q' = 1. Y 'represents a hydrogen atom or a halogen atom, Preferably it is a hydrogen atom. However, Y 'does not become a halogen atom altogether. When Y 'is a halogen atom, Preferably it is a fluorine atom, a chlorine atom, More preferably, it is a chlorine atom. When two or more Y 'exists, the same kind may be sufficient as Y', and a different kind may be sufficient as it.

P in a phthalonitrile compound (H) is an integer of 1-4, Preferably it is 1-3. When p is 2 or more, the groups represented by the formula (2) may be the same or different. In addition, q is an integer of 0-3, Preferably it is 0 or 1, and p + q is 4 or less. When q is 2 or more, the group represented by the formula (2 ') may be the same or different. Y represents a hydrogen atom or a halogen atom, Preferably it is a halogen atom, More preferably, it is a fluorine atom and a chlorine atom, More preferably, it is a chlorine atom. However, Y does not become a hydrogen atom altogether. When two or more Y exists, the same kind may be sufficient as Y, and a different kind may be sufficient as it.

Hereinafter, the synthesis example of "phthalonitrile compound G" is demonstrated.

The phthalonitrile compound G can be obtained by a conventionally well-known manufacturing method. Suitably, nitrophthalonitrile and the following formula (C) in which the hydrogen atom of the benzene ring may be substituted by one or two halogen atoms;

A ₁ -XH (C)

Compound C represented by the following, or following formula (C ');

It is obtained by reacting the compound C 'shown by. The nitro group in nitrophthalonitrile is substituted with a substituent represented by formula (2) derived from compound C or a substituent represented by formula (2 ') derived from compound C'. Formula (C) in the X and A ₁ are the same and X and A ₁ in the second formula, formula (C ') of the R', R "Because and l is 'R of', R Formula 2" equal to, and l , The description is omitted here. The phthalonitrile compound G can be obtained by reacting the compound C or the compound C 'with 3-nitrophthalonitrile or 4-nitrophthalonitrile, in which one or two hydrogen atoms of the benzene ring may be substituted with halogen atoms. Preferably, the phthalonitrile compound G can be obtained by reacting 3-nitrophthalonitrile or 4-nitrophthalonitrile with compound C or compound C '.

Although the reaction of nitrophthalonitrile, the compound C, and the compound C 'may be performed in a non-solvent or in an organic solvent, Preferably it is performed in an organic solvent. As an organic solvent which can be used at this time, Nitriles, such as acetonitrile and benzonitrile; Polar solvents such as acetone and 2-butanone; Alcohol solvents, such as compound C, when methanol, ethanol, and X are oxygen atoms, etc. are mentioned. Among these, 2-butanone, acetonitrile, benzonitrile and acetone are preferable. These solvents may be used alone or in combination of two or more thereof. The amount of the organic solvent used when the solvent is used is such that the concentration of nitrophthalonitrile is usually 1 to 50 (w / v)%, preferably 10 to 30 (w / v)%.

The use ratio of nitrophthalonitrile, compound C, and compound C 'is appropriately selected depending on the structure of the desired phthalonitrile compound, and is not particularly limited, but is usually used for compound C and 1 mole of nitrophthalonitrile. Compound C 'is used in an amount of 1.0 to 2.0 moles, preferably 1.0 to 1.5 moles.

The reaction between nitrophthalonitrile, compound C, and compound C 'is 1,8-diazabicyclo [5.4.0] -7-undecene (DBU), potassium fluoride (KF), potassium carbonate (K ₂ CO ₃ ) It is preferable to carry out in presence of catalysts, such as these. Moreover, you may add a phase transfer catalyst separately. By adding a phase transfer catalyst, the rate of the nucleophilic substitution reaction of nitrophthalonitrile and compound C or compound C 'is increased. The phase transfer catalyst is not particularly limited, but quaternary ammonium salts are preferred. Specific examples include tetramethylammonium chloride, tetramethylammonium bromide, tetrabutylammonium chloride, tetrabutylammonium bromide, benzyltriethylammonium chloride, benzyltriethylammonium bromide, benzyltributylammonium chloride, benzyltributylammonium bromide and the like. Can be. At this time, the amount of the catalyst containing the phase transfer catalyst is not particularly limited as long as the reaction proceeds satisfactorily. Specifically, the catalyst is preferably added in an amount of usually 1.0 to 2.0 moles, more preferably 1.0 to 1.5 moles, per 1 mole of nitrophthalonitrile.

The reaction conditions of the nitrophthalonitrile, the compound C and the compound C 'are not particularly limited as long as the reaction proceeds satisfactorily. Specifically, at the time of reaction of nitrophthalonitrile, compound C and compound C ', Preferably it is made to react at the temperature of 30-150 degreeC, More preferably, 60-90 degreeC, Preferably it is 1-50 hours.

Next, the synthesis example of "phthalonitrile compound H" is demonstrated. As a synthesis example of "phthalonitrile compound H", the following formula (D):

The phthalonitrile derivative (hereinafter also referred to simply as phthalonitrile derivative D) represented by the following formula (E):

A ₁ -XH (E)

Compounds represented by the following (hereinafter also referred to simply as "compound E") and / or the following formula (E ');

And a compound represented by the following (hereinafter, simply referred to as "compound E '").

In said Formula (D), X <_1> , X <_2> , X <_3> and X <_4> are a hydrogen atom or a halogen atom each independently, and all of X <_1> , X <_2> , X <_3> and X <_4> do not become a hydrogen atom. Preferably, all of X ₁ , X ₂ , X ₃ and X ₄ are halogen atoms. As a halogen atom, a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom are mentioned, Preferably it is a fluorine atom and a chlorine atom from a viewpoint of reactivity, molecular weight, and a steric effect, More preferably, it is a chlorine atom.

Since Equation (E) of the X and A ₁ are the same and X and A ₁ in the second formula, formula (E ') of the R', R "and l is 'R of', R Formula 2" equal to, and l , The description is omitted here.

In the reaction of the compound E and the compound E ', the halogen atom is substituted with the group represented by the formula (2) or the group represented by the formula (2'). What is necessary is just to adjust suitably the ratio of the usage-amount of the phthalonitrile derivative D, the compound E, and the compound E 'at the time of reaction by the number which introduce | transduces the group shown by Formula (2) or the group shown by Formula (2'). For example, when introducing two groups represented by the general formula (2) and two groups represented by the general formula (2 '), it is preferable to react the compound E and the compound E' with 2-3 moles with respect to 1 mole of the phthalonitrile derivative D. In addition, in the case of introducing three groups represented by the formula (2) and three groups represented by the formula (2 '), it is preferable to react the compound E and the compound E' with 3 to 4 moles with respect to 1 mole of the phthalonitrile derivative D. Moreover, when introducing one group represented by General formula (2), it is preferable to make 1-1.5 mol of compound E and compound E 'react with 1 mol of phthalonitrile derivatives D.

The reaction of the phthalonitrile derivative D with the compound E or the compound E 'may be carried out in a solvent-free or in an organic solvent, but is preferably carried out in an organic solvent. As an organic solvent which can be used at this time, Nitriles, such as acetonitrile and benzonitrile; Polar solvents such as acetone and 2-butanone; Alcohol solvents, such as methanol and ethanol, etc. are mentioned. Among these, 2-butanone, acetonitrile, benzonitrile and acetone are preferable. These solvents may be used alone or in combination of two or more thereof. The usage-amount of the organic solvent at the time of using a solvent is the quantity whose nitrophthalonitrile concentration is 1-60 (w / v)% normally, Preferably it is 10-30 (w / v)%.

In the reaction of the phthalonitrile derivative (D) with the compound (E) and the compound (E '), a trapping agent is preferably used in order to remove hydrogen halide (for example, hydrogen fluoride) or the like generated during the reaction. Examples of the specific trapping agent when using the trapping agent include potassium fluoride, potassium carbonate, calcium carbonate, calcium hydroxide, magnesium hydroxide, magnesium chloride and magnesium carbonate, among which potassium fluoride, calcium carbonate and calcium hydroxide are preferable. And potassium fluoride is most preferred. In addition, the usage-amount of a trapping agent at the time of using a trapping agent will not be restrict | limited especially if it is an amount which can remove hydrogen halide etc. which generate | occur | produce efficiently during a reaction, It is usual with respect to 1 mol of compound (E) and compound (E '). 1.0-4.0 mol, Preferably it is 1-1.5 mol.

The reaction conditions of the phthalonitrile derivative (D), the compound (E) and the compound (E ') are not particularly limited as long as the reaction proceeds well. Specifically, at the time of reaction of nitrophthalonitrile with compound (E) and compound (E '), it is preferably at a temperature of 30 to 150 ° C, more preferably 50 to 100 ° C, preferably 1 to 50 hours. More preferably, it is made to react for 1 to 10 hours.

In addition, the phthalonitrile compound (H) manufactured by such a method may exist in the form of a mixture in addition to the case of one type of compound. The phthalonitrile compound (H) prepared in the following examples is also present in the form of a mixture. This is because the group represented by the formula (2) or the group represented by the formula (2 ') is substituted at the position of the halogen atom, but it is difficult to control which position is substituted. For this reason, in such a case, the number of substituents represented by the formula (2) and the substituents represented by the formula (2 ') in the substituent at the α-position or β-position in the formula (H) is represented by the formula (2) and the formula (2') in each phthalocyanine compound. Since it appears as an average of the number of substituents, it does not necessarily become an integer. And phthalonitrile compound (H) exists in the form of a mixture, and when a phthalocyanine compound is manufactured as a raw material, a phthalocyanine compound also exists in the form of a mixture.

The phthalocyanine compound (1-3) can be manufactured by carrying out the cyclization reaction with 1 type chosen from the group which consists of a metal compound using the phthalonitrile compound (G) and phthalonitrile compound (H) thus obtained as a raw material. . Under the present circumstances, the mixing molar ratio of a phthalonitrile compound (G) and a phthalonitrile compound (H) may be suitably adjusted so that it may be the number of substituents of a desired phthalocyanine compound. Suitably, the mixing ratio of the phthalonitrile compound (G) and the phthalonitrile compound (H) is 1.0 to 3.5 mol, more preferably 1.0 to 3.3 mol with respect to 1.0 mol of the phthalonitrile compound (G). By mixing in such a range, the phthalocyanine compound with high solubility in an ether solvent can be obtained.

As another aspect of obtaining a phthalocyanine compound (1), following formula (F):

The phthalocyanine derivative (henceforth only called a "phthalocyanine derivative (F)") obtained after performing a cyclization reaction with a phthalonitrile compound and a metal compound shown by this, and following formula (E):

A ₁ -XH (E)

Represented by the following (hereinafter also referred to simply as "compound (E)") and / or the following formula (E ');

The compound shown below (henceforth only a "compound (E ')"); The method of making it react is mentioned.

In formula (F), Y <_1> , Y <_2> , Y <_3> and Y <_4> are respectively independently halogen atoms, such as a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom, or a hydrogen atom. As a halogen atom, Preferably they are a fluorine atom and a chlorine atom, More preferably, they are a chlorine atom. In the reaction of the compound (E) and the compound (E '), since the halogen atom is substituted with the substituent represented by the formula (2) or the substituent represented by the formula (2'), the halogen is finally introduced at the position to introduce the group represented by the formula (2) or (2 '). What is necessary is just to select the phthalonitrile which an atom exists as a raw material. For example, when introducing one substituent represented by the general formula (2) or the general formula (2 ') at the α position of the phthalocyanine compound, phthalonitrile in which Y ₁ or Y ₄ is a halogen atom may be used.

A ₁ and X in the formula (E) are the same as those used in the formula (2), and R ', R "and l in the formula (E') are the same as those used in the formula (2 ').

The cyclization reaction between the phthalonitrile compound and the metal compound represented by the formula (F) can be cyclized under the same conditions as the cyclization reaction between the phthalonitrile compound and the metal compound of the above formulas (I) to (IV). Therefore, description is omitted here.

Reaction of a phthalocyanine derivative (F), a compound (E), or a compound (E ') can be performed by a conventionally well-known method. It is preferable to perform reaction in presence of an inert solvent which is not reactive with the compound used for reaction. For example, nitriles such as benzonitrile and acetonitrile, and amides such as N-methylpyrrolidone or dimethylformamide; Dichlorobenzene and toluene are mentioned. In the reaction, it is preferable to add inorganic powders such as calcium carbonate, calcium hydroxide, potassium fluoride, calcium carbonate, magnesium hydroxide, magnesium chloride and magnesium carbonate.

The phthalocyanine compound of the present invention is a heat ray shielding material for the purpose of shielding heat rays while having translucency or transparency, a heat absorbing glass for automobiles, a heat ray shielding film or a heat ray shielding resin glass, a plasma having high visible light transmittance and high cut efficiency of near infrared light. As a near-infrared absorber for non-contact fixing toners such as filters for displays, flash fixing, etc., near-infrared absorbers for heat-retaining heat-retaining fibers, infrared absorbers for fibers having camouflage performance (camouflage performance) against reconnaissance by infrared rays, and semiconductor lasers. Optical recording media using a light, a filter for a liquid crystal display using a xenon lamp as a backlight, a near infrared absorbing dye for writing or reading in an optical character reader, a near infrared light sensitizer, an optical heat exchanger such as a thermal transfer and thermal stencil, a laser Laser welding to heat fusion resin using beam Photosensitive pigments for tumor treatment, color CRT tube selective absorption filters, color toners, inkjet inks, for absorption of light in longer wavelengths with better tissue permeability, such as optical heat exchangers, near-infrared absorbing filters, stable fatigue inhibitors, or light conductive materials. , Anti-counterfeiting ink, anti-counterfeiting bar code ink, near-infrared absorbing ink, marking agent for positioning photographs and films, lens or shield of goggles, dyeing agent for sorting during plastic recycling, and PET bottle molding processing It is excellent in the case of using for preheating preparation etc. of city. In particular, in view of the above characteristics, the phthalocyanine compound of the present invention can be suitably used for a near infrared absorbing dye, a heat ray shielding material, a plasma display filter, and a near infrared absorbing material.

Since the phthalocyanine compound which has a specific structure as mentioned above shows the maximum absorption wavelength in the specific wavelength range of 640-750 nm, it is possible to selectively cut the light of these areas. For this reason, when the phthalocyanine compound of this invention is used for the filter for flat panel displays, the light of the near-infrared light (700-750 nm) of the dance which PDP and LCD generate | occur | produce, for example, or the impurity red wavelength (640 called so-called crimson) It is expected that the light of ˜700 nm) can be cut, for example, to prevent the malfunction of the optical communication system corresponding to the flow of increasing information amount, and at the same time, to produce the effect of vivid red color. In particular, since the PDP shows extra large light emission near 710 nm, the phthalocyanine compound of the present invention that absorbs 710 nm light and has high transmittance of visible light such as 520 nm is useful.

Therefore, this invention also relates to the filter for flat panel displays containing the phthalocyanine compound (1). As a use of the filter for flat panel displays, what is used for a plasma display and a liquid crystal display is suitable, and especially what is used for a plasma display is suitable.

Although it is essential to contain the phthalocyanine compound (1), the filter of this invention may further contain the pigment | dye which has another maximum absorption wavelength. Examples of the other dyes that can be used in such a case are appropriately selected depending on the desired maximum absorption wavelength depending on the application. For example, a dye for absorbing near-infrared absorbing dyes of 800 to 1000 nm or neon light of orange color of 570 to 600 nm is exemplified. Can be. Among these, as a near-infrared absorbing dye of 800-1000 nm, a cyanine pigment | dye, a phthalocyanine pigment | dye, a nickel complex dye, a dimonium pigment | dye, etc. are mentioned. Among these, as the phthalocyanine-based dyes, the phthalocyanine-based dyes described in JP 2001-106689 A, especially the phthalocyanine produced in Example 8 of JP 2001-106689 A [CuPc (2,5-Cl ₂ PhO) ₈ {2,6- (CH ₃ ) ₂ PhO} ₄ (PhCH ₂ NH) ₄ ] (λ max: 807 nm), phthalocyanine [VOPc (2,5-Cl ₂ PhO) ₈ {2] prepared in Example 7 of the publication. , 6- (CH ₃ ) ₂ PhO} ₄ (PhCH ₂ NH) ₄ ] (λ max: 870 nm), phthalocyanine [VOPc (PhS) ₈ {2,6- (CH ₃ ) ₂ prepared in Example 9 of the publication. PhO} ₄ (PhCH ₂ NH) ₄ ] (λ max: 912 nm); Phthalocyanine-based pigments described in Japanese Patent Application Laid-Open No. 2004-18561, especially phthalocyanine [VOPc (PhS) ₈ {2,6- (CH ₃ ) ₂ PhO} ₄ prepared in Example 8 of Japanese Patent Application Laid-Open No. 2004-18561; {CH ₃ CH ₂ O (CH ₂ ) ₃ NH} ₄ ] (λ max: 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 ₅ ) CH ₂ NH} ₄ ] (λ max: 962 nm); The following formula:

Phthalocyanine compound [hereinafter also referred to as {CuPc (3-methoxycarbonylphenoxy) ₈ (2-chlorobenzylamino) ₇ F}] (? Max: 916 nm), the following formula:

Phthalocyanine compounds (hereinafter referred to as {CuPc (3-methoxycarbonylphenoxy) ₈ (2-ethylhexylamino) ₈ })) (? Max: 963 nm) and the like are preferably used. In this case, in consideration of durability and weather resistance, it is particularly preferable that the phthalocyanine-based dye of 800 to 1000 nm is copper as the center metal of the phthalocyanine skeleton. Moreover, the phthalocyanine compound described in the Example of Unexamined-Japanese-Patent No. 10-78509 can also be used. Examples of the dimonium pigment include (N, N, N ', N'-tetrakis (p-diethylaminophenyl) -p-benzoquinone-bis (monium) -hexafluoroantimonate, N, N, N ', N'-tetrakis (p-dibutylaminophenyl) -p-phenylenediamine-bis (bis (trifluoromethanesulfonyl) imide acid) immonium salt (manufactured by Nippon-Kallet Co., Ltd., brand: CIR- 1085), N, N, N ', N'-tetrakis (p-dibutylaminophenyl) -p-phenylenediamine-bis (antimony hexafluoride) immonium salt (manufactured by Nippon Kalet, Ltd., brand: CIR -1081), and dimonium pigments (manufactured by Nippon Kalet, Trademark: CIR-RL) composed of a dimonium cation and a bis (trifluoromethanesulfon) imide anion are preferably used. As the dye, bis (1,2-diphenylethene-1,2-dithiol) nickel, etc. are preferably used, and as the cyanine dye, a stabilized cyanine dye can be used. , Cyanine-based cations and quenchers Among these, cyanine-based cations include, for example, cations No. 1 and No. 2 shown below, and as quencher anions, for example, anion Nos. 11 and No. 22 shown below. The compound of can be used preferably, and the salt compound which combined these suitably is used suitably as a stabilized cyanine pigment | dye.

Moreover, as a pigment | dye which absorbs the orange neon light of 570-600 nm, a tetraaza porphyrin pigment, a cyanine pigment, a squarylium pigment, an anthraquinone pigment, a subphthalocyanine pigment, a phthalocyanine pigment, a polymethyl pigment, And polyazo dyes. Among these, as a tetraaza porphyrin type pigment | dye, the tetra- t-butyl- tetraaza porphyrin copper complex, the tetra- t-butyl- tetraaza porphyrin vanadium complex, etc. are used preferably. As the cyanine dye and squarylium dye, cyanine dyes, squarylium dyes and the like described in JP-A-2002-189422 are preferably used. As a subphthalocyanine pigment | dye, the subphthalocyanine pigment | dye etc. of Unexamined-Japanese-Patent No. 2006-124593 are used preferably. When 570-600 nm phthalocyanine type pigment | dye considers durability and weather resistance, it is especially preferable that the center metal of a phthalocyanine skeleton is copper.

In addition to the phthalocyanine compound (1), a dye having a maximum absorption wavelength at 600 to 750 nm may be included. Specific examples of such dyes include 1-ethyl-2- [3-chloro-5- (1-ethyl-2 (1H) -quinolinylidene) -1,3-pentadienyl] quinolinium bromide (106 times; λ max: 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; lambda max: 675.6 nm), 3-ethyl-2- [5- (3-ethyl-2-benzothiazolinylidene) -1,3-pentadier And cyanine dyes such as nil] benzothiazolium iodine (475 times; lambda max: 651.6 nm). In addition, in the above, the magnification in parentheses is the magnification of the absorbance at the maximum absorption wavelength with respect to the absorbance at 460 nm, and indicates the maximum absorption wavelength (λ max) in parentheses.

Moreover, the said other pigment | dye may be used independently and may be used in the form of 2 or more types of mixtures.

The filter for flat panel displays of this invention contains the pigment | dye / phthalocyanine pigment | dye (henceforth only a "color / phthalocyanine pigment | dye" hereafter) which can be used in the filter for flat panel displays, The base material said by this invention In addition, it is contained in the inside of a base material, and also means the state apply | coated to the surface of a base material, the state interposed between the base material and a base material, etc. As a base material, a transparent resin plate, a transparent film, transparent glass, etc. are mentioned. Although it does not specifically limit as a method of manufacturing the filter for flat panel displays of this invention using the said phthalocyanine compound, For example, the following four methods can be used.

That is, (1) a method of kneading a dye / phthalocyanine dye into a resin, followed by heat molding to produce a resin plate or a film; (2) a method of producing a coating material (liquid to paste form) containing a dye / phthalocyanine dye and coating on a transparent resin plate, a transparent film, or a transparent glass plate; (3) a method in which a dye / phthalocyanine dye is contained in an adhesive to produce a custom resin plate, a custom resin film, a custom glass, or the like; And (4) a dye / phthalocyanine dye is contained in an adhesive and applied to an antireflective film or the like and adhered to a PDP panel or PDP front filter glass.

In the present invention, since the near-infrared light emitted from the display is provided in front of the display, a low visible light transmittance lowers the sharpness of the image. Therefore, the higher the visible light transmittance of the filter, the better, at least 30%, Preferably at least 40% is required. In addition, the cut region of near-infrared light is 640-1100 nm, and it is designed so that the average light transmittance of this region may be 20% or less, Preferably it is 15% or less. For this purpose, you may combine 2 or more types of pigment | dye / phthalocyanine pigment | dye if necessary. It is also desirable to add other pigments with absorption in the visible region to change the color tone of the filter. Moreover, the filter containing only the pigment | dye for color tone can be produced, and it can also join later. In particular, when an electromagnetic wave cut layer such as sputtering is provided, the color tone is important because the color may be significantly 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 an antiglare (AG) layer that block electromagnetic waves emitted from the flat panel display may be provided. Their production method is not particularly limited. E., By example, a laminated wave-cutting layer is a metal oxide can be used the sputtering method such as, but is usually, but is normally In ₂ O ₃ (ITO) by the addition of Sn, such as alternating dielectric and metal layers on a substrate, sputtering, It is also possible to cut light of 1100 nm or more from near infrared rays and far infrared rays to electromagnetic waves. As a dielectric layer, it is a transparent metal oxide, such as indium oxide and zinc oxide, and as a metal layer, silver or a silver-palladium alloy is common, and usually it starts with a dielectric layer and laminates about 3, 5, 7 or 11 layers. In this case, heat emitted from the display can also be cut at the same time. However, since the dye / phthalocyanine dye has an excellent heat ray shielding effect, the heat resistance effect can be further improved. As a base material, the filter containing a pigment | dye / phthalocyanine pigment | dye may be used as it is, and after sputtering on a resin film or glass, you may join with the filter containing this pigment | dye / phthalocyanine pigment | dye. In the case where the electromagnetic wave is actually cut, it is necessary to provide an earth electrode. In order to suppress the reflection of the surface and improve the transmittance of the filter, the antireflection layer is formed by vacuum deposition, sputtering, ion plating, ion beam assisting, etc. of inorganic materials such as metal oxides, fluorides, borides, carbides, nitrides, and sulfides. For example, the method of laminating | stacking in single layer or multiple layers, the method of laminating | stacking resin in which refractive indexes, such as an acrylic resin and a fluororesin, differ in a single layer or a multilayer, etc. are mentioned. In addition, the antireflective film may be adhered onto the filter. In addition, an antiglare (AG) layer may be provided if necessary. As the antiglare (AG) layer, in order to scatter the transmitted light for the purpose of widening the viewing angle of the filter, a method of coating the surface by ink-making fine powder such as silica, melamine, and acrylic may be used. As the curing of the ink, thermal curing or photo curing can be used. Moreover, the film which carried out the antiglare process can also be adhere | attached on the said filter. If necessary, a hard coat layer may be provided.

The structure of the filter for flat panel displays can be changed as needed. Usually, an antireflective layer is provided on the filter containing a near-infrared absorbing compound, or an antiglare layer is provided on the opposite side to an antireflective layer if necessary. In addition, when combining an electromagnetic wave cut layer, a filter containing a near-infrared absorptive compound may be used as a base material, or an electromagnetic wave cut layer may be provided thereon, or a filter containing a near-infrared absorptive compound and a filter having an electromagnetic wave cut capability may be bonded to each other. I can make it. In that case, an antireflection layer may be further produced on both sides, or an antireflection layer may be produced on one side if necessary, and an antiglare layer may be produced on the opposite side. In addition, when the pigment | dye which has absorption in the visible region is added for color correction, the method is not restrict | limited.

Example

Hereinafter, an Example and a comparative example are demonstrated. However, the technical scope of the present invention is not limited only to the following examples. In addition, in the name of the following compound, Pc represents a phthalocyanine nucleus and PN represents a phthalonitrile.

Synthesis Example 1-1 Synthesis of Phtharonitrile Compound [α-{(2-NO ₂ ) C ₆ H ₄ O} PN] (Intermediate 1-1)

25.10 g (0.145 mol) of 3-nitrophthalonitrile (hereinafter referred to as 3NO ₂ PN), 24.21 g (0.174 mol) of 2-nitrophenol, 24.05 g (0.174 mol) of potassium carbonate, n-tetrabutylammonium in a 150 ml flask 0.47 g (0.001 mol) of bromide (hereinafter referred to as TBAB) and 100.42 g of acetonitrile were added thereto, and the mixture was reacted for about 12 hours while stirring at an internal temperature of 80 ° C. using a magnetic stirrer. After cooling, 200 g of water was added dropwise to the solution obtained by suction filtration to precipitate crystals. After the obtained crystals were suction-filtered, 200 g of water was further added, and it wash | cleaned and refine | purified by stirring and washing. After suction filtration, the crystals taken out were vacuum dried at about 60 ° C. overnight to yield about 36.1 g (yield 93.9 mol% for 3NO ₂ PN).

Synthesis Example 1-2 Synthesis of Phtharonitrile Compound [α-{(2,6-Cl ₂ ) C ₆ H ₃ O} PN] (Intermediate 1-2)

25.10 g (0.145 mole) of 3NO ₂ PN, 26.00 g (0.160 mole) of 2,6-dichlorophenol, 22.04 g (0.160 mole) of potassium carbonate, 0.93 g (0.002 mole) of TBAB, and 100.42 g of acetonitrile were added to a 150 ml flask. The mixture was reacted for about 5 hours while stirring using a magnetic stirrer at an internal temperature of 80 ° C. After cooling, a mixed solution of 50 g of methanol and 150 g of water was added dropwise to the solution obtained by suction filtration to precipitate crystals. The obtained crystals were suction filtered and then washed and purified by adding a mixed solution of 200 g of methanol and 200 g of water, followed by stirring and washing. After suction filtration, the crystals taken out were vacuum dried at about 60 ° C. overnight to yield about 38.9 g (yield 92.8 mol% for 3NO ₂ PN).

Synthesis Example 1-3 Synthesis of Phtharonitrile Compound [α-{(2-CH ₃ O) C ₆ H ₄ O} PN] (Intermediate 1-3)

5.19 g (0.030 mol) of 3NO ₂ PN, 4.10 g (0.033 mol) of 2-methoxyphenol, 4.56 g (0.033 mol) of potassium carbonate and 20.78 g of acetonitrile were added to a 150 ml flask. It was made to react for about 3 hours, stirring. After cooling, a mixed solution of 10 g of methanol and 50 g of water was added dropwise to the solution obtained by suction filtration to precipitate crystals. The obtained crystals were suction filtered and then washed and purified by adding a mixed solution of 20 g of methanol and 100 g of water, followed by stirring and washing. After suction filtration, the extracted crystals were vacuum dried at about 60 ° C. overnight to yield about 7.03 g (yield 93.6 mol% for 3NO ₂ PN).

Synthesis Example 1-4 Synthesis of Phtharonitrile Compound [α-{(2-Ph) C ₆ H ₄ O} PN] (Intermediate 1-4)

Into a 150 ml flask, 3.29 g (0.019 mol) of 3NO ₂ PN, 3.56 g (0.021 mol) of 2-phenylphenol, 2.89 g (0.021 mol) of potassium carbonate, 0.12 g (0.0004 mol) of TBAB and 19.74 g of acetonitrile were added. It reacted for about 28 hours, stirring using temperature 60 degreeC and the magnetic stirrer. After cooling, a mixed solution of 10 g of methanol and 50 g of water was added dropwise to the solution obtained by suction filtration to precipitate crystals. The obtained crystals were suction filtered and then washed and purified by adding a mixed solution of 20 g of methanol and 100 g of water, followed by stirring and washing. After suction filtration, the crystals taken out were vacuum dried at about 60 ° C. overnight to yield about 5.12 g (yield 90.9 mol% for 3NO ₂ PN).

Synthesis Example 1-5 Synthesis of Phtharonitrile Compound [α-{(2-COOCH ₃ ) C ₆ H ₄ O} PN] (Intermediate 1-5)

Into a 150 ml flask, 2.60 g (0.015 mole) of 3NO ₂ PN, 2.74 g (0.018 mole) of methyl salicylate, 2.49 g (0.018 mole) of potassium carbonate, 0.10 g (0.0003 mole) of TBAB, and 10.39 g of acetonitrile were added. The reaction was carried out for 9 hours while stirring using a magnetic stirrer. After cooling, the solvent was removed from the solution obtained by suction filtration by evaporation, and 10 g of methyl ethyl ketone (hereinafter referred to as MEK) was added thereto. The solution thus obtained was dripped in 100 g of hexane to precipitate crystals. The obtained crystals were suction filtered and then washed and purified by adding a mixed solution of 10 g of MEK and 100 g of hexane and stirring and washing. After suction filtration, the crystals taken out were dried in vacuo at about 60 ° C. overnight to yield about 3.71 g (88.8 mol% for 3NO ₂ PN).

Synthesis Example 1-6 Synthesis of Phtharonitrile Compound [β-{(2-COOCH ₃ ) C ₆ H ₄ O} PN] (Intermediate 1-6)

25.10 g (0.145 mole) of 4-nitrophthalonitrile (hereinafter referred to as 4NO ₂ PN), 30.89 g (0.203 mole) of methyl salicylate, 22.04 g (0.160 mole) of potassium carbonate, 0.93 g (0.003 mole) of TBAB And 100.42 g of acetonitrile were added and reacted for about 40 hours while stirring using an internal temperature of 80 ° C. and a magnetic stirrer. After cooling, a mixed solution of 50 g of methanol and 150 g of water was added dropwise to the solution obtained by suction filtration to precipitate crystals. The obtained crystals were suction filtered and then washed and purified by adding a mixed solution of 200 g of methanol and 200 g of water, followed by stirring and washing. After suction filtration, the crystals taken out were vacuum dried at about 60 ° C. overnight to yield about 34.8 g (a yield of 86.3 mol% for 4NO ₂ PN).

Synthesis Example 1-7 Synthesis of Phtharonitrile Compound [β-{(2-COOC ₂ H ₄ OCH ₃ ) C ₆ H ₄ O} PN] (Intermediate 1-7)

2.60 g (0.015 mol) of 4NO ₂ PN and 3.53 g (0.018 mol) of 2- (methoxyethyl) carboxyphenol, 2.49 g (0.018 mol) of potassium carbonate, 0.10 g (0.0003 mol) of TBAB, 20.78 in acetonitrile g was added and reacted for about 48 hours while stirring using an internal temperature of 80 ° C. and a magnetic stirrer. After cooling, the solvent was removed from the solution obtained by suction filtration by evaporation, and 10 g of MEK was added thereto. The solution thus obtained was dripped in 100 g of hexane to precipitate crystals. The obtained crystals were suction filtered and then washed and purified by adding a mixed solution of 10 g of MEK and 100 g of hexane and stirring and washing. After suction filtration, the extracted crystals were vacuum dried at about 60 ° C. overnight to yield about 4.12 g (yield 85.2 mol% for 4NO ₂ PN).

Synthesis Example 1-8 Synthesis of Phtharonitrile Compound [α-{(2,6- (CH ₃ ) ₂ ) C ₆ H ₃ O} PN] (Intermediate 1-8)

6.06 g (0.035 mol) of 3NO ₂ PN, 4.70 g (0.039 mol) of 2,6-xylenol, 5.32 g (0.039 mol) of potassium carbonate, 0.23 g (0.0007 mol) of TBAB, and 24.24 g of acetonitrile were charged into a 150 ml flask. Then, the mixture was reacted for about 20 hours with stirring using an internal temperature of 80 ° C. and a magnetic stirrer. After cooling, a mixed solution of 25 g of methanol and 50 g of water was added dropwise to the solution obtained by suction filtration to precipitate crystals. The obtained crystals were suction filtered and then washed and purified by adding a mixed solution of 50 g of methanol and 50 g of water, followed by stirring and washing. After suction filtration, the extracted crystals were vacuum dried at about 60 ° C. overnight to yield about 5.3 g (60.4 mol% of yield for 3NO ₂ PN).

Synthesis Example 1-9 Synthesis of Phtharonitrile Compound [α-{(2-CN) C ₆ H ₄ O} PN] (Intermediate 1-9)

6.06 g (0.035 mol) of 3NO ₂ PN, 4.59 g (0.039 mol) of 2-cyanophenol, 5.32 g (0.039 mol) of potassium carbonate, 0.23 g (0.0007 mol) of TBAB, and 24.24 g of acetonitrile were added to a 150 ml flask. The reaction was carried out for about 2 hours while stirring using an internal temperature of 85 ° C. and a magnetic stirrer. After cooling, a mixed solution of 25 g of methanol and 50 g of water was added dropwise to the solution obtained by suction filtration to precipitate crystals. The obtained crystals were suction filtered and then washed and purified by adding a mixed solution of 50 g of methanol and 50 g of water, followed by stirring and washing. After suction filtration, the extracted crystals were vacuum dried at about 60 ° C. overnight to yield about 5.6 g (yield 65.0 mol% for 3NO ₂ PN).

Synthesis Example 1-10 Synthesis of Phtharonitrile Compound [α-{(2- (CF ₃ ) C ₆ H ₄ O) PN} (Intermediate 1-10)

In a 150 ml flask, 6.06 g (0.035 mol) of 3NO ₂ PN, 6.24 g (0.039 mol) of 2-hydroxybenzotrifluoride, 5.32 g (0.039 mol) of potassium carbonate, 0.23 g (0.0007 mol) of TBAB, and 24.24 g of acetonitrile It injected | thrown-in, and made it react for about 2 hours, stirring using an internal temperature of 85 degreeC and the magnetic stirrer. After cooling, a mixed solution of 25 g of methanol and 50 g of water was added dropwise to the solution obtained by suction filtration to precipitate crystals. The obtained crystals were suction filtered and then washed and purified by adding a mixed solution of 50 g of methanol and 50 g of water, followed by stirring and washing. After suction filtration, the crystals taken out were vacuum dried at about 60 ° C. overnight to yield about 9.7 g (yield 95.7 mol% for 3NO ₂ PN).

Synthesis Example 1-11 Synthesis of Phtharonitrile Compound [α-{(C ₆ F ₅ O) PN}] (Intermediate 1-11)

6.06 g (0.035 mol) of 3NO ₂ PN, 7.11 g (0.039 mol) of tetrafluorophenol, 5.32 g (0.039 mol) of potassium carbonate, 0.23 g (0.0007 mol) of TBAB, 24.24 g of acetonitrile were added to a 150 ml flask. It reacted for about 2 hours, stirring using temperature 85 degreeC and the magnetic stirrer. After cooling, a mixed solution of 25 g of methanol and 50 g of water was added dropwise to the solution obtained by suction filtration to precipitate crystals. The obtained crystals were suction filtered and then washed and purified by adding a mixed solution of 50 g of methanol and 50 g of water, followed by stirring and washing. After suction filtration, the extracted crystals were dried in vacuo at about 60 ° C. overnight to yield about 9.7 g (yield 89.0 mol% for 3NO ₂ PN).

Synthesis Example 1-12 Synthesis of Phtharonitrile Compound [β-{(2-COOCH _3-4 -I) C ₆ H ₃ O} PN] (Intermediate 1-12)

6.93 g (0.040 mol) of 4NO ₂ PN, 12.23 g (0.044 mol) of methyl 5-iodine salicylate, 6.08 g (0.044 mol) of potassium carbonate, 0.26 g (0.0008 mol) of TBAB, and 27.70 g of acetonitrile were charged into a 150 ml flask. The reaction was carried out for about 6 hours while stirring using an internal temperature of 85 ° C. and a magnetic stirrer. After cooling, a mixed solution of 28 g of methanol and 55 g of water was added dropwise to the solution obtained by suction filtration to precipitate crystals. The obtained crystals were suction filtered and then washed and purified by adding a mixed solution of 55 g of methanol and 55 g of water, followed by stirring and washing. After suction filtration, the crystals taken out were vacuum dried at about 60 ° C. overnight to yield about 14.3 g (a yield of 88.5 mol% for 4NO ₂ PN).

Synthesis Example 1-13 Synthesis of Phtharonitrile Compound [β-{(2,6- (CH ₃ ) ₂ ) C ₆ H ₃ O} PN] (Intermediate 1-13)

6.93 g (0.040 mole) of 4NO ₂ PN, 6.84 g (0.056 mole) of 2,6-xylenol, 6.08 g (0.044 mole) of potassium carbonate, 0.26 g (0.0008 mole) of TBAB, and 27.70 g of acetonitrile The reaction was carried out for about 12 hours while stirring using an internal temperature of 85 ° C. and a magnetic stirrer. After cooling, a mixed solution of 28 g of methanol and 55 g of water was added dropwise to the solution obtained by suction filtration to precipitate crystals. The obtained crystals were suction filtered and then washed and purified by adding a mixed solution of 55 g of methanol and 55 g of water, followed by stirring and washing. After suction filtration, the crystals taken out were vacuum dried at about 60 ° C. overnight to yield about 9.48 g (yield 95.5 mol% for 4NO ₂ PN).

Synthesis Example 1-14 Synthesis of Phtharonitrile Compound [β-{(2,6- (OCH ₃ ) ₂ ) C ₆ H ₃ O} PN] (Intermediate 1-14)

6.93 g (0.040 mole) of 4NO ₂ PN, 6.78 g (0.044 mole) of 2,6-dimethoxyphenol, 6.08 g (0.044 mole) of potassium carbonate, 0.26 g (0.0008 mole) of TBAB, and 27.70 g of acetonitrile The mixture was reacted for about 3 hours while stirring using an internal temperature of 85 ° C. and a magnetic stirrer. After cooling, a mixed solution of 28 g of methanol and 55 g of water was added dropwise to the solution obtained by suction filtration to precipitate crystals. The obtained crystals were suction filtered and then washed and purified by adding a mixed solution of 55 g of methanol and 55 g of water, followed by stirring and washing. After suction filtration, the extracted crystals were vacuum dried at about 60 ° C. overnight to yield about 8.65 g (a yield of 77.2 mol% for 4NO ₂ PN).

Synthesis Example 1-15 Synthesis of Phtharonitrile Compound [β-{(2-COOCH ₃ -5-OMe) C ₆ H ₃ O} PN] (Intermediate 1-15)

6.93 g (0.040 mol) of 4NO ₂ PN, 8.02 g (0.044 mol) of 4-methoxy salicylate, 6.08 g (0.044 mol) of potassium carbonate, 0.26 g (0.0008 mol) of TBAB, and 27.70 g of acetonitrile were charged into a 150 ml flask. The reaction was continued for 12 hours while stirring using a magnetic stirrer at an internal temperature of 85 ° C. After cooling, a mixed solution of 28 g of methanol and 55 g of water was added dropwise to the solution obtained by suction filtration to precipitate crystals. The obtained crystals were suction filtered and then washed again and purified by adding a mixed solution of 55 g of methanol and 55 g of water, followed by stirring and washing. After suction filtration, the extracted crystals were vacuum dried at about 60 ° C. overnight to be about 11.25 g (4NO). Yield 91.2 mol%) for ₂ PN was obtained.

Synthesis Example 1-16 Synthesis of Phtharonitrile Compound [β-{(2,6-Cl ₂ ) C ₆ H ₃ O} PN] (Intermediate 1-16)

Into a 150 ml flask was placed 8.66 g (0.050 mole) of 4NO ₂ PN, 8.97 g (0.055 mole) of 2,6-dichlorophenol, 7.60 g (0.055 mole) of potassium carbonate, 0.32 g (0.001 mole) of TBAB, and 34.63 g of acetonitrile. The reaction was carried out for 24 hours while stirring using a magnetic stirrer at an internal temperature of 85 ° C. After cooling, a mixed solution of 50 g of methanol and 150 g of water was added dropwise to the solution obtained by suction filtration to precipitate crystals. The obtained crystals were suction filtered and then washed and purified by adding a mixed solution of 200 g of methanol and 200 g of water, followed by stirring and washing. After suction filtration, the crystals taken out were vacuum dried at about 60 ° C. overnight to yield about 12.86 g (a yield of 89.0 mol% for 4NO ₂ PN).

Synthesis Example 1-17 Synthesis of Phtharonitrile Compound [α-{(2-COOC ₂ H ₄ OCH ₃ ) C ₁₀ H ₆ O} PN] (Intermediate 1-17)

8.42 g (0.048 mol) of 3NO ₂ PN and 12.41 g (0.050 mol) of 3-hydroxy-2-naphthoic acid 2-methoxyethyl, 7.30 g (0.053 mol) of potassium carbonate, 0.77 g (0.002 mol) of TBAB And 33.24 g of acetonitrile were added and reacted for about 9 hours with stirring using an internal temperature of 85 ° C. and a magnetic stirrer. After cooling, a mixed solution of 50 g of methanol and 150 g of water was added dropwise to the solution obtained by suction filtration to precipitate crystals. The obtained crystals were suction filtered and then washed and purified by adding a mixed solution of 200 g of methanol and 200 g of water, followed by stirring and washing. After suction filtration, the crystals taken out were vacuum dried at about 60 ° C. overnight to yield about 15.5 g (a yield of 86.7 mol% for 3NO ₂ PN).

Synthesis Example 1-18 Synthesis of Phtharonitrile Compound [α-{(4-COO (C ₂ H ₄ O) ₃ CH ₃ ) C ₆ H ₄ O} PN] (Intermediate 1-18)

6.93 g (0.040 mol) of 3NO ₂ PN, 11.94 g (0.042 mol) of 2- (2- (2-methoxyethoxy) ethoxy) ethyl, and 6.08 g (0.044 mol) of potassium carbonate in a 150 ml flask , TBAB 0.41 g (0.001 mol) and acetonitrile 27.70 g were added thereto, and the mixture was reacted for about 5 hours while stirring using an internal temperature 90 ° C. and a magnetic stirrer. After cooling, the solution obtained by suction filtration removed the solvent by the evaporation operation on condition of 100 degreeC x 1hr. The resulting crystals were dried in vacuo at about 80 ° C. overnight to yield about 16.15 g (98.4 mole% yield for 3NO ₂ PN).

Synthesis Example 1-19 Synthesis of Phtharonitrile Compound [β-{(2,6-((CH ₃ ) ₂ CH) ₂ C ₆ H ₃ O} PN) (Intermediate 1-19)

15 g (0.087 mol) of 4NO ₂ PN, 19.31 g (0.1083 mol) of 2,6-diisopropylphenol, 14.97 g (0.1083 mol) of potassium carbonate, and 50 g of acetonitrile were added to a 200 ml flask. The reaction was carried out for about 12 hours while stirring. After cooling, a mixed solution of 110 g of methanol and 110 g of water was added dropwise to the solution obtained by suction filtration to precipitate crystals. The obtained crystals were suction filtered and then washed and purified by adding a mixed solution of 110 g of methanol and 110 g of water, followed by stirring and washing. After suction filtration, the crystals taken out were vacuum dried at about 60 ° C. overnight to yield about 24.8 g (yield 93.6 mol% for 4NO ₂ PN).

Synthesis Example 1-20 Synthesis of Phtharonitrile Compound [β-{(2,4-Cl ₂ ) C ₆ H ₃ O} PN] (Intermediate 1-20)

10.39 g (0.060 mole) of 4NO ₂ PN, 10.27 g (0.063 mole) of 2,4-dichlorophenol, 9.12 g (0.066 mole) of potassium carbonate, and 41.55 g of acetonitrile were added to a 150 ml flask. The reaction was carried out for about 12 hours while stirring. After cooling, a solution of 100 ml of acetone and 300 ml of water was added dropwise to the solution obtained by suction filtration to precipitate crystals. The obtained crystals were dried in vacuo at about 80 ° C. overnight to yield about 17.1 g (98.6 mol% for 4NO ₂ PN).

Synthesis Example 1-21 Synthesis of Phtharonitrile Compound [β-{(2-COOCH ₃ ) C ₆ H ₄ S} PN] (Intermediate 1-21)

Into a 150 ml flask, 8.66 g (0.050 mole) of 4NO ₂ PN, 9.25 g (0.055 mole) of methyl thiosalicylate, 7.60 g (0.055 mole) of potassium carbonate, 0.32 g (0.001 mole) of TBAB, and 34.63 g of acetonitrile were added. It reacted for about 20 hours, stirring using 85 degreeC and the magnetic stirrer. After cooling, a mixed solution of 50 g of methanol and 150 g of water was added dropwise to the solution obtained by suction filtration to precipitate crystals. The obtained crystals were suction filtered and then washed and purified by adding a mixed solution of 200 g of methanol and 200 g of water, followed by stirring and washing. After suction filtration, the extracted crystals were vacuum dried at about 60 ° C. overnight to yield about 6.14 g (41.7 mol% of yield for 4NO ₂ PN).

Synthesis Example 1-22 Synthesis of Phtharonitrile Compound [β-{(2,6-Cl ₂ ) C ₆ H ₃ S} PN] (Intermediate 1-22)

8.66 g (0.050 mole) of 4NO ₂ PN, 9.85 g (0.055 mole) of 2,6-dichlorothiophenol, 7.60 g (0.055 mole) of potassium carbonate, 0.32 g (0.001 mole) of TBAB, and 34.63 g of acetonitrile The reaction was carried out for about 20 hours while stirring using an internal temperature of 85 ° C. and a magnetic stirrer. After cooling, a mixed solution of 50 g of methanol and 150 g of water was added dropwise to the solution obtained by suction filtration to precipitate crystals. The obtained crystals were suction filtered and then washed and purified by adding a mixed solution of 200 g of methanol and 200 g of water, followed by stirring and washing. After suction filtration, the crystals taken out were vacuum dried at about 60 ° C. overnight to yield about 8.49 g (yield 55.6 mol% for 4NO ₂ PN).

Synthesis Example 1-23 Synthesis of Phtharonitrile Compound [β-{(4-NO ₂ ) C ₆ H ₄ S} PN] (Intermediate 1-23)

8.66 g (0.050 mole) of 4NO ₂ PN, 8.53 g (0.055 mole) of 4-nitrothiophenol, 7.60 g (0.055 mole) of potassium carbonate, 0.32 g (0.001 mole) of TBAB, and 34.63 g of acetonitrile were charged into a 150 ml flask. The reaction was carried out for about 20 hours while stirring using an internal temperature of 85 ° C. and a magnetic stirrer. After cooling, a mixed solution of 50 g of methanol and 150 g of water was added dropwise to the solution obtained by suction filtration to precipitate crystals. The obtained crystals were suction filtered and then washed and purified by adding a mixed solution of 200 g of methanol and 200 g of water, followed by stirring and washing. After suction filtration, the crystals taken out were vacuum dried at about 60 ° C. overnight to yield about 3.4 g (24.2 mol% in terms of 4NO ₂ PN).

Synthesis Example 1-24 Synthesis of Phtharonitrile Compound [α-{(4-COO (C ₂ H ₄ O) ₂ CH ₃ ) C ₆ H ₄ O} PN] (Intermediate 1-24)

10.39 g (0.06 mol) of 3NO ₂ PN, 15.14 g (0.063 mol) of 2- (2-methoxyethoxy) ethyl p-hydroxy benzoic acid, 9.12 g (0.066 mol) of potassium carbonate, 0.61 g TBAB (0.002) in a 150 ml flask Mole) and 41.55 g of acetonitrile were added, and the mixture was reacted for about 4 hours with stirring using an internal temperature of 85 ° C. and a magnetic stirrer. After cooling, a mixed solution of 50 g of methanol and 150 g of water was added dropwise to the solution obtained by suction filtration to precipitate crystals. The obtained crystals were suction filtered and then washed and purified by adding a mixed solution of 200 g of methanol and 200 g of water, followed by stirring and washing. After suction filtration, the crystals taken out were vacuum dried at about 60 ° C. overnight to yield about 20.13 g (yield 91.6 mol% for 3NO ₂ PN).

Synthesis Example 1-25 Synthesis of Phtharonitrile Compound [β-C ₆ H ₅ OPN] (Intermediate 1-25)

10.39 g (0.06 mol) of 4NO ₂ PN, 5.93 g (0.063 mol) of phenol, 9.12 g (0.066 mol) of potassium carbonate and 41.55 g of acetonitrile were added to a 150 ml flask, and the mixture was stirred with an internal temperature of 85 ° C. and a magnetic stirrer. The reaction was carried out for about 2 hours. After cooling, a mixed solution of 50 g of methanol and 150 g of water was added dropwise to the solution obtained by suction filtration to precipitate crystals. The obtained crystals were suction filtered and then washed and purified by adding a mixed solution of 200 g of methanol and 200 g of water, followed by stirring and washing. After suction filtration, the extracted crystals were vacuum dried at about 60 ° C. overnight to yield about 12.8 g (yield 96.9 mol% for 4NO ₂ PN).

Example 1-1 Synthesis of Phthalocyanine Compound [ZnPc- {α- (2-COOCH ₃ ) C ₆ H ₄ O} ₂ , {β- (2-COOCH ₃ ) C ₆ H ₄ O} ₂ H ₁₂ ]

3.51 g (0.012 mol) of intermediate 1-5 obtained in Synthesis Example 1-5, 3.51 g (0.012 mol) of intermediate 1-6 obtained in Synthesis Example 1-6, 2.11 g (0.007 mol) of zinc iodide, and benzonitrile in a 150 ml flask 24.75 g (hereinafter, referred to as BN) were added thereto, and the mixture was reacted for about 3 hours while stirring using a magnetic stirrer under an nitrogen stream (10 ml / min), an internal temperature of 185 ° C. After cooling, 106.7 g of MEK was added to the solution obtained by suction filtration, and the obtained solution was dripped at 320.0 g of hexane, and the crystal | crystallization was deposited. The obtained crystals were filtered by suction, and then washed and purified by adding a mixed solution of 106.7 g of MEK and 320.0 g of hexane, stirring and washing. After suction filtration, the extracted crystals were dried in vacuo at about 100 ° C. overnight to yield about 6.74 g (yield 95.3 mol% for Intermediate 1-5 and Intermediate 1-6).

(Measurement of Maximum Absorption Wavelength and Gram Absorption Coefficient)

The maximum absorption wavelength ((lambda) max) and gram extinction coefficient of the obtained phthalocyanine compound in the methanol solution containing 0.8 wt% of methyl cellosolves were measured using the spectrophotometer (The Shimadzu Corporation make: UV-1600Pc). The measuring method was performed as follows.

0.04 g of the phthalocyanine compound obtained in the 50 ml volumetric flask was dissolved in 20 g of methyl cellosolve, and prepared by adding methanol so that the meniscus of the solution coincided with the mark of the 50 ml volumetric flask. Next, 1 ml of the prepared solution was aliquoted using a pipette, all the aliquots were added to a 50 ml volumetric flask, diluted with methanol, and the meniscus of the solution was prepared so as to correspond to the mark of the 50 ml volumetric flask. . The solution thus prepared was put in a 1 cm (1 cm 角) pyrex cell, and the transmission spectrum was measured using a spectrophotometer. In addition, when the measured absorbance was A, the gram extinction coefficient was computed with the following formula | equation.

[Equation 1]

Gram extinction coefficient = (A × 5000) / (0.08 × 1000)

Thus measured results are summarized in Table 1.

(Evaluation of heat resistance)

To the obtained phthalocyanine compound 8.3 mg, 1.48 g of benzylmaleimide-containing acrylic polymer (BSX-23-M4) and 3.0 g of methyl cellosolve, each manufactured by Nippon Catalysts Corporation, were added, dissolved, and mixed to prepare a resin coating liquid. The obtained resin coating liquid was apply | coated to the glass plate using the bar coater so that the pigment | dye density | concentration of 1 wt% and dry film thickness in a dry film might be set to 2 micrometers, and it dried at 80 degreeC for 30 minutes. The absorption spectrum of the coated glass plate thus obtained was measured with a spectrophotometer (UV-1600Pc manufactured by Shimadzu Corporation), which was called the spectrum before heating. Next, the coating film glass plate which measured the spectrum before a heating was heat-processed at 200 degreeC for 12 hours. The absorption spectrum of this heat-treated coated glass plate was measured with a spectrophotometer, and this was called the spectrum after heating. The absorbances from 400 nm to 1100 nm were integrated in each spectrum after heating and thus measured, and the difference in absorbance before and after heating was measured. Further, the ΔE was calculated by the following equation when the said difference in the heating after the heating before spectrum E _1, E ₂ spectrum, the measured absorbance ΔE.

[Equation 2]

ΔE = {∑ (absorbance of 400-1100 nm of E ₁ ) -∑ (400-1100 nm absorbance of E ₂ )} / ∑ (absorbance of 400-1100 nm of E ₁ ) × 100 (%)

Thus measured results are summarized in Table 1 below.

(Example 1-2) of phthalocyanine compound [ZnPc- {α- (2-CH ₃ O) C ₆ H ₄ O} ₂ , {β- (2-COOCH ₃ ) C ₆ H ₄ O} ₂ H ₁₂ ] synthesis

2.25 g (0.009 mol) of intermediate 1-3 obtained in Synthesis Example 1-3, 2.50 g (0.009 mol) of intermediate 1-6 obtained in Synthesis Example 1-6, 1.79 g (0.005 mol) of zinc iodide, and BN 18.56 in a 150 ml flask. g was added, and it reacted for about 3 hours, stirring using a magnetic stirrer under the nitrogen stream (10 ml / min), internal temperature of 185 degreeC. After cooling, the solution obtained by suction filtration was added dropwise to a mixed solution of 74.2 g of MEK and 222.7 g of hexane to precipitate crystals. The obtained crystals were suction filtered, and then a mixed solution of 74.2 g of MEK and 222.7 g of hexane was added, followed by stirring and washing. Finally, the obtained crystal was filtered by suction and then purified by adding 55.7 g of methanol and stirring again. After suction filtration, the extracted crystals were vacuum dried at about 100 ° C. overnight to yield about 5.0 g (yield 99.0 mol% for Intermediate 1-3 and Intermediate 1-6).

The maximum absorption wavelength, gram extinction coefficient, and heat resistance were obtained by the same operations as in Example 1-1, except that the phthalocyanine compound thus obtained was replaced with the phthalocyanine compound of Example 1-2. Was measured, and the result was put together in Table 1.

Example 1-3 Phthalocyanine Compound [ZnPc- {α- (2,6-Cl ₂ ) C ₆ H ₃ O} ₂ , {β- (2-COOCH ₃ ) C ₆ H ₄ O} ₂ H ₁₂ ] Synthesis of

3.76 g (0.013 mol) of intermediate 1-2 obtained in Synthesis Example 1-2, 3.81 g (0.013 mol) of intermediate 1-6 obtained in Synthesis Example 1-6, 2.28 g (0.007 mol) of zinc iodide, and BN 26.81 in a 150 ml flask. g was added, and it reacted for about 3 hours, stirring using a magnetic stirrer under the nitrogen stream (10 ml / min), internal temperature of 185 degreeC. After cooling, the solution obtained by suction filtration was dripped at the mixed solution of 115.6g of MEK and 346.7g of hexane, and the crystal | crystallization was deposited. The obtained crystals were filtered by suction, and then a mixed solution of 115.6 g of MEK and 346.7 g of hexane was added, followed by stirring and washing. Finally, the obtained crystal was filtered by suction and then purified by adding 92.5 g of methanol and stirring again. After suction filtration, the crystals taken out were vacuum dried at about 100 ° C. overnight to yield about 7.18 g (yield 92.0 mol% for Intermediate 1-2 and Intermediate 1-6).

The maximum absorption wavelength, the gram extinction coefficient, and the heat resistance were obtained by the same operation as in Example 1-1, except that the phthalocyanine compound thus obtained was replaced with the phthalocyanine compound of Example 1-3. Was measured, and the result was put together in Table 1.

Example 1-4 Synthesis of Phthalocyanine Compound [ZnPc- {α- (2-NO ₂ ) C ₆ H ₄ O} ₂ , {β- (2-COOCH ₃ ) C ₆ H ₄ O} ₂ H ₁₂ ]

7.96 g (0.030 mol) of intermediate 1-1 obtained in Synthesis Example 1-1, 8.38 g (0.030 mol) of intermediate 1-6 obtained in Synthesis Example 1-6, 5.27 g (0.017 mol) of zinc iodide, and BN 61.87 in a 150 ml flask. g was added and reacted for about 16 hours while stirring using a magnetic stirrer at 160 ° C internal temperature under a stream of nitrogen (10 ml / min). After cooling, the solution obtained by suction filtration was added dropwise to a mixed solution of 247.5 g of methanol and 61.9 g of water to precipitate crystals. The obtained crystals were suction filtered and then washed and purified by adding a mixed solution of 247.5 g of methanol and 61.9 g of water, followed by stirring and washing. After suction filtration, the extracted crystals were vacuum dried at about 100 ° C. overnight to yield about 16.0 g (yield 92.6 mol% for Intermediate 1-1 and Intermediate 1-6).

The maximum absorption wavelength, gram absorption coefficient, and heat resistance were obtained by the same operations as in Example 1-1, except that the phthalocyanine compound thus obtained was replaced with the phthalocyanine compound of Example 1-4. Was measured, and the result was put together in Table 1.

Example 1-5 Phthalocyanine Compound [ZnPc- {α- (2-NO ₂ ) C ₆ H ₄ O} ₂ , {β- (2-COOC ₂ H ₄ OCH ₃ ) C ₆ H ₄ O} ₂ H ₁₂ ]

1.93 g (0.007 mol) of intermediate 1-1 obtained in Synthesis Example 1-1 in a 150 ml flask, 2.28 g (0.007 mol) of intermediate 1-7 obtained in Synthesis Example 1-7, 0.52 g (0.004 mol) of zinc chloride, and octanol 18.23 g was added, and the mixture was reacted for about 5 hours with stirring using a magnetic stirrer at an internal temperature of 155 ° C under a nitrogen stream (10 ml / min). After cooling, 18.23 g of acetone was added to the solution obtained by suction filtration, and the obtained solution was added dropwise to 100 g of hexane to precipitate crystals. The obtained crystals were suction filtered and then washed and purified by adding a mixed solution of 10 g of acetone and 100 g of hexane, followed by stirring and washing. After suction filtration, the crystals taken out were vacuum dried at about 100 ° C. overnight to yield about 3.92 g (yield 90.3 mol% for Intermediate 1-1 and Intermediate 1-7).

The maximum absorption wavelength, gram absorption coefficient, and heat resistance were obtained by the same operation as in Example 1-1, except that the phthalocyanine compound thus obtained was replaced with the phthalocyanine compound of Example 1-5. Was measured, and the result was put together in Table 1.

Example 1-6 Synthesis of Phthalocyanine Compound [ZnPc- {α- (2-Ph) C ₆ H ₄ O} ₂ , {β- (2-COOCH ₃ ) C ₆ H ₄ O} ₂ H ₁₂ ]

1.50 g (0.005 mol) of Intermediate 1-4 obtained in Synthesis Example 1-4 in a 150 ml flask, 1.41 g (0.005 mol) of Intermediate 1-6 obtained in Synthesis Example 1-6, 0.38 g (0.003 mol) of zinc chloride, o- 6.01 g of dichlorobenzene and 1.45 g of octanol were added, and the mixture was reacted for about 4 hours with stirring using a magnetic stirrer under an air stream of nitrogen (10 ml / min), an internal temperature of 160 ° C. After cooling, 7 g of MEK was added to the solution obtained by suction filtration, and the obtained solution was dripped at 25 g of hexane, and the crystal | crystallization was deposited. The obtained crystals were suction filtered and then washed and purified by adding a mixed solution of 7 g of MEK and 25 g of hexane and stirring and washing. After suction filtration, the crystals taken out were vacuum dried at about 100 ° C. overnight to yield about 2.3 g (yield 74.8 mol% for Intermediate 1-4 and Intermediate 1-6).

The maximum absorption wavelength, gram absorption coefficient, and heat resistance were obtained by the same operation as in Example 1-1, except that the phthalocyanine compound thus obtained was replaced with the phthalocyanine compound of Example 1-6. Was measured, and the result was put together in Table 1.

Example 1-7 Phthalocyanine Compound [ZnPc- {α- (2,6- (CH ₃ ) ₂ ) C ₆ H ₃ O} ₂ , {β- (2-COOCH ₃ ) C ₆ H ₄ O} ₂ H ₁₂ ]

3.72 g (0.015 mol) of intermediate 1-8 obtained in Synthesis Example 1-8, 4.17 g (0.015 mol) of intermediate 1-6 obtained in Synthesis Example 1-6, 2.63 g (0.008 mol) of zinc iodide, and BN 30.94 in a 150 ml flask. g was added and reacted for about 12 hours while stirring using a magnetic stirrer at 185 ° C under an internal temperature of nitrogen (10 ml / min). After cooling, the solution obtained by suction filtration was added dropwise to a mixed solution of 123.7 g of methanol and 30.9 g of water to precipitate crystals. The obtained crystals were suction filtered and then washed and purified by adding a mixed solution of 61.9 g of methanol and 61.9 g of water, followed by stirring and washing. After suction filtration, the extracted crystals were vacuum dried at about 100 ° C. overnight to yield about 8.59 g (yield 102.4 mol% for Intermediate 1-8 and Intermediate 1-6).

The maximum absorption wavelength, gram absorption coefficient, and heat resistance were obtained by the same operations as in Example 1-1, except that the phthalocyanine compound thus obtained was replaced with the phthalocyanine compound of Example 1-7. Was measured, and the result was put together in Table 1.

Example 1-8 Synthesis of Phthalocyanine Compound [ZnPc- {α- (2-CN) C ₆ H ₄ O} ₂ , {β- (2-COOCH ₃ ) C ₆ H ₄ O} ₂ H ₁₂ ]

2.45 g (0.01 mol) of intermediate 1-9 obtained in Synthesis Example 1-9, 2.45 g (0.01 mol) of intermediate 1-6 obtained in Synthesis Example 1-6, 1.76 g (0.006 mol) of zinc iodide, BN 20.62 in a 150 ml flask. g was added and reacted for about 12 hours while stirring using a magnetic stirrer at 160 ° C internal temperature under a stream of nitrogen (10 ml / min). After cooling, the solution obtained by suction filtration was added dropwise to a mixed solution of 82.5 g of methanol and 20.6 g of water to precipitate crystals. The obtained crystals were suction filtered and then washed and purified by adding a mixed solution of 41.2 g of methanol and 41.2 g of water, followed by stirring and washing. After suction filtration, the crystals taken out were vacuum dried at about 100 ° C. overnight to yield about 5.21 g (yield 93.7 mol% for Intermediate 1-9 and Intermediate 1-6).

The maximum absorption wavelength, gram absorption coefficient, and heat resistance were obtained by the same operation as in Example 1-1, except that the phthalocyanine compound thus obtained was replaced with the phthalocyanine compound of Example 1-8. Was measured, and the result was put together in Table 1.

Example 1-9 Synthesis of Phthalocyanine Compound [ZnPc- {α- (2-CF ₃ ) C ₆ H ₄ O} ₂ , {β- (2-COOCH ₃ ) C ₆ H ₄ O} ₂ H ₁₂ ]

3.75 g (0.013 mol) of intermediate 1-10 obtained in Synthesis Example 1-10, 3.62 g (0.013 mol) of intermediate 1-6 obtained in Synthesis Example 1-6, 2.28 g (0.007 mol) of zinc iodide, and BN 26.81 in a 150 ml flask. g was added and reacted for about 12 hours while stirring using a magnetic stirrer at 160 ° C internal temperature under a stream of nitrogen (10 ml / min). After cooling, the solution obtained by suction filtration was added dropwise to a mixed solution of 107.2 g of methanol and 26.8 g of water to precipitate crystals. The obtained crystals were suction filtered and further washed and purified by adding a mixed solution of 53.6 g of methanol and 53.6 g of water, followed by stirring and washing. After suction filtration, the crystals taken out were vacuum dried at about 100 ° C. overnight to yield about 7.11 g (yield 91.3 mol% for Intermediate 1-10 and Intermediate 1-6).

The maximum absorption wavelength, gram absorption coefficient, and heat resistance were obtained by the same operation as in Example 1-1, except that the phthalocyanine compound thus obtained was replaced with the phthalocyanine compound of Example 1-9. Was measured, and the result was put together in Table 1.

Example 1-10 Synthesis of Phthalocyanine Compound [ZnPc- {α- (C ₆ F ₅ O)} ₂ , {β- (2-COOCH ₃ ) C ₆ H ₄ O} ₂ H ₁₂ ]

4.03 g (0.013 mol) of intermediate 1-11 obtained in Synthesis Example 1-11, 3.62 g (0.013 mol) of intermediate 1-6 obtained in Synthesis Example 1-6, 2.28 g (0.007 mol) of zinc iodide, and BN 26.81 in a 150 ml flask. g was added and reacted for about 12 hours while stirring using a magnetic stirrer at 160 ° C internal temperature under a stream of nitrogen (10 ml / min). After cooling, the solution obtained by suction filtration was added dropwise to a mixed solution of 107.2 g of methanol and 26.8 g of water to precipitate crystals. The obtained crystals were suction filtered and further washed and purified by adding a mixed solution of 53.6 g of methanol and 53.6 g of water, followed by stirring and washing. After suction filtration, the extracted crystals were vacuum dried at about 100 ° C. overnight to yield about 7.38 g (yield 91.4 mol% for Intermediate 1-11 and Intermediate 1-6).

The maximum absorption wavelength, gram absorption coefficient, and heat resistance were obtained by the same operation as in Example 1-1, except that the phthalocyanine compound thus obtained was replaced with the phthalocyanine compound of Example 1-10. Was measured, and the result was put together in Table 1.

Example 1-11 Phthalocyanine Compound [ZnPc- {α- (2-NO ₂ ) C ₆ H ₄ O} ₂ , {β- (2-COOCH ₃ -4-I) C ₆ H ₃ O} ₂ H ₁₂ ]

2.65 g (0.01 mol) of intermediate 1-1 obtained in Synthesis Example 1-1, 4.04 g (0.01 mol) of intermediate 1-12 obtained in Synthesis Example 1-12, 1.76 g (0.006 mol) of zinc iodide, and BN 20.62 in a 150 ml flask. g was added and reacted for about 14 hours with stirring using a magnetic stirrer at 160 ° C internal temperature under a stream of nitrogen (10 ml / min). After cooling, the solution obtained by suction filtration was added dropwise to a mixed solution of 82.5 g of methanol and 20.6 g of water to precipitate crystals. The obtained crystals were suction filtered and then washed and purified by adding a mixed solution of 41.2 g of methanol and 41.2 g of water, followed by stirring and washing. After suction filtration, the extracted crystals were vacuum dried at about 100 ° C. overnight to yield about 6.95 g (yield 99.0 mol% for Intermediate 1-1 and Intermediate 1-12).

The maximum absorption wavelength, gram absorbance coefficient, and heat resistance were obtained by the same operation as in Example 1-1, except that the phthalocyanine compound thus obtained was substituted with the phthalocyanine compound of Example 1-11. Was measured, and the result was put together in Table 1.

Example 1-12 Phthalocyanine Compound [ZnPc- {α- (2-NO ₂ ) C ₆ H ₄ O} ₂ , {β- (2,6- (CH ₃ ) ₂ ) C ₆ H ₃ O} ₂ H ₁₂ ]

3.45 g (0.013 mol) of intermediate 1-1 obtained in Synthesis Example 1-1, 3.23 g (0.013 mol) of intermediate 1-13 obtained in Synthesis Example 1-13, 2.28 g (0.007 mol) of zinc iodide, and BN 26.81 in a 150 ml flask. g was added and reacted for about 12 hours while stirring using a magnetic stirrer at 160 ° C internal temperature under a stream of nitrogen (10 ml / min). After cooling, the solution obtained by suction filtration was added dropwise to a mixed solution of 107.2 g of methanol and 26.8 g of water to precipitate crystals. The obtained crystals were suction filtered and further washed and purified by adding a mixed solution of 53.6 g of methanol and 53.6 g of water, followed by stirring and washing. After suction filtration, the crystals taken out were vacuum dried at about 100 ° C. overnight to yield about 7.93 g (yield 111.7 mol% for Intermediate 1-1 and Intermediate 1-13).

The maximum absorption wavelength, gram absorption coefficient, and heat resistance were obtained by the same operations as in Example 1-1, except that the phthalocyanine compound thus obtained was replaced with the phthalocyanine compound of Example 1-1. Was measured, and the result was put together in Table 1.

Example 1-13 Phthalocyanine compound [ZnPc- {α- (2-NO ₂ ) C ₆ H ₄ O} ₂ , {β- (2,6- (OCH ₃ ) ₂ ) C ₆ H ₃ O} ₂ H ₁₂ ]

3.45 g (0.013 mol) of intermediate 1-1 obtained in Synthesis Example 1-1, 3.64 g (0.013 mol) of intermediate 1-14 obtained in Synthesis Example 1-14, 2.28 g (0.007 mol) of zinc iodide, and BN 26.81 in a 150 ml flask. g was added and reacted for about 12 hours while stirring using a magnetic stirrer at 160 ° C internal temperature under a stream of nitrogen (10 ml / min). After cooling, the solution obtained by suction filtration was added dropwise to a mixed solution of 107.2 g of methanol and 26.8 g of water to precipitate crystals. The obtained crystals were suction filtered and further washed and purified by adding a mixed solution of 53.6 g of methanol and 53.6 g of water, followed by stirring and washing. After suction filtration, the crystals taken out were vacuum dried at about 100 ° C. overnight to yield about 7.75 g (103.1 mol% of the yields for Intermediate 1-1 and Intermediate 1-14).

Except for replacing the phthalocyanine compound of Example 1-1 with the phthalocyanine compound of Example 1-13 by replacing the phthalocyanine compound thus obtained with the phthalocyanine compound of Example 1-13, the maximum absorption wavelength, gram absorption coefficient and heat resistance Was measured, and the result was put together in Table 1.

Example 1-14 Phthalocyanine Compound [ZnPc- {α- (2-NO ₂ ) C ₆ H ₄ O} ₂ , {β- (2-COOCH ₃ -5-OCH ₃ ) C ₆ H ₃ O} ₂ H ₁₂ ]

2.65 g (0.01 mol) of intermediate 1-1 obtained in Synthesis Example 1-1, 3.08 g (0.01 mol) of intermediate 1-15 obtained in Synthesis Example 1-15, 1.76 g (0.006 mol) of zinc iodide, and BN 20.62 in a 150 ml flask. g was added and reacted for about 7 hours while stirring using a magnetic stirrer at 160 ° C and an internal temperature under a stream of nitrogen (10 ml / min). After cooling, the solution obtained by suction filtration was added dropwise to a mixed solution of 82.5 g of methanol and 20.6 g of water to precipitate crystals. The obtained crystals were suction filtered and then washed and purified by adding a mixed solution of 41.2 g of methanol and 41.2 g of water, followed by stirring and washing. After suction filtration, the crystals taken out were vacuum dried at about 100 ° C. overnight to yield about 5.7 g (yield 94.0 mol% for Intermediate 1-1 and Intermediate 1-15).

The maximum absorption wavelength, gram absorption coefficient, and heat resistance were obtained by the same operation as in Example 1-1, except that the phthalocyanine compound thus obtained was replaced with the phthalocyanine compound of Example 1-14. Was measured, and the result was put together in Table 1.

Example 1-15 Phthalocyanine Compound [ZnPc- {α- (2-NO ₂ ) C ₆ H ₄ O} ₂ , {β- (2,6-Cl ₂ ) C ₆ H ₃ O} ₂ H ₁₂ ] Synthesis of

3.18 g (0.012 mol) of intermediate 1-1 obtained in Synthesis Example 1-1, 3.47 g (0.012 mol) of intermediate 1-16 obtained in Synthesis Example 1-16, 2.11 g (0.007 mol) of zinc iodide, BN 24.75 in a 150 ml flask g was added and reacted for about 8 hours while stirring using a magnetic stirrer at 160 ° C internal temperature under a stream of nitrogen (10 ml / min). After cooling, the solution obtained by suction filtration was dripped at the mixed solution of 99.0 g of methanol and 24.7 g of water, and the crystal | crystallization was deposited. The obtained crystals were suction filtered and then washed and purified by adding a mixed solution of 49.5 g of methanol and 49.5 g of water, followed by stirring and washing. After suction filtration, the extracted crystals were vacuum dried at about 100 ° C. overnight to yield about 6.9 g (yield 101.4 mol% for Intermediate 1-1 and Intermediate 1-16).

The maximum absorption wavelength, gram absorption coefficient, and heat resistance were obtained by the same operations as in Example 1-1, except that the phthalocyanine compound thus obtained was replaced with the phthalocyanine compound of Example 1-15. Was measured, and the result was put together in Table 1.

Example 1-16 Phthalocyanine Compound [ZnPc- {α- (2-CN) C ₆ H ₄ O} ₂ , {β- (2-COOCH ₃ -5-OCH ₃ ) C ₆ H ₃ O} ₂ H ₁₂ ]

2.94 g (0.012 mol) of Intermediate 1-9 obtained in Synthesis Example 1-9, 3.70 g (0.012 mol) of Intermediate 1-15 obtained in Synthesis Example 1-15, 2.11 g (0.007 mol) of zinc iodide, BN 24.75 in a 150 ml flask g was added and reacted for about 8 hours while stirring using a magnetic stirrer at 160 ° C internal temperature under a stream of nitrogen (10 ml / min). After cooling, the solution obtained by suction filtration was dripped at the mixed solution of 99.0 g of methanol and 24.7 g of water, and the crystal | crystallization was deposited. The obtained crystals were suction filtered and then washed and purified by adding a mixed solution of 49.5 g of methanol and 49.5 g of water, followed by stirring and washing. After suction filtration, the extracted crystals were vacuum dried at about 100 ° C. overnight to yield about 6.4 g (yield 91.0 mol% for Intermediate 1-9 and Intermediate 1-15).

The maximum absorption wavelength, the gram absorbance coefficient, and the heat resistance were obtained by the same operation as in Example 1-1, except that the phthalocyanine compound thus obtained was replaced with the phthalocyanine compound of Example 1-16. Was measured, and the result was put together in Table 1.

(Example 1-17) of phthalocyanine compound [ZnPc- {α- (2-CN) C ₆ H ₄ O} ₂ , {β- (2,6-Cl ₂ ) C ₆ H ₃ O} ₂ H ₁₂ ] synthesis

2.94 g (0.012 mol) of intermediate 1-9 obtained in Synthesis Example 1-9, 3.47 g (0.012 mol) of intermediate 1-16 obtained in Synthesis Example 1-16, 2.11 g (0.007 mol) of zinc iodide, BN 24.75 in a 150 ml flask g was added and reacted for about 8 hours while stirring using a magnetic stirrer at 160 ° C internal temperature under a stream of nitrogen (10 ml / min). After cooling, the solution obtained by suction filtration was dripped at the mixed solution of 99.0 g of methanol and 24.7 g of water, and the crystal | crystallization was deposited. The obtained crystals were suction filtered and then washed and purified by adding a mixed solution of 49.5 g of methanol and 49.5 g of water, followed by stirring and washing. After suction filtration, the extracted crystals were vacuum dried at about 100 ° C. overnight to yield about 6.5 g (yield 95.5 mol% for Intermediate 1-9 and Intermediate 1-16).

The maximum absorption wavelength, gram absorption coefficient, and heat resistance were obtained by the same operation as in Example 1-1, except that the phthalocyanine compound thus obtained was replaced with the phthalocyanine compound of Example 1-17. Was measured, and the result was put together in Table 1.

Example 1-18 Synthesis of Phthalocyanine Compound [ZnPc- {α- (2-NO ₂ ) C ₆ H ₄ O} _2.5 , {β- (2-COOCH ₃ ) C ₆ H ₄ O} _1.5 H ₁₂ ]

4.97 g (0.01875 mol) of intermediate 1-1 obtained in Synthesis Example 1-1, 3.13 g (0.01125 mol) of intermediate 1-6 obtained in Synthesis Example 1-6, 2.63 g (0.008 mol) of zinc iodide, and BN 30.94 in a 150 ml flask. g was added and reacted for about 16 hours while stirring using a magnetic stirrer at 160 ° C internal temperature under a stream of nitrogen (10 ml / min). After cooling, the solution obtained by suction filtration was added dropwise to a mixed solution of 123.7 g of methanol and 30.9 g of water to precipitate crystals. The obtained crystals were filtered by suction, and then washed and purified by adding a mixed solution of 123.7 g of methanol and 30.9 g of water, followed by stirring and washing. After suction filtration, the extracted crystals were vacuum dried at about 100 ° C. overnight to yield about 9.0 g (yield 104.1 mol% for Intermediate 1-1 and Intermediate 1-6).

The maximum absorption wavelength, gram absorption coefficient, and heat resistance were obtained by the same operation as in Example 1-1, except that the phthalocyanine compound thus obtained was replaced with the phthalocyanine compound of Example 1-18. Was measured, and the result was put together in Table 1.

Example 1-19 Synthesis of Phthalocyanine Compound [ZnPc- {α- (2-NO ₂ ) C ₆ H ₄ O} ₃ , {β- (2-COOCH ₃ ) C ₆ H ₄ O} ₁ H ₁₂ ]

5.97 g (0.0225 mol) of intermediate 1-1 obtained in Synthesis Example 1-1, 2.09 g (0.0075 mol) of intermediate 1-6 obtained in Synthesis Example 1-6, 2.63 g (0.008 mol) of zinc iodide, and BN 30.94 in a 150 ml flask. g was added and reacted for about 16 hours while stirring using a magnetic stirrer at 160 ° C internal temperature under a stream of nitrogen (10 ml / min). After cooling, the solution obtained by suction filtration was added dropwise to a mixed solution of 123.7 g of methanol and 30.9 g of water to precipitate crystals. The obtained crystals were filtered by suction, and then washed and purified by adding a mixed solution of 123.7 g of methanol and 30.9 g of water, followed by stirring and washing. After suction filtration, the extracted crystals were dried in vacuo at about 100 ° C. overnight to yield about 9.4 g (108.8 mol% of the yields of Intermediate 1-1 and Intermediate 1-6).

The maximum absorption wavelength, gram absorption coefficient, and heat resistance were obtained by the same operation as in Example 1-1, except that the phthalocyanine compound thus obtained was replaced with the phthalocyanine compound of Example 1-19. Was measured, and the result was put together in Table 1.

Example 1-20 Synthesis of Phthalocyanine Compound [CuPc- {α- (2-NO ₂ ) C ₆ H ₄ O} ₂ , {β- (2-COOCH ₃ ) C ₆ H ₄ O} ₂ H ₁₂ ]

3.18 g (0.012 mol) of intermediate 1-1 obtained in Synthesis Example 1-1, 3.34 g (0.0012 mol) of intermediate 1-6 obtained in Synthesis Example 1-6, 0.71 g (0.007 mol) of copper chloride, in a 150 ml flask 14.11 g of dichlorobenzene and 6.25 g of 1-octanol were added, and the mixture was reacted for about 2 hours with stirring using a magnetic stirrer under an air stream of nitrogen (10 ml / min), an internal temperature of 160 ° C. After cooling, the solution obtained by suction filtration was dripped at the mixed solution of 81.5g of MEK and 244.4g of hexane, and the crystal | crystallization was deposited. After the obtained crystal was suction filtered, 61.1 g of methanol was further added, followed by stirring and washing to perform washing and purification. After suction filtration, the extracted crystals were vacuum dried at about 100 ° C. overnight to yield about 6.2 g (yield 89.8 mol% for Intermediate 1-1 and Intermediate 1-6).

The maximum absorption wavelength, gram absorption coefficient, and heat resistance were obtained by the same operations as in Example 1-1, except that the phthalocyanine compound thus obtained was replaced with the phthalocyanine compound of Example 1-20. Was measured, and the result was put together in Table 1.

Example 1-21 Phthalocyanine Compound [ZnPc- {α- (2-CN) C ₆ H ₄ O} ₂ , {β- (2,6-((CH ₃ ) ₂ CH) ₂ ) C ₆ H ₃ O} ₂ H ₁₂ ]

3.19 g (0.013 mol) of intermediate 1-9 obtained in Synthesis Example 1-9, 3.96 g (0.017 mol) of intermediate 1-19 obtained in Synthesis Example 1-19, 2.28 g (0.007 mol) of zinc iodide, BN 26.81 in a 150 ml flask. g was added and reacted for about 6 hours with stirring using a magnetic stirrer at 160 ° C internal temperature under a stream of nitrogen (10 ml / min). After cooling, the solution obtained by suction filtration was added dropwise to a mixed solution of 160.9 g of methanol and 40.2 g of water to precipitate crystals. The obtained crystals were suction filtered and further washed and purified by adding a mixed solution of 53.6 g of methanol and 53.6 g of water, followed by stirring and washing. After suction filtration, the extracted crystals were vacuum dried at about 100 ° C. overnight to yield about 6.35 g (yield 83.9 mol% for Intermediate 1-9 and Intermediate 1-19).

The maximum absorption wavelength, the gram absorbance coefficient, and the heat resistance were obtained by the same operation as in Example 1-1, except that the phthalocyanine compound thus obtained was replaced with the phthalocyanine compound of Example 1-21. Was measured, and the result was put together in Table 1.

Example 1-22 Phthalocyanine Compound [ZnPc- {α- (2-COOC ₂ H ₄ OCH ₃ ) C ₁₀ H ₆ O} ₂ , {β- (2-COOC ₂ H ₄ OCH ₃ ) C ₆ H ₄ O} ₂ H ₁₂ ]

3.72 g (0.01 mol) of intermediate 1-17 obtained in Synthesis Example 1-17, 3.22 g (0.01 mol) of intermediate 1-7 obtained in Synthesis Example 1-7 in a 150 ml flask, 1.76 g (0.006 mol) of zinc iodide, BN 20.62 g was added and reacted for about 14 hours with stirring using a magnetic stirrer at 160 ° C internal temperature under a stream of nitrogen (10 ml / min). After cooling, the solution obtained by suction filtration was added dropwise to a mixed solution of 123.7 g of methanol and 30.9 g of water to precipitate crystals. The obtained crystals were suction filtered and then washed and purified by adding a mixed solution of 41.2 g of methanol and 41.2 g of water, followed by stirring and washing. After suction filtration, the extracted crystals were vacuum dried at about 100 ° C. overnight to yield about 6.85 g (yield 94.2 mol% for Intermediate 1-17 and Intermediate 1-7).

The maximum absorption wavelength, gram absorbance coefficient, and heat resistance were obtained by the same operations as in Example 1-1, except that the phthalocyanine compound thus obtained was replaced with the phthalocyanine compound of Example 1-22. Was measured, and the result was put together in Table 1.

Example 1-23 Phthalocyanine Compound [ZnPc- {α- (4-COO (C ₂ H ₄ O) ₃ CH ₃ ) C ₆ H ₄ O} ₂ , {β- (2,4-Cl ₂ ) C ₆ H ₃ O} ₂ H ₁₂ ]

4.51 g (0.011 mol) of intermediate 1-18 obtained in Synthesis Example 1-18, 3.18 g (0.011 mol) of intermediate 1-20 obtained in Synthesis Example 1-20 in a 150 ml flask, 1.93 g (0.006 mol) of zinc iodide, BN 22.69 g was added and reacted for about 12 hours while stirring using a magnetic stirrer at 160 ° C internal temperature under a stream of nitrogen (10 ml / min). After cooling, a mixed solution of 90.7 g of methanol and 90.7 g of water was added to the solution obtained by suction filtration, and then decantation was performed. The supernatant was discarded, and a mixed solution of 90.7 g of methanol and 90.7 g of water was further added to the obtained solid to perform decantation. The supernatant was discarded and the resulting crystals were vacuum dried at about 100 ° C. overnight to yield about 7.9 g (yield 98.1 mol% for intermediates 1-18 and 1-20).

The maximum absorption wavelength, the gram absorbance coefficient, and the heat resistance were obtained by the same operation as in Example 1-1, except that the phthalocyanine compound thus obtained was replaced with the phthalocyanine compound of Example 1-23. Was measured, and the result was put together in Table 1.

Example 1-24 Synthesis of Phthalocyanine Compound [ZnPc- {α- (2-CN) C ₆ H ₄ O} ₂ , {β- (2-COOCH ₃ ) C ₆ H ₄ S} ₂ H ₁₂ ]

3.19 g (0.013 mol) of intermediate 1-9 obtained in Synthesis Example 1-9, 3.83 g (0.013 mol) of intermediate 1-21 obtained in Synthesis Example 1-21, 2.28 g (0.007 mol) of zinc iodide, and BN 26.81 in a 150 ml flask. g was added and reacted for about 10 hours while stirring using a magnetic stirrer at 160 ° C internal temperature under a stream of nitrogen (10 ml / min). After cooling, the solution obtained by suction filtration was added dropwise to a mixed solution of 160.9 g of methanol and 40.2 g of water to precipitate crystals. The obtained crystals were suction filtered and further washed and purified by adding a mixed solution of 53.6 g of methanol and 53.6 g of water, followed by stirring and washing. After suction filtration, the crystals taken out were vacuum dried at about 100 ° C. overnight to yield about 5.95 g (yield 80.0 mol% for Intermediate 1-9 and Intermediate 1-21).

The maximum absorption wavelength, the gram absorbance coefficient, and the heat resistance were obtained by the same operations as in Example 1-1, except that the phthalocyanine compound thus obtained was replaced with the phthalocyanine compound of Example 1-24. Was measured, and the result was put together in Table 1.

(Example 1-25) of the phthalocyanine compound [ZnPc- {α- (2-CN) C ₆ H ₄ O} ₂ , {β- (2,6-Cl ₂ ) C ₆ H ₃ S} ₂ H ₁₂ ] synthesis

3.19 g (0.013 mol) of intermediate 1-9 obtained in Synthesis Example 1-9, 3.97 g (0.013 mol) of intermediate 1-22 obtained in Synthesis Example 1-22, 2.28 g (0.007 mol) of zinc iodide, and BN 26.81 in a 150 ml flask. g was added and reacted for about 10 hours while stirring using a magnetic stirrer at 160 ° C internal temperature under a stream of nitrogen (10 ml / min). After cooling, the solution obtained by suction filtration was added dropwise to a mixed solution of 160.9 g of methanol and 40.2 g of water to precipitate crystals. The obtained crystals were suction filtered and further washed and purified by adding a mixed solution of 53.6 g of methanol and 53.6 g of water, followed by stirring and washing. After suction filtration, the crystals taken out were vacuum dried at about 100 ° C. overnight to yield about 7.53 g (yield 99.3 mol% for Intermediate 1-9 and Intermediate 1-22).

The maximum absorption wavelength, gram absorption coefficient, and heat resistance were obtained by the same operations as in Example 1-1, except that the phthalocyanine compound thus obtained was replaced with the phthalocyanine compound of Example 1-25. Was measured, and the result was put together in Table 1.

Example 1-26 Synthesis of Phthalocyanine Compound [ZnPc- {α- (2-CN) C ₆ H ₄ O} ₂ , {β- (4-NO ₂ ) C ₆ H ₄ S} ₂ H ₁₂ ]

2.94 g (0.012 mol) of intermediate 1-9 obtained in Synthesis Example 1-9, 3.38 g (0.012 mol) of intermediate 1-23 obtained in Synthesis Example 1-23, 2.11 g (0.007 mol) of zinc iodide, BN 24.75 in a 150 ml flask g was added and reacted for about 7 hours while stirring using a magnetic stirrer at 160 ° C and an internal temperature under a stream of nitrogen (10 ml / min). After cooling, the solution obtained by suction filtration was added dropwise to a mixed solution of 148.5 g of methanol and 37.1 g of water to precipitate crystals. The obtained crystals were suction filtered and then washed and purified by adding a mixed solution of 49.5 g of methanol and 49.5 g of water, followed by stirring and washing. After suction filtration, the crystals taken out were vacuum dried at about 100 ° C. overnight to yield about 5.6 g (the yield 83.4 mol% for Intermediate 1-9 and Intermediate 1-23).

The maximum absorption wavelength, gram absorbance coefficient, and heat resistance were obtained by the same operations as in Example 1-1, except that the phthalocyanine compound thus obtained was replaced with the phthalocyanine compound of Example 1-26. Was measured, and the result was put together in Table 1.

Example 1-27 Phthalocyanine Compound [ZnPc- {α- (4-COO (C ₂ H ₄ O) ₂ CH ₃ ) C ₆ H ₄ O} ₂ , {β-C ₆ H ₅ O} ₂ H ₁₂ Synthesis

2.93 g (0.008 mol) of Intermediate 1-24 obtained in Synthesis Example 1-24, 1.76 g (0.008 mol) of Intermediate 1-25 obtained in Synthesis Example 1-25, 1.40 g (0.004 mol) of zinc iodide, BN 16.50 in a 150 ml flask g was added, and it reacted for about 5 hours, stirring using a magnetic stirrer with 160 degreeC of internal temperature under nitrogen stream (10 ml / min). After cooling, the solution obtained by suction filtration was dripped at the mixed solution of 99.0 g of methanol and 24.7 g of water, and the crystal | crystallization was deposited. The obtained crystals were suction filtered and then washed and purified by adding a mixed solution of 33.0 g of methanol and 33.0 g of water, followed by stirring and washing. After suction filtration, the extracted crystals were dried in vacuo at about 100 ° C. overnight to yield about 4.64 g (yield 93.7 mol% for Intermediate 1-24 and Intermediate 1-25).

The maximum absorption wavelength, gram absorption coefficient, and heat resistance were obtained by the same operation as in Example 1-1, except that the phthalocyanine compound thus obtained was replaced with the phthalocyanine compound of Example 1-27. Was measured, and the result was put together in Table 1.

Comparative Example 1-1 Synthesis of Phthalocyanine Compound [ZnPc- {α- (2-COOCH ₃ ) C ₆ H ₄ O} ₄ H ₁₂ ]

4.17 g (0.015 mol) of intermediate 1-5 obtained in Synthesis Example 1-5, 1.32 g (0.004 mol) of zinc iodide, and 30.94 g of BN were added to a 150 ml flask, and a nitrogen stream (10 ml / min) and an internal temperature of 185 ° C. It was made to react for about 5 hours, stirring using the magnetic stirrer. After cooling, a mixed solution of 123.7 g of methanol and 30.9 g of water was added dropwise to the solution obtained by suction filtration to precipitate crystals. The obtained crystals were filtered by suction, and then washed and purified by adding a mixed solution of 123.7 g of methanol and 30.9 g of water, followed by stirring and washing. After suction filtration, the crystals taken out were vacuum dried at about 100 ° C. overnight to yield about 3.3 g (74.2 mol% in terms of Intermediate 1-5).

The maximum absorption wavelength, gram absorbance coefficient, and heat resistance were obtained by the same operations as in Example 1-1, except that the phthalocyanine compound obtained in this manner was replaced with the phthalocyanine compound of Example 1-1 by the phthalocyanine compound of Example 1-1. Was measured, and the result was put together in Table 1.

Comparative Example 1-2 Synthesis of Phthalocyanine Compound [ZnPc- {β- (2-COOCH ₃ ) C ₆ H ₄ O} ₄ H ₁₂ ]

4.17 g (0.015 mol) of Intermediate 1-6 obtained in Synthesis Example 1-6, 1.32 g (0.004 mol) of zinc iodide, and 30.94 g of BN were added to a 150 ml flask, and under an air stream of nitrogen (10 ml / min), the internal temperature was 185 ° C. It was made to react for about 5 hours, stirring using the magnetic stirrer. After cooling, a mixed solution of 123.7 g of methanol and 30.9 g of water was added dropwise to the solution obtained by suction filtration to precipitate crystals. The obtained crystals were filtered by suction, and then washed and purified by adding a mixed solution of 123.7 g of methanol and 30.9 g of water, followed by stirring and washing. After suction filtration, the crystals taken out were vacuum dried at about 100 ° C. overnight to yield about 3.8 g (84.9 mol% for Intermediate 1-6).

The maximum absorption wavelength, the gram extinction coefficient, and the heat resistance were obtained by the same operation as in Example 1-1, except that the phthalocyanine compound obtained in this manner was replaced with the phthalocyanine compound of Example 1-1 by the phthalocyanine compound of Example 1-1. Was measured, and the result was put together in Table 1.

εg Heat resistance (ΔE) λmax / nm Example 1-1 83 30 681.0 Example 1-2 81 29 684.5 Example 1-3 103 26 683.0 Example 1-4 97 27 679.0 Examples 1-5 71 28 678.0 Example 1-6 91 26 683.0 Example 1-7 96 29 687.0 Example 1-8 105 25 677.5 Example 1-9 111 23 679.0 Example 1-10 93 27 678.0 Example 1-11 84 26 678.5 Example 1-12 114 30 681.0 Example 1-13 98 29 682.0 Example 1-14 88 26 679.5 Example 1-15 119 24 678.0 Example 1-16 94 29 678.0 Example 1-17 121 26 677.0 Example 1-18 108 28 680.5 Example 1-19 118 30 681.0 Example 1-20 70 27 679.5 Example 1-21 128 30 680.0 Example 1-22 78 23 683.0 Example 1-23 65 24 677.0 Example 1-24 100 30 679.5 Example 1-25 103 27 681.0 Example 1-26 83 23 679.0 Example 1-27 75 29 678.0 Comparative Example 1-1 80 36 689.5 Comparative Example 1-2 48 22 672.0

In the α-position 4-substituted phthalocyanine compound synthesized in Comparative Example 1-1, the gram absorption coefficient (εg) was approximately twice that of the β-position 4-substituted phthalocyanine compound synthesized in Comparative Example 1-2, but the difference in absorbance due to heating was observed. (ΔE) was large and the heat resistance deteriorated. On the other hand, in the phthalocyanine compound synthesized in Examples 1-1 to 27, the difference in absorbance (ΔE) by heating was close to the β-position 4-substituted phthalocyanine compound synthesized in Comparative Example 1-2, and the gram absorbance coefficient (εg) was It was equivalent to or more than the α-position tetrasubstituted phthalocyanine compound synthesized in Comparative Example 1-1. Therefore, as shown in Table 1, the (alpha), (beta) -position mixed substituted phthalocyanine compounds similar to Examples 1-1 to 27 which have the superior characteristic of both (alpha) -substituted phthalocyanine and (beta) -substituted phthalocyanine were obtained.

Synthesis Example 2-1 Synthesis of Phtharonitrile Compound [α-{(4-COOC ₂ H ₄ OCH ₃ ) C ₆ H ₄ O} PN] (Intermediate 2-1)

3.72 g (0.022 mol) of 3-nitrophthalonitrile, 4.26 g (0.022 mol) of p-hydroxy benzoic acid methyl cellosolve, 3.27 g (0.024 mol) of potassium carbonate, and 14.89 g of acetonitrile were added to a 150 ml flask. The reaction was carried out for about 4 hours while stirring using a magnetic stirrer at a temperature of 85 ° C. After cooling, 100 g of distilled water was added dropwise to a solution obtained by suction filtration while washing the residue with 20 g of acetone to precipitate crystals. After suction filtration, the extracted crystals were dried in vacuo at about 100 ° C. overnight to yield about 6.07 g (yield 87.6 mol% relative to 3-nitrophthalonitrile).

Synthesis Example 2-2 Synthesis of Phtharonitrile Compound [α-{(4-COOC ₂ H ₄ OC ₂ H ₄ OCH ₃ ) C ₆ H ₄ O} PN] (Intermediate 2-2)

6.93 g (0.04 mol) of 3-nitrophthalonitrile, 10.09 g (0.042 mol) of p-hydroxy methyl benzoate, 6.08 g (0.044 mol) of potassium carbonate, and 27.7 g of acetonitrile were added to a 150 ml flask. It reacted for about 24 hours, stirring using 85 degreeC and the magnetic stirrer. After cooling, the solution obtained by suction filtration was evaporated under the conditions of about 110 ° C. × 1 hour. Moreover, it dried in vacuum overnight at about 110 degreeC, and obtained about 14.32g (tetrachlorophthalonitrile yield 97.7 mol%).

Synthesis Example 2-3 Synthesis of Phtharonitrile Compound [α-{(4-CN) C ₆ H ₄ O} PN] (Intermediate 2-3)

In a 150 ml flask, 25.10 (0.145 mol) of 3-nitrophthalonitrile and 17.79 g (0.149 mol) of 4-cyanophenol, 22.04 g (0.16 mol) of potassium carbonate, 0.41 g (0.001 mol) of n-tetrabutylammonium bromide, aceto 100.42 g of nitrile was added and reacted for about 4 hours with stirring using an internal temperature of 85 ° C. and a magnetic stirrer. After cooling, 200 g of distilled water was added dropwise to a solution obtained by suction filtration while washing the residue with 20 g of acetone to precipitate crystals. After the obtained crystals were suction filtered, 200 g of distilled water was further added, followed by stirring and washing to perform washing and purification. After suction filtration, the extracted crystals were dried in vacuo at about 100 ° C. overnight to yield about 34.05 g (yield 95.8 mol% for 3-nitrophthalonitrile).

Synthesis Example 2-4 Synthesis of Phtharonitrile Compound [α-{(2,6-Cl ₂ ) C ₆ H ₃ O} PN] (Intermediate 2-4)

25.10 g (0.145 mol) of 3-nitrophthalonitrile, 26.0 g (0.16 mol) of 2,6-dichlorophenol, 22.04 g (0.160 mol) of potassium carbonate, 0.93 g (0.002 mol) of n-tetrabutylammonium bromide And 100.42 g of acetonitrile were added and reacted for about 5 hours with stirring using an internal temperature of 80 ° C. and a magnetic stirrer. After cooling, a mixed solution of 50 g of methanol and 150 g of distilled water was added dropwise to the solution obtained by suction filtration to precipitate crystals. The obtained crystals were suction filtered and then washed and purified by adding a mixed solution of 200 g of methanol and 200 g of distilled water, followed by stirring and washing. After suction filtration, the extracted crystals were vacuum dried at about 60 ° C. overnight to yield about 38.9 g (yield 92.8 mol% for 3-nitrophthalonitrile).

Synthesis Example 2-5 Synthesis of Phtharonitrile Compound [α-{(4-C ₆ H ₅ ) C ₆ H ₄ O} PN] (Intermediate 2-5)

3.29 g (0.019 mol) of 3-nitrophthalonitrile, 3.56 g (0.021 mol) of 4-phenylphenol, 2.89 g (0.021 mol) of potassium carbonate, 0.12 g (0.0004 mol) of n-tetrabutylammonium bromide, aceto in 150 ml flask 19.74 g of nitriles were added and reacted for about 28 hours with stirring using an internal temperature of 60 ° C. and a magnetic stirrer. After cooling, a mixed solution of 10 g of methanol and 50 g of distilled water was added dropwise to the solution obtained by suction filtration to precipitate crystals. The obtained crystals were suction filtered and then washed and purified by adding a mixed solution of 20 g of methanol and 100 g of distilled water, followed by stirring and washing. After suction filtration, the crystals taken out were vacuum dried at about 60 ° C. overnight to yield about 5.12 g (yield of 90.9 mol% for 3-nitrophthalonitrile).

Synthesis Example 2-6 Synthesis of Phtharonitrile Compound [α-{(4-NO ₂ ) C ₆ H ₄ S} PN] (Intermediate 2-6)

9.52 g (0.055 mole) of 3-nitrophthalonitrile, 8.96 g (0.058 mole) of 4-nitrothiophenol, 8.36 g (0.061 mole) of potassium carbonate, 38.09 g of acetonitrile were added to a 150 ml flask. The reaction was carried out for about 22 hours while stirring using a magnetic stirrer. After cooling, 200 g of distilled water was added dropwise to a solution obtained by suction filtration while washing the residue with 20 g of acetone to precipitate crystals. After suction filtration, the extracted crystals were dried in vacuo at about 100 ° C. overnight to yield about 8.7 g (yield 56.2 mol% for 3-nitrophthalonitrile).

Synthesis Example 2-7 Synthesis of Phtharonitrile Compound [α- (C ₆ F ₅ O) PN] (Intermediate 2-7)

In a 150 ml flask, 8.66 g (0.05 mole) of 3-nitrophthalonitrile, 10.12 g (0.055 mole) of pentafluorophenol, 7.6 g (0.055 mole) of potassium carbonate, 0.32 g (0.001 mole) of n-tetrabutylammonium bromide, aceto 34.63 g of nitrile were added and reacted for about 10 hours while stirring using an internal temperature of 85 ° C. and a magnetic stirrer. After cooling, a mixed solution of 50 g of methanol and 150 g of distilled water was added dropwise to the solution obtained by suction filtration to precipitate crystals. The obtained crystals were suction filtered and then washed and purified by adding a mixed solution of 200 g of methanol and 200 g of distilled water, followed by stirring and washing. After suction filtration, the extracted crystals were dried in vacuo at about 60 ° C. overnight to yield about 14.6 g (yield 94.1 mol% for 3-nitrophthalonitrile).

Synthesis Example 2-8 Synthesis of Phtharonitrile Compound [α-{(2-NO ₂ ) C ₆ H ₄ O} PN] (Intermediate 2-8)

In a 150 ml flask, 25.10 g (0.145 mole) of 3-nitrophthalonitrile, 24.21 g (0.174 mole) of 2-nitrophenol, 24.05 g (0.174 mole) of potassium carbonate, 100.42 g of acetonitrile, 0.47 g of n-tetrabutylammonium bromide ( 0.001 mol) was added and reacted for about 25 hours while stirring using an internal temperature of 85 ° C. and a magnetic stirrer. After cooling, 200 g of distilled water was added dropwise to the solution obtained by suction filtration to precipitate crystals. After the obtained crystals were suction filtered, 200 g of distilled water was further added, followed by stirring and washing to perform washing and purification. After suction filtration, the crystals taken out were dried in vacuo at about 100 ° C. overnight to yield about 36.1 g (yield of 93.9 mol% for 3-nitrophthalonitrile).

Synthesis Example 2-9 Synthesis of Phtharonitrile Compound [α-{(2-CN) C ₆ H ₄ O} PN] (Intermediate 2-9)

Into a 150 ml flask, 25.10 g (0.145 mole) of 3-nitrophthalonitrile, 19.0 g (0.16 mole) of 2-cyanophenol, 22.04 g (0.16 mole) of potassium carbonate, and 100.42 g of acetonitrile were added to an internal temperature of 85 ° C., The reaction was carried out for about 3 hours while stirring using a magnetic stirrer. After cooling, a mixed solution of 100 g of methanol and 200 g of distilled water was added dropwise to the solution obtained by suction filtration to precipitate crystals. The obtained crystals were suction filtered and then washed and purified by adding a mixed solution of 200 g of methanol and 200 g of distilled water, followed by stirring and washing. After suction filtration, the extracted crystals were dried in vacuo at about 100 ° C. overnight to yield about 32.6 g (yield of 91.7 mol% for 3-nitrophthalonitrile).

Synthesis Example 2-10 Synthesis of Phtharonitrile Compound [α-{(4-Cl) C ₆ H ₄ O} PN] (Intermediate 2-10)

10.39 g (0.06 mol) of 3-nitrophthalonitrile, 8.1 g (0.063 mol) of 4-chlorophenol, 9.12 g (0.066 mol) of potassium carbonate, and 41.55 g of acetonitrile were added to a 150 ml flask. The reaction was carried out for about 1 hour while stirring using a stirrer. After cooling, 200 g of distilled water was added dropwise to a solution obtained by suction filtration while washing the residue with 20 g of acetone to precipitate crystals. After suction filtration, the extracted crystals were dried in vacuo at about 100 ° C. overnight to yield about 14.7 g (yield of 96.2 mol% relative to 3-nitrophthalonitrile).

Synthesis Example 2-11 Synthesis of Phtharonitrile Compound [α- (OC ₂ H ₄ OC ₂ H ₄ OCH ₃ ) PN] (Intermediate 2-11)

7 g (0.04 mole) of 3-nitrophthalonitrile, 25 g (0.202 mole) of ethylene glycol monomethyl ether and 2.82 g (0.048 mole) of potassium fluoride were added to a 150 ml flask, and the mixture was stirred with an internal stirrer at 80 ° C. and a magnetic stirrer. The reaction was carried out for about 5 hours. After cooling, the solution obtained by suction filtration was dripped at 200 g of distilled water, and the crystal | crystallization was deposited. The obtained crystals were suction filtered and then washed and purified by stirring and washing with 150 g of distilled water again. After suction filtration, the extracted crystals were dried in vacuo at about 50 ° C. overnight to yield about 6.46 g (yield 65.0 mol% relative to 3-nitrophthalonitrile).

Synthesis Example 2-12 Synthesis of Phtharonitrile Compound [α- (OCH (CH ₃ ) CH ₂ OCH ₃ ) PN] (Intermediate 2-12)

7 g (0.04 mol) of 3-nitrophthalonitrile, 18.5 g (0.202 mol) of 1-methoxy-2-propanol, and 2.82 g (0.048 mol) of potassium fluoride were added to a 150 ml flask. It was made to react for about 5 hours, stirring. After cooling, 200 ml of methyl isobutyl ketone (hereinafter referred to as MIBK) was added to the reaction solution, and the separated MIBK phase was extracted. Thereafter, the solvent was removed by evaporation of the extracted MIBK solution, and the extracted crystals were dried in vacuo at about 50 ° C. overnight to yield about 6.58 g (yield of 75.3 mol% relative to 3-nitrophthalonitrile).

Synthesis Example 2-13 Synthesis of Phtharonitrile Compound [β-{(4-COOC ₂ H ₄ OC ₂ H ₄ OCH ₃ ) C ₆ H ₄ O} PN] (Intermediate 2-13)

Into a 150 ml flask, 7.01 g (0.041 mole) of 4-nitrophthalonitrile, 10.22 g (0.043 mole) of p-hydroxy benzoate methylcarbitol, 6.16 g (0.045 mole) of potassium carbonate, and 28.04 g of acetonitrile were added. It reacted for about 16 hours, stirring using 85 degreeC and the magnetic stirrer. After cooling, the solution obtained by suction filtration was evaporated under the conditions of about 110 ° C. × 1 hour. Moreover, it dried in vacuum overnight at about 110 degreeC, and obtained about 14.53g (4-7.9-% yield of 4-nitrophthalonitrile).

Synthesis Example 2-14 Synthesis of Phtharonitrile Compound [β-{(4-COOC ₂ H ₄ OCH ₃ ) C ₆ H ₄ O} PN] (Intermediate 2-14)

In a 150 ml flask, 6.93 g (0.04 mol) of 4-nitrophthalonitrile, 8.24 g (0.042 mol) of p-hydroxy benzoic acid methylcellosolve, 6.08 g (0.044 mol) of potassium carbonate, 0.41 g of n-tetrabutylammonium bromide ( 0.001 mol) and 27.70 g of acetonitrile were added and reacted for about 16 hours while stirring using an internal temperature of 85 ° C. and a magnetic stirrer. After cooling, 200 g of distilled water was added dropwise to a solution obtained by suction filtration while washing the residue with 20 g of acetone to precipitate crystals. After suction filtration, the crystals taken out were dried in vacuo at about 100 ° C. overnight to yield about 11.23 g (yield 87.1 mol% for 4-nitrophthalonitrile).

Synthesis Example 2-15 Synthesis of Phtharonitrile Compound [β-{(4-CN) C ₆ H ₄ O} PN] (Intermediate 2-15)

Into a 150 ml flask, 13.85 g (0.08 mole) of 4-nitrophthalonitrile, 10.48 g (0.088 mole) of 4-cyanophenol, 12.16 g (0.088 mole) of potassium carbonate, 55.4 g of acetonitrile were added. The reaction was carried out for about 4 hours while stirring using a magnetic stirrer. After cooling, a mixed solution of 50 g of methanol and 100 g of distilled water was added dropwise to the solution obtained by suction filtration to precipitate crystals. The obtained crystals were suction filtered and then washed and purified by adding a mixed solution of 100 g of methanol and 100 g of distilled water, followed by stirring and washing. After suction filtration, the extracted crystals were dried in vacuo at about 100 ° C. overnight to yield about 18.5 g (yield 94.3 mol% relative to 4-nitrophthalonitrile).

Synthesis Example 2-16 Synthesis of Phtharonitrile Compound [β-{(2,6-Cl ₂ ) C ₆ H ₃ O} PN] (Intermediate 2-16)

8.66 g (0.05 mole) of 4-nitrophthalonitrile, 8.97 g (0.055 mole) of 2,6-dichlorophenol, 7.6 g (0.055 mole) of potassium carbonate, 0.32 g (0.001 mole) of n-tetrabutylammonium bromide in a 150 ml flask And 34.63 g of acetonitrile were added and reacted for about 24 hours while stirring using an internal temperature of 85 ° C. and a magnetic stirrer. After cooling, a mixed solution of 50 g of methanol and 150 g of distilled water was added dropwise to the solution obtained by suction filtration to precipitate crystals. The obtained crystals were suction filtered and then washed and purified by adding a mixed solution of 200 g of methanol and 200 g of distilled water, followed by stirring and washing. After suction filtration, the extracted crystals were dried in vacuo at about 60 ° C. overnight to yield about 12.86 g (yield 89.0 mol% for 4-nitrophthalonitrile).

Synthesis Example 2-17 Synthesis of Phtharonitrile Compound [β-{(4-NO ₂ ) C ₆ H ₄ O} PN] (Intermediate 2-17)

Into a 150 ml flask, 13.85 g (0.08 mole) of 4-nitrophthalonitrile, 12.24 g (0.088 mole) of 4-nitrophenol, 12.16 g (0.088 mole) of potassium carbonate, and 55.4 g of acetonitrile were added. The reaction was carried out for about 5 hours while stirring using a stirrer. After cooling, a mixed solution of 50 g of methanol and 100 g of distilled water was added dropwise to the solution obtained by suction filtration to precipitate crystals. The obtained crystals were suction filtered and then washed and purified by adding a mixed solution of 100 g of methanol and 100 g of distilled water, followed by stirring and washing. After suction filtration, the extracted crystals were vacuum dried at about 100 ° C. overnight to yield about 20.4 g (yield of 96.1 mol% relative to 4-nitrophthalonitrile).

Synthesis Example 2-18 Synthesis of Phtharonitrile Compound [β- (C ₆ F ₅ O) PN] (Intermediate 2-18)

8.66 g (0.05 mole) of 4-nitrophthalonitrile, 10.12 g (0.055 mole) of pentafluorophenol, 7.6 g (0.055 mole) of potassium carbonate, 0.32 g (0.001 mole) of n-tetrabutylammonium bromide, aceto in a 150 ml flask 34.63 g of nitriles were added and reacted for about 48 hours with stirring using an internal temperature of 85 ° C. and a magnetic stirrer. After cooling, a mixed solution of 50 g of methanol and 150 g of distilled water was added dropwise to the solution obtained by suction filtration to precipitate crystals. The obtained crystals were suction filtered and then washed and purified by adding a mixed solution of 200 g of methanol and 200 g of distilled water, followed by stirring and washing. After suction filtration, the crystals taken out were dried in vacuo at about 60 ° C. overnight to yield about 12.8 g (82.5 mol% of yield for 4-nitrophthalonitrile).

Synthesis Example 2-19 Phtharonitrile compound [α-{(4-COOC ₂ H ₄ OCH ₃ ) C ₆ H ₄ O} _a , β-{(4-COOC ₂ H ₄ OCH ₃ ) C ₆ H ₄ O} _2-a Cl ₂ PN] (0 ≦ a <2) (Intermediate 2-19)

10.64 g (0.04 mol) of tetrachlorophthalonitrile, 15.70 g (0.08 mol) of p-hydroxy benzoic acid methyl cellosolve, 12.16 g (0.088 mol) of potassium carbonate, and 42.55 g of acetonitrile were added to a 150 ml flask. It reacted for about 2 hours, stirring using 75 degreeC and the magnetic stirrer. After cooling, the solution obtained by suction filtration was evaporated under the conditions of about 110 ° C. × 1 hour. Moreover, it dried in vacuum overnight at about 110 degreeC, and obtained about 23.09 g (98.6 mol% of tetrachlorophthalonitrile).

In addition, in the name of the said compound, it is described as "(alpha)-(substituent A) _a , (beta)-(substituent A) _xa PN (0 <= a <x)", The phthalonitrile compound or phthalocyanine compound obtained is (alpha). This means that an average of a and xa substituents A are introduced at the position, that is, a total of x substituents A are introduced at the α and β positions. For this reason, for example, the phthalonitrile compound of the synthesis example 2-19 [α-{(4-COOC ₂ H ₄ OCH ₃ ) C ₆ H ₄ O} _a , β-{(4-COOC ₂ H ₄ OCH ₃ ) C ₆ H ₄ O} _{2- a} Cl ₂ PN] (0≤a <2) is an average of a (4-COOC ₂ H ₄ OCH ₃ ) C at a position corresponding to the α position when the phthalocyanine skeleton is used. ₆ H ₄ O group, it indicates that with the average of the 2-a _{(4-COOC 2 H 4 OCH} 3) C 6 H 4 O a, and the chlorine atom is introduced in the rest position structure to a position corresponding to the position β. The same applies to the descriptions of the following phthalonitrile compounds.

Synthesis Example 2-20 Phtharonitrile compound [α-{(2-COOC ₂ H ₄ OC ₂ H ₄ OCH ₃ ) C ₆ H ₄ O} _a , β-{(2-COOC ₂ H ₄ OC ₂ H ₄ OCH ₃ ) C ₆ H ₄ O} _2-a Cl ₂ PN] (0 ≦ a <2) (Intermediate 2-20)

10.64 g (0.04 mole) of tetrachlorophthalonitrile, 19.22 g (0.08 mole) of methyl salicylate, 12.16 g of potassium carbonate (0.088 mole), and 42.55 g of acetonitrile were added to a 150 ml flask. The reaction was carried out for about 12 hours while stirring. After cooling, the solution obtained by suction filtration was evaporated under the conditions of about 110 ° C. × 1 hour. Moreover, it dried in vacuum overnight at about 110 degreeC, and obtained about 25.89g (tetrachlorophthalonitrile yield 96.1 mol%).

Synthesis Example 2-21 Phtharonitrile compound [α-{(4-COOC ₂ H ₄ OC ₂ H ₄ OCH ₃ ) C ₆ H ₄ O} _a , β-{(4-COOC ₂ H ₄ OC ₂ H ₄ OCH ₃ ) C ₆ H ₄ O} _2-a Cl ₂ PN] (0 ≦ a <2) (Intermediate 2-21)

5.32 g (0.02 mole) of tetrachlorophthalonitrile, 9.61 g (0.04 mole) of p-hydroxybenzoic acid methylcarbitol, 6.08 g (0.044 mole) of potassium carbonate and 21.27 g of acetonitrile were added to a 150 ml flask. The reaction was carried out for about 12 hours while stirring using a magnetic stirrer. After cooling, the solution obtained by suction filtration was evaporated under the conditions of about 110 ° C. × 1 hour. Moreover, it vacuum-dried overnight at about 110 degreeC, and obtained about 11.3 g (tetrachlorophthalonitrile yield 96.5 mol%).

Synthesis Example 2-22 Phtharonitrile compound [α-{(4-COOCH ₂ OC ₄ H ₇ ) C ₆ H ₄ O} _a , β-{(4-COOCH ₂ OC ₄ H ₇ ) C ₆ H ₄ O} _2-a Cl ₂ PN] (0 ≦ a <2) (Intermediate 2-22)

5.32 g (0.02 mol) of tetrachlorophthalonitrile, 8.33 g (0.04 mol) of p-hydroxy benzoic acid tetrahydrofurfuryl alcohol, 6.08 g (0.044 mol) of potassium carbonate, and 21.27 g of acetonitrile were added to a 150 ml flask. It reacted for about 3 hours, stirring using temperature 85 degreeC and the magnetic stirrer. After cooling, the solution obtained by suction filtration was evaporated under the conditions of about 110 ° C. × 1 hour. Moreover, it vacuum-dried overnight at about 110 degreeC, and obtained about 12.4g (tetrachlorophthalonitrile yield 97.3 mol%).

Synthesis Example 2-23 Phtharonitrile compound [α-{(3-COOC ₂ H ₄ OCH ₃ ) C ₆ H ₄ O} _a , β-{(3-COOC ₂ H ₄ OCH ₃ ) C ₆ H ₄ O} _2-a Cl ₂ PN] (0 ≦ a <2) (Intermediate 2-23)

10.64 g (0.04 mole) tetrachlorophthalonitrile, 15.70 g (0.08 mole) ethyl m-hydroxy benzoate, 12.16 g (0.088 mole) potassium carbonate, and 42.55 g of acetonitrile were added to a 150 ml flask. The reaction was carried out for about 2 hours while stirring using a magnetic stirrer.

After cooling, the solution obtained by suction filtration was evaporated under the conditions of about 110 ° C. × 1 hour. Moreover, it vacuum-dried overnight at about 110 degreeC, and obtained about 20.95 g (tetrachlorophthalonitrile yield 96.7 mol%).

Synthesis Example 2-24 Phtharonitrile compound [α-{(4-COOC ₂ H ₄ OCH ₃ ) C ₆ H ₄ O} _a , β-{(4-COOC ₂ H ₄ OCH ₃ ) C ₆ H ₄ O} _3-a ClPN] (0 ≦ _a <3) (intermediate 2-24)

7.98 g (0.03 mol) of tetrachlorophthalonitrile, 17.66 g (0.09 mol) of p-hydroxybenzoic acid methylcellosolve, 13.68 g (0.099 mol) of potassium carbonate, and 31.91 g of acetonitrile were added to a 150 ml flask. It reacted for about 2 hours, stirring using 70 degreeC and the magnetic stirrer. After cooling, the solution obtained by suction filtration was evaporated under the conditions of about 110 ° C. × 1 hour. In addition, vacuum drying was performed overnight at about 110 ° C., and about 22 g (tetrachlorophthalonitrile yield 98.4 mol%) was obtained.

Synthesis Example 2-25 Phtharonitrile compound [α-{(2-COOCH ₃ ) C ₆ H ₄ O} _a , β-{(2-COOCH ₃ ) C ₆ H ₄ O} _2-a Cl ₂ PN ] (0≤a <2) (Intermediate 2-25)

7.98 g (0.03 mole) of tetrachlorophthalonitrile, 9.13 g (0.06 mole) of methyl salicylate, 9.12 g (0.066 mole) of potassium carbonate and 31.91 g of acetonitrile were added to a 150 ml flask, and the internal temperature was 80 ° C. using a magnetic stirrer. It was made to react for about 5 hours, stirring. After cooling, the solution obtained by suction filtration was evaporated under the conditions of about 110 ° C. × 1 hour. Moreover, it dried in vacuum overnight at about 110 degreeC, and obtained about 14.35 g (tetrachlorophthalonitrile yield 96.2 mol%).

Synthesis Example 2-26 Phtharonitrile compound [α-{(2,6-Cl ₂ ) C ₆ H ₃ O} _a , β-{(2,6-Cl ₂ ) C ₆ H ₃ O} _{1- a} Cl ₃ PN] (0 ≦ a <1) (intermediate 2-26)

8 g (0.03 mole) of tetrachlorophthalonitrile, 4.9 g (0.03 mole) of 2,6-dichlorophenol, 4.16 g (0.03 mole) of potassium carbonate and 25 g of acetone were added to a 150 ml flask. It was made to react for about 4 hours, stirring. After cooling, a mixed solution of 200 g of distilled water was added dropwise to a solution obtained by suction filtration to precipitate crystals. The obtained crystals were suction filtered and then washed and purified by adding a mixed solution of 100 g of methanol and 100 g of distilled water, followed by stirring and washing. After suction filtration, the crystals taken out were vacuum dried at about 60 ° C. overnight to yield about 11.64 g (yield of 98.9 mol% relative to tetrachlorophthalonitrile).

Synthesis Example 2-27 Phtharonitrile compound [α-{(2,6-Cl ₂ ) C ₆ H ₃ O} _a , β-{(2,6-Cl ₂ ) C ₆ H ₃ O} _{2- a} Cl ₂ PN] (0 ≦ a <2) (Intermediate 2-27)

Into a 150 ml flask, 7.18 g (0.027 mole) of tetrachlorophthalonitrile, 8.8 g (0.054 mole) of 2,6-dichlorophenol, 8.21 g of potassium carbonate (0.059 mole), and 28.72 g of acetonitrile were added to an internal temperature of 85 ° C., The reaction was carried out for about 4 hours while stirring using a magnetic stirrer. After cooling, a mixed solution of 200 g of distilled water was added dropwise to a solution obtained by suction filtration to precipitate crystals. The obtained crystals were suction filtered and then washed and purified by adding a mixed solution of 100 g of methanol and 100 g of distilled water, followed by stirring and washing. After suction filtration, the extracted crystals were dried in vacuo at about 60 ° C. overnight to yield about 13.63 g (yield 97.3 mol% relative to tetrachlorophthalonitrile).

Synthesis Example 2-28 Phtharonitrile compound [α-{(4-COOC ₂ H ₄ OCH ₃ ) C ₆ H ₄ O} _a , α-{(4-COOC ₂ H ₄ OC ₂ H ₄ OCH ₃ ) C ₆ H ₄ O} _b , β-{(4-COOC ₂ H ₄ OCH ₃ ) C ₆ H ₄ O} _1-a , β-{(4-COOC ₂ H ₄ OC ₂ H ₄ OCH ₃ ) C ₆ H ₄ O} _1-b Cl ₂ PN] (0 ≦ a <1, 0 ≦ b <1) (intermediate 2-28)

7.98 g (0.03 mol) of tetrachlorophthalonitrile, 7.21 g (0.03 mol) of p-hydroxy benzoic acid methylcarbitol, 5.89 g (0.03 mol) of p-hydroxy benzoic acid methylcellosolve, 9.12 g of potassium carbonate in a 150 ml flask (0.066 mol) and 31.91 g of acetonitrile were added, and it was made to react for about 3.5 hours, stirring using an internal temperature of 85 degreeC and the magnetic stirrer. After cooling, the solution obtained by suction filtration was evaporated under the conditions of about 110 ° C. × 1 hour. Furthermore, it dried in vacuum overnight at about 110 degreeC, and obtained about 18.07g (tetrachlorophthalonitrile yield 97.9 mol%).

Synthesis Example 2-29 Phtharonitrile compound [α-{(4-COOC ₂ H ₄ OCH ₃ ) C ₆ H ₄ O} _a , α-{(2,6-Cl ₂ ) C ₆ H ₃ O} _b , β-{(4-COOC ₂ H ₄ OCH ₃ ) C ₆ H ₄ O} _1-a , β-{(2,6-Cl ₂ ) C ₆ H ₃ O} _{1- b} Cl ₂ PN] ( Synthesis of 0 ≦ a <1, 0 ≦ b <1) (Intermediate 2-29)

7.18 g (0.027 mol) of tetrachlorophthalonitrile, 4.84 g (0.03 mol) of 2,6-dichlorophenol, 4.10 g (0.03 mol) of potassium carbonate and 28.72 g of acetonitrile were added to a 150 ml flask, and the internal temperature was 60 ° C, The reaction was carried out for about 10 hours while stirring using a magnetic stirrer. When 2,6-dichlorophenol was lost by the reaction, 5.83 g (0.03 mol) of p-hydroxy benzoic acid methyl cellosolve and 4.10 g (0.03 mol) of potassium carbonate were added to add methyl p-hydroxy benzoate. The cellosolve was allowed to react until it was lost by the reaction. After cooling, the solution obtained by suction filtration was evaporated under the conditions of about 110 ° C. × 1 hour. Moreover, it dried in vacuum overnight at about 110 degreeC, and obtained about 9.85 g (tetrachlorophthalonitrile yield 95.5 mol%).

Synthesis Example 2-30 Phtharonitrile compound [α-{(4-COOC ₂ H ₄ OCH ₃ ) C ₆ H ₄ O} _a , α-{(4-CN) C ₆ H ₄ O} _b , β -{(4-COOC ₂ H ₄ OCH ₃ ) C ₆ H ₄ O} _2-a , β-{(4-CN) C ₆ H ₄ O} _{1- b} ClPN] (0≤a <2, 0≤ Synthesis of b <1) (Intermediate 2-30)

7.98 g (0.03 mol) of tetrachlorophthalonitrile, 11.77 g (0.06 mol) of p-hydroxy benzoic acid methyl cellosolve, 13.68 g (0.099 mol) of potassium carbonate, and 31.91 g of acetonitrile were added to a 150 ml flask. It reacted for about 7 hours, stirring using 85 degreeC and the magnetic stirrer. At the time point where p-hydroxy benzoic acid methylcellosolve was lost by reaction, 3.57 g (0.03 mol) of 4-cyanophenol was added and it reacted until 4-cyanophenol was lost by reaction. After cooling, the solution obtained by suction filtration was evaporated under the conditions of about 110 ° C. × 1 hour. Moreover, it dried in vacuum overnight at about 110 degreeC, and obtained about 18.34g (tetrachlorophthalonitrile yield 98.0 mol%).

Synthesis Example 2-31 Phtharonitrile compound [α-{(4-COOC ₂ H ₄ OCH ₃ ) C ₆ H ₄ O} _a , α-{(4-CN) C ₆ H ₄ O} _b , β -{(4-COOC ₂ H ₄ OCH ₃ ) C ₆ H ₄ O} _1.5-a , β-{(4-CN) C ₆ H ₄ O} _{0.5- b} Cl ₂ PN] (0≤a <1.5, 0≤b <0.5) (intermediate 2-31)

7.98 g (0.03 mol) of tetrachlorophthalonitrile, 8.83 g (0.045 mol) of p-hydroxybenzoic acid methyl cellosolve, 9.12 g (0.066 mol) of potassium carbonate, and 31.91 g of acetonitrile were added to a 150 ml flask. It reacted for about 7 hours, stirring using 85 degreeC and the magnetic stirrer. At the time point where p-hydroxy benzoic acid methylcellosolve was lost by reaction, 1.79 g (0.015 mol) of 4-cyanophenol was newly added, and it reacted until 4-cyanophenol was lost by reaction. After cooling, the solution obtained by suction filtration was evaporated under the conditions of about 110 ° C. × 1 hour. Moreover, it dried in vacuum overnight at about 110 degreeC, and obtained about 16.11 g (98.2 mol% of tetrachloro phthalonitrile).

Synthesis Example 2-32 Phtharonitrile compound [α-{(4-COOC ₂ H ₄ OCH ₃ ) C ₆ H ₄ O} _a , α-{(4-CN) C ₆ H ₄ O} _b , β -{(4-COOC ₂ H ₄ OCH ₃ ) C ₆ H ₄ O} _1-a , β-{(4-CN) C ₆ H ₄ O} _{1- b} Cl ₂ PN] (0 ≦ a <1, Synthesis of 0≤b <1) (Intermediate 2-32)

7.98 g (0.03 mol) of tetrachlorophthalonitrile, 5.89 g (0.03 mol) of p-hydroxybenzoic acid methyl cellosolve, 9.12 g (0.066 mol) of potassium carbonate, and 31.91 g of acetonitrile were added to a 150 ml flask. It reacted for about 4 hours, stirring using 60 degreeC and the magnetic stirrer. At the time point where p-hydroxy benzoic acid methylcellosolve was lost by reaction, 3.57 g (0.03 mol) of 4-cyanophenol was added and it reacted until 4-cyanophenol was lost by reaction. After cooling, the solution obtained by suction filtration was evaporated under the conditions of about 110 ° C. × 1 hour. Moreover, it vacuum-dried overnight at about 110 degreeC, and obtained about 15.03g (98.6 mol% of tetrachlorophthalonitrile).

Synthesis Example 2-33 Phtharonitrile compound [α-{(4-CN) C ₆ H ₄ O} _a , β-{(4-CN) C ₆ H ₄ O} _2-a Cl ₂ PN] ( Synthesis of 0 ≦ a <2) (Intermediate 2-33)

Into a 150 ml flask, 7.98 g (0.03 mol) of tetrachlorophthalonitrile, 7.15 g (0.06 mol) of 4-cyanophenol, 9.12 g (0.066 mol) of potassium carbonate, 31.91 g of acetonitrile were added. The reaction was carried out for about 2 hours while stirring using a stirrer. After cooling, the solution obtained by suction filtration was evaporated under the conditions of about 110 ° C. × 1 hour. Moreover, it vacuum-dried overnight at about 110 degreeC, and about 14.6g (tetrachlorophthalonitrile yield 95.7 mol%) was obtained.

Synthesis Example 2-34 Phtharonitrile compound [α-{(2-COOC ₂ H ₄ OCH ₃ ) C ₆ H ₄ O} _a , β-{(2-COOC ₂ H ₄ OCH ₃ ) C ₆ H ₄ O} _2-a Cl ₂ PN] (0 ≦ a <2) (Intermediate 2-34)

10.64 g (0.04 mole) tetrachlorophthalonitrile, 15.70 g (0.08 mole) methyl salicylate, 12.16 g (0.088 mole) potassium carbonate, 0.26 g (0.001 mole) n-tetrabutylammonium bromide, aceto in a 150 ml flask 42.55 g of nitriles were added and reacted for about 10 hours while stirring using an internal temperature of 85 ° C. and a magnetic stirrer. After cooling, the solution obtained by suction filtration was evaporated under the conditions of about 110 ° C. × 1 hour. Moreover, it vacuum-dried overnight at about 110 degreeC, and about 22.8g (tetrachlorophthalonitrile yield 97.4 mol%) was obtained.

Synthesis Example 2-35 Phtharonitrile compound [α-{(4-COOCH ₃ ) C ₆ H ₄ O} _a , β-{(4-COOCH ₃ ) C ₆ H ₄ O} _2-a Cl ₂ PN ] (0≤a <2) (Intermediate 2-35)

13.30 g (0.05 mol) of tetrachlorophthalonitrile, 15.22 g (0.1 mol) of methyl p-hydroxybenzoate, 15.20 g (0.11 mol) of potassium carbonate, 53.18 g of acetonitrile were added to a 150 ml flask, and the internal temperature was 70 ° C. The reaction was carried out for about 2 hours while stirring using a magnetic stirrer. After cooling, the solution obtained by suction filtration was evaporated under the conditions of about 110 ° C. × 1 hour. Moreover, it dried in vacuum overnight at about 110 degreeC, and obtained about 24.3g (tetrachlorophthalonitrile yield 97.7 mol%).

Synthesis Example 2-36 Phtharonitrile compound [α-{(4-COOC ₂ H ₄ OCH ₃ ) C ₆ H ₄ O} _a , β-{(4-COOC ₂ H ₄ OCH ₃ ) C ₆ H ₄ O} _3-a ClPN] (0 ≦ _a <3) (intermediate 2-36)

5.32 g (0.02 mol) of tetrachlorophthalonitrile, 11.77 g (0.06 mol) of p-hydroxybenzoic acid methyl cellosolve, 9.12 g (0.066 mol) of potassium carbonate, and 21.27 g of acetonitrile were added to a 150 ml flask. It reacted for about 2 hours, stirring using 70 degreeC and the magnetic stirrer. After cooling, the solution obtained by suction filtration was evaporated under the conditions of about 110 ° C. × 1 hour. Moreover, it dried in vacuum overnight at about 110 degreeC, and obtained about 14.11 g (tetrachlorophthalonitrile yield 94.7 mol%).

Synthesis Example 2-37 Phtharonitrile compound [α-{(2-COOCH ₃ ) C ₆ H ₄ O} _a , β-{(2-COOCH ₃ ) C ₆ H ₄ O} _3-a ClPN] ( Synthesis of 0 ≦ a <3) (Intermediate 2-37)

10.64 g (0.04 mole) of tetrachlorophthalonitrile, 18.26 g (0.12 mole) of methyl salicylate, 18.24 g (0.132 mole) of potassium carbonate and 42.55 g of acetonitrile were added to a 150 ml flask, and the internal temperature was 70 ° C. using a magnetic stirrer. It was made to react for about 2 hours, stirring. After cooling, the solution obtained by suction filtration was evaporated under the conditions of about 110 ° C. × 1 hour. Moreover, it dried in vacuum overnight at about 110 degreeC, and obtained about 23.55 g (tetrachlorophthalonitrile yield 96.0 mol%).

Synthesis Example 2-38 Phtharonitrile compound [α-{(4-CN) C ₆ H ₄ O} _a , β-{(4-CN) C ₆ H ₄ O} _3-a ClPN] (0 ≦ synthesis of a <3) (intermediate 2-38)

15.95 g (0.06 mole) of tetrachlorophthalonitrile, 21.44 g (0.18 mole) of 4-cyanophenol, 9.12 g (0.066 mole) of potassium carbonate and 63.82 g of acetonitrile were added to a 150 ml flask. The reaction was carried out for about 8 hours while stirring using a stirrer. After cooling, the solution obtained by suction filtration was evaporated under the conditions of about 110 ° C. × 1 hour. Moreover, it dried in vacuum overnight at about 110 degreeC, and obtained about 30.01 g (tetrachlorophthalonitrile yield 97.3 mol%).

Synthesis Example 2-39 Phtharonitrile compound [α-{(3-COOC ₂ H ₅ ) C ₆ H ₄ O} _a , β-{(3-COOC ₂ H ₅ ) C ₆ H ₄ O} _{3- a} ClPN] (0 ≦ _a <3) (Intermediate 2-39)

7.98 g (0.03 mol) of tetrachlorophthalonitrile, 14.96 g (0.09 mol) of m-hydroxy benzoate, 13.68 g (0.099 mol) of potassium carbonate and 31.91 g of acetonitrile were added to a 150 ml flask. The reaction was carried out for about 8 hours while stirring using a magnetic stirrer. After cooling, the solution obtained by suction filtration was evaporated under the conditions of about 110 ° C. × 1 hour. Moreover, it vacuum-dried overnight at about 110 degreeC, and about 18.9g (tetrachlorophthalonitrile yield 96.2 mol%) was obtained.

Synthesis Example 2-40 Synthesis of Phtharonitrile Compound [α-{(2-COOCH ₃ ) C ₆ H ₄ O} PN] (Intermediate 2-40)

2.60 g (0.015 mol) of 3-nitrophthalonitrile, 2.74 g (0.018 mol) of methyl salicylate, 2.49 g (0.018 mol) of potassium carbonate, 0.10 g (0.0003 mol) of n-tetrabutylammonium bromide, 10.39 acetonitrile g was added and reacted for about 9 hours while stirring using an internal temperature of 80 ° C. and a magnetic stirrer. After cooling, the solvent was removed from the solution obtained by suction filtration by evaporation, and 10 g of methyl ethyl ketone was added thereto. The solution thus obtained was dripped in 100 g of hexane to precipitate crystals. The obtained crystals were suction filtered and then washed and purified by adding a mixed solution of 10 g of methyl ethyl ketone and 100 g of hexane and stirring and washing. After suction filtration, the crystals taken out were dried in vacuo at about 60 ° C. overnight to yield about 3.71 g (yield 88.8 mol% relative to 3-nitrophthalonitrile).

Synthesis Example 2-41 Synthesis of Phtharonitrile Compound [β-{(2-COOCH ₃ ) C ₆ H ₄ O} PN] (Intermediate 2-41)

25.10 g (0.145 mol) of 4-nitrophthalonitrile, 30.89 g (0.203 mol) of methyl salicylate, 22.04 g (0.16 mol) of potassium carbonate, 0.93 g (0.003 mol) of n-tetrabutylammonium bromide, 100.42 in acetonitrile g was added and reacted for about 40 hours while stirring using an internal temperature of 80 degreeC and a magnetic stirrer. After cooling, a mixed solution of 50 g of methanol and 150 g of water was added dropwise to the solution obtained by suction filtration to precipitate crystals. The obtained crystals were suction filtered and then washed and purified by adding a mixed solution of 200 g of methanol and 200 g of water, followed by stirring and washing. After suction filtration, the extracted crystals were dried in vacuo at about 60 ° C. overnight to yield about 34.8 g (86.3 mol% of yield for 4-nitrophthalonitrile).

Synthesis Example 2-42 Phtharonitrile compound [α-{(2-COOC ₂ H ₄ OCH ₃ ) C ₁₀ H ₈ O} _a , β-{(2-COOC ₂ H ₄ OCH ₃ ) C ₁₀ H ₈ O} _2-a Cl ₂ PN] (0 ≦ a <2) (intermediate 2-42)

7.98 g (0.03 mol) of tetrachlorophthalonitrile, 18.46 g (0.06 mol) of 3-hydroxy-2-naphthoic acid methylcellosolve, 9.12 g (0.066 mol) of potassium carbonate, and 31.91 g of acetonitrile were charged into a 150 ml flask. The mixture was reacted for about 6 hours with stirring using an internal temperature of 85 ° C. and a magnetic stirrer. After cooling, the same process as in Synthesis Example 2-39 was carried out, and about 23.1 g (yield 112.3 mol% of tetrachlorophthalonitrile) were obtained.

Example 2-1 Phthalocyanine Compound [ZnPc- {α- (4-COOC ₂ H ₄ OCH ₃ ) C ₆ H ₄ O} _{2 + x} , {β- (4-COOC ₂ H ₄ OCH ₃ ) C ₆ H ₄ O} _4-x Cl ₄ H ₆ ] (0≤x <4)

2.58 g (0.008 mol) of intermediate 2-1 obtained in Synthesis Example 2-1, 4.68 g (0.008 mol) of intermediate 2-19 obtained in Synthesis Example 2-19, 1.40 g (0.004 mol) of zinc iodide, and benzonitrile in a 150 ml flask 16.50 g was added, and the mixture was reacted for about 16 hours while stirring using a magnetic stirrer with an internal temperature of 160 ° C. under a stream of nitrogen (10 ml / min). After cooling, the solution obtained by suction filtration was dripped in 6 times methanol (99.0g) of benzonitrile, and it stirred for 30 minutes. Thereafter, 1/4 times distilled water (24.7 g) of methanol was added dropwise thereto, followed by further stirring for 1 hour to precipitate crystals. The obtained crystals were filtered by suction, followed by washing and purifying by adding a first 1/3 weight of methanol (33.0 g) and a mixed solution of the methanol and the same amount of distilled water (33.0 g) with stirring and washing. After suction filtration, the extracted crystals were vacuum dried at about 60 ° C. overnight to yield about 6.00 g (yield 79.8 mol% for Intermediate 2-1 and Intermediate 2-19).

In addition, in the name of the said compound, it is described as "(alpha)-(substituent A) _a , (beta)-(substituent A) _xa Pc (0 <= a <x)", The phthalonitrile compound or phthalocyanine compound obtained is (alpha). This means that an average of a and xa substituents A are introduced at the position, that is, a total of x substituents A are introduced at the α and β positions. For this reason, for example, [ZnPc- {α- (4-COOC ₂ H ₄ OCH ₃ ) C ₆ H ₄ O} _{2 + x} of Example 2-1, {β- (4-COOC ₂ H ₄ OCH ₃₎ ) C ₆ H ₄ O} _4-x Cl ₄ H ₆ ] (0≤x <4) is a 2 + x (4-COOC ₂ H ₄ OCH ₃ ) C ₆ H ₄ O group in the α position of the phthalocyanine skeleton. , 4-x (4-COOC ₂ H ₄ OCH ₃ ) C ₆ H ₄ O groups at the β-position have a structure in which 4 chlorine atoms and 6 hydrogen atoms are introduced at the remaining positions. I.e. 16 substituents of the phthalocyanine compounds of Examples 2-1, are, and 6 _{(4-COOC 2 H 4 OCH} 3) C 6 H 4 O group, made up with four halogen atoms and the six hydrogen atoms. The same applies to the descriptions of the following phthalocyanine compounds.

(Measurement of maximum absorption wavelength, gram absorption coefficient and absorbance ratio of 710nm and 520nm)

The maximum absorption wavelength ((lambda) max) and the gram extinction coefficient of the obtained phthalocyanine compound in the methanol solution containing 0.8 wt% of methyl cellosolves were measured using the spectrophotometer (The Hitachi Corporation make: U-2910). The measuring method was performed as follows.

0.04 g of the phthalocyanine compound obtained in a 50 ml volumetric flask was dissolved in 20 g of methyl cellosolve, and methanol was added so that the meniscus of the solution coincided with the mark of the 50 ml volumetric flask. Subsequently, 1 ml of the prepared solution was aliquoted using a pipette, and all the separated solutions were put in a 50 ml volumetric flask and diluted with methanol, and the meniscus of the solution was prepared so as to coincide with the mark of the 50 ml volumetric flask. The solution thus prepared was placed in a 1 cm wide Pyrex cell and the transmission spectrum was measured using a spectrophotometer. In addition, when the measured absorbance was A, the absorbance per 1g (called the gram extinction coefficient) was computed with the following formula | equation.

&Quot; (3) &quot;

Gram extinction coefficient = (A × 5000) / (0.08 × 1000)

In addition, absorbance at 710 nm showing extra emission of PDP and 520 nm, which is a wavelength of representative visible light, was measured, and the absorbance at absorbance ratio = 710 nm / absorbance at 520 nm was obtained.

Thus measured results are summarized in Table 2.

(Evaluation of heat resistance)

0.42 g of binder polymer (BSX-SN-1) manufactured by Nippon Catalysts Corporation, 1.22 g of propylene glycol monomethyl ether acetate (hereinafter referred to as PGMEA), and 0.112 g of dipentaerythritol hexaacrylate, 0.01 g of Chiba Specialty Chemicals Co., Ltd. product (IRGACURE 369) was added, melt | dissolved, and mixed, and the resin coating liquid was prepared. The obtained resin coating liquid was apply | coated to the glass plate using the bar coater so that the pigment | dye density | concentration of 30 wt% in dry film and dry film thickness might be 2 micrometers, and it dried at 80 degreeC for 30 minutes. The absorption spectrum of the coated glass plate thus obtained was measured with a spectrophotometer (manufactured by Hitachi, Ltd .: U-2910), which was referred to as a spectrum before heating. Next, the coating film glass plate which measured the spectrum before a heating was heat-processed at 220 degreeC for 20 minutes. The absorption spectrum of this heat-treated coated glass plate was measured with a spectrophotometer, and this was called the spectrum after heating. In each spectrum after heating, the absorbances up to 380 nm to 900 nm were integrated before heating and thus the difference between the absorbances before heating and after heating was measured. Further, the ΔE was calculated by the following equation when the said difference in the heating after the heating before spectrum E _1, E ₂ spectrum, the measured absorbance ΔE.

&Quot; (4) &quot;

ΔE = {∑ (absorbance of 380 to 900 nm of E ₁ ) -∑ (absorbance of 380 to 900 nm of E ₂ )} / ∑ (absorbance of 380 to 900 nm of E ₁ ) × 100 (%)

Thus measured results are summarized in Table 2 below.

(Evaluation of Solubility)

0.9 g of PGMEA was added to 0.1 g of the obtained phthalocyanine compound to prepare a preparation containing 10 wt% of a dye. After the preparation liquid was stirred for 1 hour with a magnetic stirrer, the whole amount was collected with a syringe and filtered using a membrane filter (φ = 0.45 μm). When the preparation liquid can pass through without being blocked by the membrane filter, a filtration test that determines that the dye is dissolved in the preparation liquid is carried out. The case where this was shown was made into (triangle | delta) and the case where clogging of a filter was made into x, and solubility was evaluated.

Example 2-2 Phthalocyanine Compound [ZnPc- {α- (4-COOC ₂ H ₄ OC ₂ H ₄ OCH ₃ ) C ₆ H ₄ O} ₂ , {α- (2-COOC ₂ H ₄ OC ₂ H ₄ OCH ₃ ) C ₆ H ₄ O} _x , {β- (2-COOC ₂ H ₄ OC ₂ H ₄ OCH ₃ ) C ₆ H ₄ O} _{4- x} Cl ₄ H ₆ ] (0≤x <4) Synthesis of

2.59 g (0.007 mol) of intermediate 2-2 obtained in Synthesis Example 2-2, 4.72 g (0.007 mol) of intermediate 2-20 obtained in Synthesis Example 2-20, 1.23 g (0.004 mol) of zinc iodide, and benzonitrile in a 150 ml flask 14.44g was added, and it reacted for about 8 hours, stirring using a magnetic stirrer under the nitrogen stream (10 ml / min), the internal temperature of 160 degreeC. After cooling, about 6.42 g (yield 85.5 mol% of Intermediate 2-2 and Intermediate 2-20) were obtained in the same manner as in Example 2-1. The phthalocyanine compound thus obtained was measured for maximum absorption wavelength, gram absorption coefficient, absorbance ratio and heat resistance by the same operation as in Example 2-1, and the results are summarized in Table 2.

Example 2-3 Phthalocyanine Compound [ZnPc- {α- (4-CN) C ₆ H ₄ O} ₂ , {α- (2-COOC ₂ H ₄ OC ₂ H ₄ OCH ₃ ) C ₆ H ₄ O } _x , synthesis of {β- (2-COOC ₂ H ₄ OC ₂ H ₄ OCH ₃ ) C ₆ H ₄ O} _{4- x} Cl ₄ H ₆ ] (0≤x <4)

1.72 g (0.007 mol) of intermediate 2-3 obtained in Synthesis Example 2-3, 4.71 g (0.007 mol) of intermediate 2-20 obtained in Synthesis Example 2-20, 1.23 g (0.004 mol) of zinc iodide, and benzonitrile in a 150 ml flask 14.44 g was added and reacted for about 9 hours while stirring using a magnetic stirrer under an air stream of nitrogen (10 ml / min) at an internal temperature of 160 ° C. After cooling, about 5.95 g (yield 89.3 mol% of Intermediate 2-3 and Intermediate 2-20) were obtained in the same manner as in Example 2-1.

The phthalocyanine compound thus obtained was measured for maximum absorption wavelength, gram absorption coefficient, absorbance ratio and heat resistance by the same operation as in Example 2-1, and the results are summarized in Table 2.

Example 2-4 Phthalocyanine Compound [ZnPc- {α- (4-CN) C ₆ H ₄ O} ₂ , {α- (4-COOC ₂ H ₄ OCH ₃ ) C ₆ H ₄ O} _x , { Synthesis of β- (4-COOC ₂ H ₄ OCH ₃ ) C ₆ H ₄ O} _{4- x} Cl ₄ H ₆ ] (0≤x <4)

2.45 g (0.01 mol) of intermediate 2-3 obtained in Synthesis Example 2-3, 5.85 g (0.01 mol) of intermediate 2-19 obtained in Synthesis Example 2-19, 1.76 g (0.006 mol) of zinc iodide, and benzonitrile in a 150 ml flask 20.62 g was added, and the mixture was reacted for about 3 hours while stirring using a magnetic stirrer under an air stream of nitrogen (10 ml / min) at an internal temperature of 160 ° C. After cooling, about 6.4 g (yield 74.1 mol% of intermediate 2-3 and intermediate 2-19) were obtained by operation similar to Example 2-1. The phthalocyanine compound thus obtained was measured for maximum absorption wavelength, gram absorption coefficient, absorbance ratio and heat resistance by the same operation as in Example 2-1, and the results are summarized in Table 2.

Example 2-5 Phthalocyanine Compound [ZnPc- {α- (2,6-Cl ₂ ) C ₆ H ₃ O} ₂ , {α- (4-COOC ₂ H ₄ OC ₂ H ₄ OCH ₃ ) C ₆ H ₄ O} _x , {β- (4-COOC ₂ H ₄ OC ₂ H ₄ OCH ₃ ) C ₆ H ₄ O} _{4- x} Cl ₄ H ₆ ] (0≤x <4)

2.31 g (0.008 mol) of Intermediate 2-4 obtained in Synthesis Example 2-4, 5.16 g (0.008 mol) of Intermediate 2-21 obtained in Synthesis Example 2-21, 1.40 g (0.004 mol) of zinc iodide, and benzonitrile in a 150 ml flask 8.26g was added, and it reacted for about 3 hours, stirring using a magnetic stirrer under the nitrogen stream (10 ml / min), the internal temperature of 160 degreeC. After cooling, the solution obtained by suction filtration was added dropwise into methanol (186.3 g) having a weight of 21 times the sum of the weight of intermediate 2 and the sum of the weight of zinc iodide and stirred for 30 minutes. Thereafter, half the amount of distilled water (93.1 g) of methanol was added dropwise thereto, followed by further stirring for 1 hour to precipitate crystals. The obtained crystals were filtered by suction, followed by washing and purifying by first adding a mixed solution of methanol (93.1 g) and distilled water (46.6 g) with stirring. After suction filtration, the extracted crystals were dried in vacuo at about 60 ° C. overnight to yield about 7.05 g (yield 91.1 mol% for Intermediate 2-4 and Intermediate 2-21).

The phthalocyanine compound thus obtained was measured for maximum absorption wavelength, gram absorption coefficient, absorbance ratio and heat resistance by the same operation as in Example 2-1, and the results are summarized in Table 2.

Example 2-6 Phthalocyanine Compound [ZnPc- {α- (4-C ₆ H ₅ ) C ₆ H ₄ O} ₂ , {α- (4-COOC ₂ H ₄ OC ₂ H ₄ OCH ₃ ) C ₆ H ₄ O} _x , {β- (4-COOC ₂ H ₄ OC ₂ H ₄ OCH ₃ ) C ₆ H ₄ O} _{4- x} Cl ₄ H ₆ ] (0≤x <4)

2.37 g (0.008 mol) of intermediate 2-5 obtained in Synthesis Example 2-5, 5.16 g (0.008 mol) of intermediate 2-21 obtained in Synthesis Example 2-21, 1.40 g (0.004 mol) of zinc iodide, and benzonitrile in a 150 ml flask 8.26g was added, and it was made to react for about 10 hours, stirring using a magnetic stirrer under the nitrogen stream (10 ml / min), the internal temperature of 160 degreeC. After cooling, about 6.56 g (yield 84.1 mol% of Intermediate 2-5 and Intermediate 2-21) were obtained in the same manner as in Example 2-5.

The phthalocyanine compound thus obtained was measured for maximum absorption wavelength, gram absorption coefficient, absorbance ratio and heat resistance by the same operation as in Example 2-1, and the results are summarized in Table 2.

Example 2-7 Phthalocyanine Compound [ZnPc- {α- (4-CN) C ₆ H ₄ O} ₂ , {α- (4-COOCH ₂ OC ₄ H ₇ ) C ₆ H ₄ O} _x , { Synthesis of β- (4-COOCH ₂ OC ₄ H ₇ ) C ₆ H ₄ O} _{4- x} Cl ₄ H ₆ ] (0≤x <4)

2.94 g (0.012 mol) of intermediate 2-3 obtained in Synthesis Example 2-3, 7.65 g (0.012 mol) of intermediate 2-22 obtained in Synthesis Example 2-22, 2.11 g (0.007 mol) of zinc iodide, and benzonitrile in a 150 ml flask 12.24 g was added, and the mixture was reacted for about 10 hours while stirring using a magnetic stirrer at 160 ° C. under an air stream of nitrogen (10 ml / min). After cooling, about 8.42 g (yield 115.0 mol% of intermediate 2-3 and intermediate 2-22) were obtained by operation similar to Example 2-5.

The phthalocyanine compound thus obtained was measured for maximum absorption wavelength, gram absorption coefficient, absorbance ratio and heat resistance by the same operation as in Example 2-1, and the results are summarized in Table 2.

Example 2-8 Phthalocyanine compound [ZnPc- {α- (4-CN) C ₆ H ₄ O} ₂ , {α- (3-COOC ₂ H ₄ OCH ₃ ) C ₆ H ₄ O} _x , { Synthesis of β- (3-COOC ₂ H ₄ OCH ₃ ) C ₆ H ₄ O} _{4- x} Cl ₄ H ₆ ] (0≤x <4)

2.45 g (0.01 mol) of intermediate 2-3 obtained in Synthesis Example 2-3, 6.24 g (0.01 mol) of intermediate 2-23 obtained in Synthesis Example 2-23, 1.76 g (0.006 mol) of zinc iodide, and benzonitrile in a 150 ml flask 9.98 g was added, and it reacted for about 5 hours, stirring using a magnetic stirrer with 160 degreeC of internal temperature under nitrogen stream (10 ml / min). After cooling, about 5.0 g (yield 55.4 mol% of Intermediate 2-3 and Intermediate 2-23) were obtained in the same manner as in Example 2-5.

The phthalocyanine compound thus obtained was measured for maximum absorption wavelength, gram absorption coefficient, absorbance ratio and heat resistance by the same operation as in Example 2-1, and the results are summarized in Table 2.

Example 2-9 Phthalocyanine Compound [ZnPc- {α- (4-CN) C ₆ H ₄ O} ₂ , {α- (4-COOC ₂ H ₄ OCH ₃ ) C ₆ H ₄ O} _x , { Synthesis of β- (4-COOC ₂ H ₄ OCH ₃ ) C ₆ H ₄ O} _{6- x} Cl ₂ H ₆ ] (0≤x <6)

1.96 g (0.008 mol) of intermediate 2-3 obtained in Synthesis Example 2-3, 5.96 g (0.008 mol) of intermediate 2-24 obtained in Synthesis Example 2-24, 1.40 g (0.004 mol) of zinc iodide, and benzonitrile in a 150 ml flask 2.64g was added, and it reacted for about 8 hours, stirring using a magnetic stirrer with 160 degreeC of internal temperature under nitrogen stream (10 ml / min). After cooling, about 6.70 g (yield 81.9 mol% of Intermediate 2-3 and Intermediate 2-24) were obtained in the same manner as in Example 2-5.

The phthalocyanine compound thus obtained was measured for maximum absorption wavelength, gram absorption coefficient, absorbance ratio and heat resistance by the same operation as in Example 2-1, and the results are summarized in Table 2.

(Example 2-10) Phthalocyanine compound [ZnPc- {α- (4-NO ₂ ) C ₆ H ₄ S} ₂ , {α- (4-COOC ₂ H ₄ OCH ₃ ) C ₆ H ₄ O} _x , Synthesis of {β- (4-COOC ₂ H ₄ OCH ₃ ) C ₆ H ₄ O} _{4- x} Cl ₄ H ₆ ] (0≤x <4)

1.97 g (0.007 mol) of intermediate 2-6 obtained in Synthesis Example 2-6, 4.10 g (0.007 mol) of intermediate 2-19 obtained in Synthesis Example 2-19, 1.23 g (0.004 mol) of zinc iodide, and benzonitrile in a 150 ml flask 6.56 g was added, and the mixture was reacted for about 8 hours while stirring using a magnetic stirrer under an air stream of nitrogen (10 ml / min) at an internal temperature of 160 ° C. After cooling, the solution obtained by suction filtration was dripped in 20 times methanol (121.3 g) of the total weight of the intermediate 2, and it stirred for 30 minutes. Thereafter, half of distilled water (60.7 g) in methanol was added dropwise, followed by stirring for 1 hour to precipitate crystals. After the obtained crystals were suction filtered, the first half of the mixture (methanol (60.7 g) and distilled water (30.3 g)) was added thereto, followed by stirring and washing, followed by washing and purification. After suction filtration, the crystals taken out were vacuum dried at about 60 ° C. overnight to yield about 5.29 g (yield 84.0 mol% for Intermediate 2-6 and Intermediate 2-19).

The phthalocyanine compound thus obtained was measured for maximum absorption wavelength, gram absorption coefficient, absorbance ratio and heat resistance by the same operation as in Example 2-1, and the results are summarized in Table 2.

Example 2-11 Phthalocyanine Compound [ZnPc- {α-C ₆ F ₅ O} ₂ , {α- (2-COOCH ₃ ) C ₆ H ₄ O} _x , {β- (2-COOCH ₃ ) C ₆ H ₄ O} _{4- x} Cl ₄ H ₆ ] (0≤x <4)

2.17 g (0.007 mol) of intermediate 2-7 obtained in Synthesis Example 2-7, 3.48 g (0.007 mol) of intermediate 2-25 obtained in Synthesis Example 2-25, 1.23 g (0.004 mol) of zinc iodide, and benzonitrile in a 150 ml flask 14.44 g was added and reacted for about 10 hours with stirring using a magnetic stirrer under an air stream of nitrogen (10 ml / min), an internal temperature of 160 ° C. After cooling, about 4.7 g (yield 79.9 mol% of Intermediate 2-7 and Intermediate 2-25) were obtained in the same manner as in Example 2-1.

The phthalocyanine compound thus obtained was measured for maximum absorption wavelength, gram absorption coefficient, absorbance ratio and heat resistance by the same operation as in Example 2-1, and the results are summarized in Table 2.

Example 2-12 Phthalocyanine Compound [ZnPc- {α- (2-NO ₂ ) C ₆ H ₄ O} ₂ , {α- (2,6-Cl ₂ ) C ₆ H ₃ O} _x , {β _Synthesis of-(2,6-Cl ₂ ) C ₆ H ₃ O} _{2- x} Cl ₆ H ₆ ] (0≤x <2)

2.12 g (0.008 mol) of intermediate 2-8 obtained in Synthesis Example 2-8, 4.15 g (0.008 mol) of intermediate 2-26 obtained in Synthesis Example 2-26, 1.40 g (0.004 mol) of zinc iodide, and benzonitrile in a 150 ml flask 16.50 g was added, and the mixture was reacted for about 8 hours while stirring using a magnetic stirrer with an internal temperature of 160 ° C. under a stream of nitrogen (10 ml / min). After cooling, the solution obtained by suction filtration was dripped in 66.0 g of methanol, and it stirred for 30 minutes. Thereafter, 16.5 g of distilled water was added dropwise thereto, followed by further stirring for 1 hour to precipitate crystals. The obtained crystals were suction filtered and then washed and purified by adding a mixed solution of 33.0 g of methanol and 33.0 g of distilled water, followed by stirring and washing. After suction filtration, the crystals taken out were vacuum dried at about 60 ° C. overnight to yield about 5.43 g (yield 83.1 mol% for Intermediate 2-8 and Intermediate 2-26).

The phthalocyanine compound thus obtained was measured for maximum absorption wavelength, gram absorption coefficient, absorbance ratio and heat resistance by the same operation as in Example 2-1, and the results are summarized in Table 2.

Example 2-13 Phthalocyanine Compound [ZnPc- {α- (2-CN) C ₆ H ₄ O} ₂ , {α- (2,6-Cl ₂ ) C ₆ H ₃ O} _x , {β- _{Synthesis of} (2,6-Cl ₂ ) C ₆ H ₃ O} _{4- x} Cl ₄ H ₆ ] (0≤x <4)

2.94 g (0.012 mol) of intermediate 2-9 obtained in Synthesis Example 2-9, 6.23 g (0.012 mol) of intermediate 2-27 obtained in Synthesis Example 2-27, 2.11 g (0.007 mol) of zinc iodide, and benzonitrile in a 150 ml flask 24.75 g was added, and the mixture was reacted for about 6 hours while stirring using a magnetic stirrer with an internal temperature of 160 ° C. under a stream of nitrogen (10 ml / min). After cooling, about 9.2 g (yield 96.2 mol% of intermediate 2-9 and intermediate 2-27) were obtained by operation similar to Example 2-1.

The phthalocyanine compound thus obtained was measured for maximum absorption wavelength, gram absorption coefficient, absorbance ratio and heat resistance by the same operation as in Example 2-1, and the results are summarized in Table 2.

Example 2-14 Phthalocyanine Compound [ZnPc- {α- (4-CN) C ₆ H ₄ O} ₁ , {α- (4-COOC ₂ H ₄ OCH ₃ ) C ₆ H ₄ O} _x , { Synthesis of β- (4-COOC ₂ H ₄ OCH ₃ ) C ₆ H ₄ O} _{6- x} Cl ₆ H ₃ ] (0≤x <6)

0.80 g (0.003 mol) of intermediate 2-3 obtained in Synthesis Example 2-3, 6.12 g (0.01 mol) of intermediate 2-19 obtained in Synthesis Example 2-19, 1.15 g (0.004 mol) of zinc iodide, and benzonitrile in a 150 ml flask 9.78 g was added, and the mixture was reacted for about 10 hours while stirring using a magnetic stirrer with an internal temperature of 160 ° C. under a stream of nitrogen (10 ml / min). After cooling, the solution obtained by suction filtration was dripped in 220.2 g of methanol, and it stirred for 30 minutes. Then, 110.1 g of distilled water was added dropwise, and the mixture was further stirred for 1 hour to precipitate crystals. The obtained crystals were suction filtered and then washed and purified by adding a mixed solution of 110.1 g of methanol and 55.0 g of distilled water, followed by stirring and washing. After suction filtration, the extracted crystals were dried in vacuo at about 60 ° C. overnight to yield about 6.19 g (86.8 mol% of yields for Intermediate 2-3 and Intermediate 2-19).

The phthalocyanine compound thus obtained was measured for maximum absorption wavelength, gram absorption coefficient, absorbance ratio and heat resistance by the same operation as in Example 2-1, and the results are summarized in Table 2.

Example 2-15 Phthalocyanine Compound [ZnPc- {α- (4-COOC ₂ H ₄ OCH ₃ ) C ₆ H ₄ O} ₁ , {α- (4-COOC ₂ H ₄ OCH ₃ ) C ₆ H ₄ O} _x , {β- (4-COOC ₂ H ₄ OCH ₃ ) C ₆ H ₄ O} _{6- x} Cl ₆ H ₃ ] (0≤x <6)

0.64 g (0.002 mol) of intermediate 2-1 obtained in Synthesis Example 2-1, 3.51 g (0.006 mol) of intermediate 2-19 obtained in Synthesis Example 2-19, 0.70 g (0.002 mol) of zinc iodide, and benzonitrile in a 150 ml flask 5.62 g was added, and it was made to react for about 10 hours, stirring using a magnetic stirrer under the nitrogen stream (10 ml / min), the internal temperature of 160 degreeC. After cooling, the solution obtained by suction filtration was dripped in 126.4 g of methanol, and it stirred for 30 minutes. Thereafter, 42.1 g of distilled water was added dropwise thereto, followed by further stirring for 1 hour to precipitate crystals. The obtained crystals were suction filtered and then washed and purified by adding a mixed solution of 63.2 g of methanol and 21.1 g of distilled water, followed by stirring and washing. After suction filtration, the crystals taken out were dried in vacuo at about 60 ° C. overnight to yield about 3.72 g (yield 88.1 mol% for Intermediate 2-1 and Intermediate 2-19).

The phthalocyanine compound thus obtained was measured for maximum absorption wavelength, gram absorption coefficient, absorbance ratio and heat resistance by the same operation as in Example 2-1, and the results are summarized in Table 2.

Example 2-16 Phthalocyanine Compound [ZnPc- {α- (4-Cl) C ₆ H ₄ O} ₂ , {α- (4-COOC ₂ H ₄ OCH ₃ ) C ₆ H ₄ O} _x , { α- (4-COOC ₂ H ₄ OC ₂ H ₄ OCH ₃ ) C ₆ H ₄ O} _y , {β- (4-COOC ₂ H ₄ OCH ₃ ) C ₆ H ₄ O} _2-x , {β- Synthesis of (4-COOC ₂ H ₄ OC ₂ H ₄ OCH ₃ ) C ₆ H ₄ O} _2-y Cl ₄ H ₆ ] (0≤x <2, 0≤y <2)

2.08 g (0.008 mol) of intermediate 2-10 obtained in Synthesis Example 2-10, 5.02 g (0.008 mol) of intermediate 2-28 obtained in Synthesis Example 2-28, 1.43 g (0.004 mol) of zinc iodide, and benzonitrile in a 150 ml flask 8.02g was added, and it reacted for about 6 hours, stirring using a magnetic stirrer with 160 degreeC of internal temperature under nitrogen stream (10 ml / min). After cooling, about 6.5 g (yield 88.3 mol% for intermediate 2-10 and intermediate 2-28) were obtained in the same manner as in Example 2-5.

The phthalocyanine compound thus obtained was measured for maximum absorption wavelength, gram absorption coefficient, absorbance ratio and heat resistance by the same operation as in Example 2-1, and the results are summarized in Table 2.

Example 2-17 Phthalocyanine Compound [ZnPc- {α- (4-COOC ₂ H ₄ OCH ₃ ) C ₆ H ₄ O} ₂ , {α- (2,6-Cl ₂ ) C ₆ H ₃ O} _x , {α- (4-COOC ₂ H ₄ OCH ₃ ) C ₆ H ₄ O} _y , {β- (2,6-Cl ₂ ) C ₆ H ₃ O} _2-x , {β- (4- COOC ₂ H ₄ OCH ₃ ) C ₆ H ₄ O} _2-y Cl ₄ H ₆ ] (0≤x <2, 0≤y <2)

3.22 g (0.010 mol) of intermediate 2-1 obtained in Synthesis Example 2-1, 5.52 g (0.010 mol) of intermediate 2-29 obtained in Synthesis Example 2-29, 1.76 g (0.006 mol) of zinc iodide, and benzonitrile in a 150 ml flask 8.83 g was added, and the mixture was reacted for about 6 hours while stirring using a magnetic stirrer under an air stream of nitrogen (10 ml / min), an internal temperature of 160 ° C. After cooling, about 7.40 g (yield 81.5 mol% of Intermediate 2-1 and Intermediate 2-29) were obtained in the same manner as in Example 2-5.

The phthalocyanine compound thus obtained was measured for maximum absorption wavelength, gram absorption coefficient, absorbance ratio and heat resistance by the same operation as in Example 2-1, and the results are summarized in Table 2.

Example 2-18 Phthalocyanine Compound [ZnPc- {α- (4-CN) C ₆ H ₄ O} ₂ , {α- (4-CN) C ₆ H ₄ O} _x , {α- (4- COOC ₂ H ₄ OCH ₃ ) C ₆ H ₄ O} _y , {β- (4-CN) C ₆ H ₄ O} _2-x , {β- (4-COOC ₂ H ₄ OCH ₃ ) C ₆ H ₄ O} _4-y Cl ₂ H ₆ ]] (0 ≦ x <2, 0 ≦ y <4)

2.45 g (0.010 mol) of intermediate 2-3 obtained in Synthesis Example 2-3, 6.24 g (0.010 mol) of intermediate 2-30 obtained in Synthesis Example 2-30, 1.76 g (0.006 mol) of zinc iodide, and benzonitrile in a 150 ml flask 9.98 g was added, and it was made to react for about 6 hours, stirring using a magnetic stirrer under the nitrogen stream (10 ml / min), the internal temperature of 160 degreeC. After cooling, about 6.91 g (yield 76.6 mol% of intermediate 2-3 and intermediate 2-30) were obtained by operation similar to Example 2-5.

The phthalocyanine compound thus obtained was measured for maximum absorption wavelength, gram absorption coefficient, absorbance ratio and heat resistance by the same operation as in Example 2-1, and the results are summarized in Table 2.

Example 2-19 Phthalocyanine Compound [ZnPc- {α- (4-CN) C ₆ H ₄ O} ₂ , {α- (4-CN) C ₆ H ₄ O} _x , {α- (4- COOC ₂ H ₄ OCH ₃ ) C ₆ H ₄ O} _y , {β- (4-CN) C ₆ H ₄ O} _1-x , {β- (4-COOC ₂ H ₄ OCH ₃ ) C ₆ H ₄ O} _3-y Cl ₄ H ₆ ] (0 ≦ x <1, 0 ≦ y <3)

2.45 g (0.010 mol) of intermediate 2-3 obtained in Synthesis Example 2-3, 5.47 g (0.010 mol) of intermediate 2-31 obtained in Synthesis Example 2-31, 1.76 g (0.006 mol) of zinc iodide, and benzonitrile in a 150 ml flask 8.75g was added, and it reacted for about 6 hours, stirring using a magnetic stirrer under the nitrogen stream (10 ml / min), the internal temperature of 160 degreeC. After cooling, about 6.47 g (yield 78.5 mol% of intermediate 2-3 and intermediate 2-31) were obtained by operation similar to Example 2-5.

The phthalocyanine compound thus obtained was measured for maximum absorption wavelength, gram absorption coefficient, absorbance ratio and heat resistance by the same operation as in Example 2-1, and the results are summarized in Table 2.

Example 2-20 Phthalocyanine Compound [ZnPc- {α- (4-COOC ₂ H ₄ OCH ₃ ) C ₆ H ₄ O} ₂ , {α- (4-CN) C ₆ H ₄ O} _x , { α- (4-COOC ₂ H ₄ OCH ₃ ) C ₆ H ₄ O} _y , {β- (4-CN) C ₆ H ₄ O} _2-x , {β- (4-COOC ₂ H ₄ OCH ₃ ) C ₆ H ₄ O} Synthesis of _2-y Cl ₄ H ₆ ] (0≤x <2, 0≤y <2)

2.90 g (0.009 mol) of intermediate 2-1 obtained in Synthesis Example 2-1, 4.57 g (0.009 mol) of intermediate 2-32 obtained in Synthesis Example 2-32, 2.15 g (0.007 mol) of zinc iodide, and benzonitrile in a 150 ml flask 2.49g was added, and it reacted for about 8 hours, stirring using a magnetic stirrer with 160 degreeC of internal temperature under nitrogen stream (10 ml / min). After cooling, about 6.05 g (yield 77.9 mol% of Intermediate 2-1 and Intermediate 2-32) were obtained in the same manner as in Example 2-10.

The phthalocyanine compound thus obtained was measured for maximum absorption wavelength, gram absorption coefficient, absorbance ratio and heat resistance by the same operation as in Example 2-1, and the results are summarized in Table 2.

Example 2-21 Phthalocyanine Compound [ZnPc- {α- (4-COOC ₂ H ₄ OCH ₃ ) C ₆ H ₄ O} _{1 + x} , {α- (4-CN) C ₆ H ₄ O} _{1 + y} , {β- (4-COOC ₂ H ₄ OCH ₃ ) C ₆ H ₄ O} _2-x , {β- (4-CN) C ₆ H ₄ O} _{2- y} Cl ₄ H ₆ ] (0 Synthesis of ≤x <2, 0≤y <2)

1.61 g (0.005 mol) of Intermediate 2-1 obtained in Synthesis Example 2-1, 1.23 g (0.005 mol) of Intermediate 2-3 obtained in Synthesis Example 2-3, and Intermediate 2-19 obtained in Synthesis Example 2-19 in a 150 ml flask 2.93 g (0.005 mol), 2.16 g (0.005 mol) of the intermediate 2-33 obtained in Synthesis Example 2-33, 1.76 g (0.006 mol) of zinc iodide, and 2.64 g of benzonitrile were added thereto under a nitrogen stream (10 ml / min). The reaction was performed for 8 hours while stirring using a magnetic stirrer at an internal temperature of 160 ° C. After cooling, about 7.6 g (yield 92.1 mol% of intermediate 2-1 and intermediate 2-3, intermediate 2-19, and intermediate 2-33) were obtained by operation similar to Example 2-10.

The phthalocyanine compound thus obtained was measured for maximum absorption wavelength, gram absorption coefficient, absorbance ratio and heat resistance by the same operation as in Example 2-1, and the results are summarized in Table 2.

Example 2-22 Phthalocyanine Compound [ZnPc- {α- (4-COOC ₂ H ₄ OCH ₃ ) C ₆ H ₄ O} _{1 + x} , {α- (4-CN) C ₆ H ₄ O} ₁ , {β- (4-COOC ₂ H ₄ OCH ₃ ) C ₆ H ₄ O} _{4- x} Cl ₄ H ₆ ] (0≤x <4)

1.45 g (0.005 mole) of Intermediate 2-1 obtained in Synthesis Example 2-1, 1.10 g (0.005 mole) of Intermediate 2-3 obtained in Synthesis Example 2-3, and Intermediate 2-19 obtained in Synthesis Example 2-19 in a 150 ml flask 5.27 g (0.009 mole), zinc iodide 1.58 g (0.005 mole), and benzonitrile 2.61 g were added thereto, and the mixture was reacted for about 10 hours with stirring using a magnetic stirrer under a nitrogen stream (10 ml / min), an internal temperature of 160 ° C. . After cooling, about 6.55 g (yield 80.7 mol% of Intermediate 2-1 and Intermediate 2-3, Intermediate 2-19) were obtained in the same manner as in Example 2-10.

The phthalocyanine compound thus obtained was measured for maximum absorption wavelength, gram absorption coefficient, absorbance ratio and heat resistance by the same operation as in Example 2-1, and the results are summarized in Table 2.

Example 2-23 Phthalocyanine Compound [ZnPc- {α- (OC ₂ H ₄ OC ₂ H ₄ OCH ₃ )} ₂ , {α- (2-COOC ₂ H ₄ OCH ₃ ) C ₆ H ₄ O} _x , {β- (2-COOC ₂ H ₄ OCH ₃ ) C ₆ H ₄ O} _{4- x} Cl ₄ H ₆ ] (0≤x <4)

0.42 g (0.002 mol) of intermediate 2-11 obtained in Synthesis Example 2-11, 1.0 g (0.002 mol) of intermediate 2-34 obtained in Synthesis Example 2-34, 0.3 g (0.001 mol) of zinc iodide, and benzonitrile in a 150 ml flask 2.85g was added, and it reacted for about 6 hours, stirring using a magnetic stirrer under the nitrogen stream (10 ml / min), the internal temperature of 160 degreeC. After cooling, the solvent was removed by evaporation under the condition of 125 ° C. × 1 hr, and the crystals extracted by vacuum drying at about 60 ° C. overnight were about 1.67 g (113.0 mol% of the yield for Intermediate 2-11 and Intermediate 2-34). ) Was obtained.

The phthalocyanine compound thus obtained was measured for maximum absorption wavelength, gram absorption coefficient, absorbance ratio and heat resistance by the same operation as in Example 2-1, and the results are summarized in Table 2.

(Example 2-24) Phthalocyanine compound [ZnPc- {α- (OCH (CH ₃ ) CH ₂ OCH ₃ )} ₂ , {α- (2-COOC ₂ H ₄ OCH ₃ ) C ₆ H ₄ O} _x , Synthesis of {β- (2-COOC ₂ H ₄ OCH ₃ ) C ₆ H ₄ O} _{4- x} Cl ₄ H ₆ ] (0≤x <4)

0.41 g (0.002 mol) of intermediate 2-12 obtained in Synthesis Example 2-12, 1.1 g (0.002 mol) of intermediate 2-34 obtained in Synthesis Example 2-34, 0.33 g (0.001 mol) of zinc iodide, and benzonitrile in a 150 ml flask 2.85g was added, and it reacted for about 5 hours, stirring using a magnetic stirrer with 160 degreeC of internal temperature under nitrogen stream (10 ml / min). After cooling, the solvent was removed by evaporation under the condition of 125 ° C. × 1 hr, followed by vacuum drying at about 60 ° C. overnight to yield about 1.7 g (108.4 mol% for intermediate 2-12 and intermediate 2-34). .

The phthalocyanine compound thus obtained was measured for maximum absorption wavelength, gram absorption coefficient, absorbance ratio and heat resistance by the same operation as in Example 2-1, and the results are summarized in Table 2.

Example 2-25 Phthalocyanine Compound [ZnPc- {β- (4-COOC ₂ H ₄ OC ₂ H ₄ OCH ₃ ) C ₆ H ₄ O} ₂ , {α- (2-COOC ₂ H ₄ OC ₂ H ₄ OCH ₃ ) C ₆ H ₄ O} _x , {β- (2-COOC ₂ H ₄ OC ₂ H ₄ OCH ₃ ) C ₆ H ₄ O} _{4- x} Cl ₄ H ₆ ] (0≤x <4) Synthesis of

2.56 g (0.007 mol) of intermediate 2-13 obtained in Synthesis Example 2-13, 4.71 g (0.007 mol) of intermediate 2-20 obtained in Synthesis Example 2-20, 1.23 g (0.004 mol) of zinc iodide, and benzonitrile in a 150 ml flask 14.44g was added, and it reacted for about 8 hours, stirring using a magnetic stirrer under the nitrogen stream (10 ml / min), the internal temperature of 160 degreeC. After cooling, about 6.39 g (yield 83.9 mol% of Intermediate 2-13 and Intermediate 2-20) were obtained in the same manner as in Example 2-1.

The phthalocyanine compound thus obtained was measured for maximum absorption wavelength, gram absorption coefficient, absorbance ratio and heat resistance by the same operation as in Example 2-1, and the results are summarized in Table 2.

(Example 2-26) phthalocyanine compound [ZnPc- {β- (4-COOC ₂ H ₄ OCH ₃ ) C ₆ H ₄ O}} ₂ , {α- (4-CN) C ₆ H ₄ O} _x , Synthesis of {β- (4-CN) C ₆ H ₄ O} _{4- x} Cl ₄ H ₆ ] (0≤x <4)

3.35 g (0.01 mol) of intermediate 2-14 obtained in Synthesis Example 2-14, 4.48 g (0.01 mol) of intermediate 2-33 obtained in Synthesis Example 2-33, 1.83 g (0.006 mol) of zinc iodide, and benzonitrile in a 150 ml flask 2.61g was added, and it reacted for about 5 hours, stirring using a magnetic stirrer with 160 degreeC of internal temperature under nitrogen stream (10 ml / min). After cooling, about 7.38 g (yield 90.3 mol% of intermediates 2-14 and 2-33) were obtained in the same manner as in Example 10.

The phthalocyanine compound thus obtained was measured for maximum absorption wavelength, gram absorption coefficient, absorbance ratio and heat resistance by the same operation as in Example 2-1, and the results are summarized in Table 2.

Example 2-27 Phthalocyanine Compound [ZnPc- {β- (4-CN) C ₆ H ₄ O} ₁ , {α- (4-COOC ₂ H ₄ OCH ₃ ) C ₆ H ₄ O} _x , { Synthesis of β- (4-COOC ₂ H ₄ OCH ₃ ) C ₆ H ₄ O} _{6- x} Cl ₆ H ₃ ] (0≤x <6)

0.65 g (0.003 mol) of intermediate 2-15 obtained in Synthesis Example 2-15, 5.01 g (0.008 mol) of intermediate 2-19 obtained in Synthesis Example 2-19, 0.94 g (0.003 mol) of zinc iodide, and benzonitrile in a 150 ml flask 1.88 g was added, and the mixture was reacted for about 10 hours while stirring using a magnetic stirrer with an internal temperature of 160 ° C. under a stream of nitrogen (10 ml / min). After cooling, the solution obtained by suction filtration was dripped in 179.7 g of methanol, and it stirred for 30 minutes. Thereafter, 89.9 g of distilled water was added dropwise thereto, followed by further stirring for 1 hour to precipitate crystals. The obtained crystals were suction filtered and then washed and purified by adding a mixed solution of 89.9 g of methanol and 44.9 g of distilled water, followed by stirring and washing. After suction filtration, the extracted crystals were dried in vacuo at about 60 ° C. overnight to yield about 5.0 g (yield 85.9 mol% for Intermediate 2-15 and Intermediate 2-19).

The phthalocyanine compound thus obtained was measured for maximum absorption wavelength, gram absorption coefficient, absorbance ratio and heat resistance by the same operation as in Example 2-1, and the results are summarized in Table 2.

Example 2-28 Phthalocyanine Compound [ZnPc- {β- (2,6-Cl ₂ ) C ₆ H ₃ O} ₁ , {α- (4-COOCH ₃ ) C ₆ H ₄ O} _x , {β Synthesis of-(4-COOCH ₃ ) C ₆ H ₄ O} _{6- x} Cl ₆ H ₃ ] (0≤x <6)

1.25 g (0.004 mol) of intermediate 2-16 obtained in Synthesis Example 2-16, 6.46 g (0.013 mol) of intermediate 2-35 obtained in Synthesis Example 2-35, 1.52 g (0.005 mol) of zinc iodide, and benzonitrile in a 150 ml flask 2.57 g was added, and the mixture was reacted for about 8 hours while stirring using a magnetic stirrer with an internal temperature of 160 ° C. under a stream of nitrogen (10 ml / min). After cooling, the solution obtained by suction filtration was dripped in 232.7 g of methanol, and it stirred for 30 minutes. Thereafter, 116.4 g of distilled water was added dropwise thereto, followed by further stirring for 1 hour to precipitate crystals. The obtained crystals were suction filtered and then washed and purified by adding a mixed solution of 116.4 g of methanol and 58.2 g of distilled water, followed by stirring and washing. After suction filtration, the crystals taken out were vacuum dried at about 60 ° C. overnight to yield about 7.59 g (yield 94.9 mol% for Intermediate 2-16 and Intermediate 2-35).

The phthalocyanine compound thus obtained was measured for maximum absorption wavelength, gram absorption coefficient, absorbance ratio and heat resistance by the same operation as in Example 2-1, and the results are summarized in Table 2.

(Example 2-29) Phthalocyanine compound [ZnPc- {β- (4-NO ₂ ) C ₆ H ₄ O} ₂ , {α- (4-COOC ₂ H ₄ OCH ₃ ) C ₆ H ₄ O} _x , Synthesis of {β- (4-COOC ₂ H ₄ OCH ₃ ) C ₆ H ₄ O} _{4- x} Cl ₄ H ₆ ] (0≤x <4)

2.39 g (0.009 mol) of intermediate 2-17 obtained in Synthesis Example 2-17, 5.27 g (0.O09 mol) of intermediate 2-19 obtained in Synthesis Example 2-19, 1.58 g (0.005 mol) of zinc iodide, in a 150 ml flask 2.55 g of benzonitrile were added and reacted for about 10 hours while stirring using a magnetic stirrer under an air stream of nitrogen (10 ml / min) at an internal temperature of 160 ° C. After cooling, about 6.9 g (yield 86.8 mol% for intermediate 2-17 and intermediate 2-19) were obtained in the same manner as in Example 2-10.

The phthalocyanine compound thus obtained was measured for maximum absorption wavelength, gram absorption coefficient, absorbance ratio and heat resistance by the same operation as in Example 2-1, and the results are summarized in Table 2.

Example 2-30 Phthalocyanine Compound [ZnPc- {β-C ₆ F ₅ O} ₂ , {α- (2-COOCH ₃ ) C ₆ H ₄ O} _x , {β- (2-COOCH ₃ ) C ₆ H ₄ O} _{4- x} Cl ₄ H ₆ ] (0≤x <4)

2.17 g (0.007 mol) of intermediate 2-18 obtained in Synthesis Example 2-18, 3.48 g (0.007 mol) of intermediate 2-25 obtained in Synthesis Example 2-25, 1.23 g (0.004 mol) of zinc iodide, and benzonitrile in a 150 ml flask 14.44 g was added and reacted for about 10 hours with stirring using a magnetic stirrer under an air stream of nitrogen (10 ml / min), an internal temperature of 160 ° C. After cooling, about 4.2 g (yield 71.4 mol% of intermediates 2-18 and 2-25) were obtained in the same manner as in Example 2-1.

The phthalocyanine compound thus obtained was measured for maximum absorption wavelength, gram absorption coefficient, absorbance ratio and heat resistance by the same operation as in Example 2-1, and the results are summarized in Table 2.

Example 2-31 Phthalocyanine Compound [ZnPc- {β- (4-CN) C ₆ H ₄ O} ₂ , {α- (4-COOC ₂ H ₄ OCH ₃ ) C ₆ H ₄ O} _x , { Synthesis of β- (4-COOC ₂ H ₄ OCH ₃ ) C ₆ H ₄ O} _{6- x} Cl ₂ H ₆ ] (0≤x <6)

1.96 g (0.008 mol) of intermediate 2-15 obtained in Synthesis Example 2-15, 5.96 g (0.008 mol) of intermediate 2-36 obtained in Synthesis Example 2-36, 1.40 g (0.004 mol) of zinc iodide, and benzonitrile in a 150 ml flask 2.64 g was added and reacted for about 7 hours while stirring using a magnetic stirrer at 160 ° C internal temperature under a stream of nitrogen (10 ml / min). After cooling, about 7.2 g (yield 88.0 mol% for intermediate 2-15 and intermediate 2-36) were obtained in the same manner as in Example 2-5.

The phthalocyanine compound thus obtained was measured for maximum absorption wavelength, gram absorption coefficient, absorbance ratio and heat resistance by the same operation as in Example 2-1, and the results are summarized in Table 2.

Example 2-32 Phthalocyanine Compound [ZnPc- {β- (2,6-Cl ₂ ) C ₆ H ₃ O} ₂ , {α- (2-COOCH ₃ ) C ₆ H ₄ O} _x , {β Synthesis of-(2-COOCH ₃ ) C ₆ H ₄ O} _{6- x} Cl ₂ H ₆ ] (0≤x <6)

2.31 g (0.008 mol) of intermediate 2-16 obtained in Synthesis Example 2-16, 4.90 g (0.008 mol) of intermediate 2-37 obtained in Synthesis Example 2-37, 1.40 g (0.004 mol) of zinc iodide, and benzonitrile in a 150 ml flask 2.41 g was added, and it reacted for about 8 hours, stirring using a magnetic stirrer with 160 degreeC of internal temperature under nitrogen stream (10 ml / min). After cooling, about 5.6 g (yield 74.9 mol% for intermediate 2-16 and intermediate 2-37) were obtained in the same manner as in Example 2-5.

The phthalocyanine compound thus obtained was measured for maximum absorption wavelength, gram absorption coefficient, absorbance ratio and heat resistance by the same operation as in Example 2-1, and the results are summarized in Table 2.

Example 2-33 Phthalocyanine Compound [ZnPc- {β- (4-COOC ₂ H ₄ OCH ₃ ) C ₆ H ₄ O} ₂ , {α- (4-CN) C ₆ H ₄ O} _x , { Synthesis of β- (4-CN) C ₆ H ₄ O} _{6- x} Cl ₂ H ₆ ] (0≤x <6)

3.35 g (0.01 mol) of intermediate 2-14 obtained in Synthesis Example 2-14, 5.34 g (0.01 mol) of intermediate 2-38 obtained in Synthesis Example 2-38, 1.83 g (0.006 mol) of zinc iodide, and benzonitrile in a 150 ml flask 2.90 g was added, and the mixture was reacted for about 8 hours while stirring using a magnetic stirrer with an internal temperature of 160 ° C. under a nitrogen stream (10 ml / min). After cooling, about 7.5 g (yield 83.0 mol% of Intermediate 2-14 and Intermediate 2-38) were obtained in the same manner as in Example 2-10.

The phthalocyanine compound thus obtained was measured for maximum absorption wavelength, gram absorption coefficient, absorbance ratio and heat resistance by the same operation as in Example 2-1, and the results are summarized in Table 2.

Example 2-34 Phthalocyanine Compound [ZnPc- {β- (4-CN) C ₆ H ₄ O} ₂ , {α- (3-COOC ₂ H ₅ ) C ₆ H ₄ O} _x , {β- Synthesis of (3-COOC ₂ H ₅ ) C ₆ H ₄ O} _{6- x} Cl ₂ H ₆ ] (0≤x <6)

1.23 g (0.005 mol) of Intermediate 2-15 obtained in Synthesis Example 2-15, 3.06 g (0.005 mol) of Intermediate 2-39 obtained in Synthesis Example 2-39, 0.88 g (0.003 mol) of zinc iodide, and benzonitrile in a 150 ml flask 1.43 g was added, and the mixture was reacted for about 6 hours with stirring using a magnetic stirrer under a nitrogen stream (10 ml / min), an internal temperature of 160 ° C. After cooling, about 4.01 g (yield 90.0 mol% of Intermediate 2-15 and Intermediate 2-39) were obtained in the same manner as in Example 2-5.

The phthalocyanine compound thus obtained was measured for maximum absorption wavelength, gram absorption coefficient, absorbance ratio and heat resistance by the same operation as in Example 2-1, and the results are summarized in Table 2.

Example 2-35 Phthalocyanine Compound [ZnPc- {β- (4-CN) C ₆ H ₄ O} ₂ , {α- (4-COOC ₂ H ₄ OCH ₃ ) C ₆ H ₄ O} _x , { α- (4-CN) C ₆ H ₄ O} _y , {β- (4-COOC ₂ H ₄ OCH ₃ ) C ₆ H ₄ O} _4-x , {β- (4-CN) C ₆ H ₄ O} _2-y Cl ₂ H ₆ ] (0 ≦ x <4,0 ≦ _y <2)

1.96 g (0.008 mol) of intermediate 2-15 obtained in Synthesis Example 2-15, 5.34 g (0.008 mol) of intermediate 2-30 obtained in Synthesis Example 2-30, 1.92 g (0.006 mol) of zinc iodide, and benzonitrile in a 150 ml flask 2.44g was added, and it reacted for about 8 hours, stirring using a magnetic stirrer with 160 degreeC of internal temperature under nitrogen stream (10 ml / min). After cooling, about 6.1 g (yield 80.6 mol% of intermediates 2-15 and 2-30) were obtained in the same manner as in Example 2-5. The phthalocyanine compound thus obtained was measured for maximum absorption wavelength, gram absorption coefficient, absorbance ratio and heat resistance by the same operation as in Example 2-1, and the results are summarized in Table 2.

Example 2-36 Phthalocyanine Compound [ZnPc- {β- (2,6-Cl ₂ ) C ₆ H ₃ O} ₂ , {α- (4-COOC ₂ H ₄ OCH ₃ ) C ₆ H ₄ O} _x , {α- (4-CN) C ₆ H ₄ O} _y , {β- (4-COOC ₂ H ₄ OCH ₃ ) C ₆ H ₄ O} _4-x , {β- (4-CN) C ₆ H ₄ O} _2-y Cl ₂ H ₆ ] (0≤x <4, 0≤y <2)

2.31 g (0.008 mol) of intermediate 2-16 obtained in Synthesis Example 2-16, 5.34 g (0.008 mol) of intermediate 2-30 obtained in Synthesis Example 2-30, 1.92 g (0.006 mol) of zinc iodide, and benzonitrile in a 150 ml flask 2.55g was added, and it reacted for about 6 hours, stirring using a magnetic stirrer under the nitrogen stream (10 ml / min), the internal temperature of 160 degreeC. After cooling, about 5.65 g (yield 71.3 mol% of intermediates 2-16 and 2-30) were obtained in the same manner as in Example 2-5.

The phthalocyanine compound thus obtained was measured for maximum absorption wavelength, gram absorption coefficient, absorbance ratio and heat resistance by the same operation as in Example 2-1, and the results are summarized in Table 2.

Example 2-37 Phthalocyanine Compound [CuPc- {α- (4-COOC ₂ H ₄ OCH ₃ ) C ₆ H ₄ O} _{2 + x} , {β- (4-COOC ₂ H ₄ OCH ₃ ) C ₆ H ₄ O} _4-x Cl ₄ H ₆ ] (0≤x <4)

3.22 g (0.01 mol) of intermediate 2-1 obtained in Synthesis Example 2-1 in a 150 ml flask, 5.85 g (0.01 mol) of intermediate 2-19 obtained in Synthesis Example 2-19, 0.54 g (0.004 mol) of copper chloride, o- 11.76 g of dichlorobenzene and 5.21 g of octanol were added, and it reacted for about 6 hours, stirring using a magnetic stirrer under the nitrogen stream (10 ml / min), the internal temperature of 160 degreeC. After cooling, the solution obtained by suction filtration was dripped in 210.7 g of methanol, and it stirred for 30 minutes. Thereafter, 105.4 g of distilled water was added dropwise, followed by further stirring for 1 hour to precipitate crystals. The obtained crystals were suction filtered and then washed and purified by adding a mixed solution of 105.4 g of methanol and 52.7 g of distilled water, followed by stirring and washing. After suction filtration, the extracted crystals were vacuum dried at about 60 ° C. overnight to yield about 6.9 g (yield 73.4 mol% for Intermediate 2-1 and Intermediate 2-19).

The phthalocyanine compound thus obtained was measured for maximum absorption wavelength, gram absorption coefficient, absorbance ratio and heat resistance by the same operation as in Example 2-1, and the results are summarized in Table 2.

Example 2-38 Phthalocyanine Compound [ZnPc- {α- (4-CN) C ₆ H ₂ O} ₂ , {α- (2-COOC ₂ H ₄ OCH ₃ ) C ₁₀ H ₈ O} _x , { Synthesis of β- (2-COOC ₂ H ₄ OCH ₃ ) C ₁₀ H ₈ O} _{4- x} Cl ₄ H ₆ ] (0≤x <4)

1.96 g (0.008 mol) of intermediate 2-3 obtained in Synthesis Example 2-3, 5.14 g (0.008 mol) of intermediate 2-42 obtained in Synthesis Example 2-42, 1.32 g (0.004 mol) of zinc iodide, and benzonitrile in a 150 ml flask 2.78 g was added and reacted for about 10 hours while stirring using a magnetic stirrer under an air stream of nitrogen (10 ml / min), an internal temperature of 160 ° C.

After cooling, about 7.3 g (yield 94.2 mol% of intermediate 2-3 and intermediate 2-42) were obtained by the same operation as in Example 2-5.

The phthalocyanine compound thus obtained was measured for the maximum absorption wavelength, gram extinction coefficient, and heat resistance by the same operation as in Example 2-1, and the results are summarized in Table 2.

(Example 2-39)

The phthalocyanine compound obtained in Example 2-1 was evaluated for heat resistance by the method of the following heat resistance evaluation method 2. The results are shown in Table 2. In addition, in Table 2, it is the same value as Example 2-1 except evaluation of heat resistance.

(Heat resistance evaluation method 2)

0.42 g of binder polymer (BSX-SN-1) manufactured by Nippon Catalysts Co., Ltd., 20.0 g of propylene glycol monomethyl ether acetate (hereinafter referred to as PGMEA), 0.112 g of dipentaerythritol hexaacrylate, 0.01 g of Chiba Specialty Chemicals Co., Ltd. product (IRGACURE 369) was added, melt | dissolved, and mixed, and the resin coating liquid was prepared. The obtained resin coating liquid was apply | coated to the glass plate using the bar coater so that the pigment | dye density | concentration of 30weight% of dry film and dry film thickness might be 0.1 micrometer, and it dried at 80 degreeC for 30 minutes. The absorption spectrum of the coated glass plate thus obtained was measured with a spectrophotometer (manufactured by Hitachi, Ltd .: U-2910), which was referred to as a spectrum before heating. Next, the coating film glass plate which measured the spectrum before a heating was heat-processed at 220 degreeC for 20 minutes. The absorption spectrum of this heat-treated coated glass plate was measured with a spectrophotometer, and this was called the spectrum after heating. In each spectrum after heating, the absorbances up to 380 nm to 900 nm were integrated before heating and thus the difference between the absorbances before heating and after heating was measured. Further, the ΔE was calculated by the following equation when the said difference in the heating after the heating before spectrum E _1, E ₂ spectrum, the measured absorbance ΔE.

[Equation 5]

ΔE = {Σ (E 380 ~ 900nm absorbance of ₁₎ -Σ (absorbance at 380 ~ 900nm of the _{E 2)} × 100 / Σ} (380 ~ 900nm absorbance of E1) (%)

(Example 2-40)

In Example 2-39, the heat resistance was measured in the same manner as in Example 2-39 except that the phthalocyanine compound obtained in Example 2-1 was substituted with the phthalocyanine compound obtained in Example 2-3, and the results are shown in Table. 2 is shown. In addition, in Table 2, it is the same value as Example 2-3 except evaluation of heat resistance.

(Example 2-41)

In Example 2-39, the heat resistance was measured in the same manner as in Example 2-39 except that the phthalocyanine compound obtained in Example 2-1 was substituted with the phthalocyanine compound obtained in Example 2-10, and the results are shown in Table. 2 is shown. In addition, in Table 2, it is the same value as Example 2-10 except evaluation of heat resistance.

(Example 2-42)

In Example 2-39, the heat resistance was measured in the same manner as in Example 2-39 except that the phthalocyanine compound obtained in Example 2-1 was substituted with the phthalocyanine compound obtained in Example 2-16, and the results are shown in Table. 2 is shown. In addition, in Table 2, it is the same value as Example 2-16 except evaluation of heat resistance.

(Example 2-43)

In Example 2-39, the heat resistance was measured in the same manner as in Example 2-39 except that the phthalocyanine compound obtained in Example 2-1 was substituted with the phthalocyanine compound obtained in Example 2-21, and the results are shown in Table. 2 is shown. In addition, in Table 2, it is the same value as Example 2-21 except evaluation of heat resistance.

(Example 2-44)

In Example 2-39, the heat resistance was measured in the same manner as in Example 2-39 except that the phthalocyanine compound obtained in Example 2-1 was substituted with the phthalocyanine compound obtained in Example 2-23, and the results are shown in Table. 2 is shown. In addition, in Table 2, it is the same value as Example 2-23 except evaluation of heat resistance.

(Example 2-45)

In Example 2-39, the heat resistance was measured in the same manner as in Example 2-39 except that the phthalocyanine compound obtained in Example 2-1 was substituted with the phthalocyanine compound obtained in Example 2-28, and the results are shown in Table. 2 is shown. In addition, in Table 2, it is the same value as Example 2-28 except evaluation of heat resistance.

(Example 2-46)

In Example 2-39, the heat resistance was measured in the same manner as in Example 2-39 except that the phthalocyanine compound obtained in Example 2-1 was substituted with the phthalocyanine compound obtained in Example 2-33. 2 is shown. In addition, in Table 2, it is the same value as Example 2-33 except evaluation of heat resistance.

Comparative Example 2-1 Synthesis of Phthalocyanine Compound [ZnPc- {β- (2-COOCH ₃ ) C ₆ H ₄ O} ₄ H ₁₂ ]

4.17 g (0.015 mol) of intermediate 2-41 obtained in Synthesis Example 2-41, 1.32 g (0.004 mol) of zinc iodide, and 30.94 g of benzonitrile were added to a 150 ml flask, under a nitrogen stream (10 ml / min), and an internal temperature of 185 The reaction was carried out for about 5 hours while stirring using a magnetic stirrer. After cooling, about 3.8 g (yield 84.9 mol% of intermediates 2-41) were obtained in the same manner as in Example 2-5.

The phthalocyanine compound thus obtained was measured for maximum absorption wavelength, gram absorption coefficient, absorbance ratio and heat resistance by the same operation as in Example 2-1, and the results are summarized in Table 2.

(Comparative Example 2-2)

The phthalocyanine compound {ZnPc (3-CH ₃ OOCPhO) ₆ (3-HOOCPhO) ₂ F ₈ } described in Example 2-18 of JP-A-2008-50599 was subjected to the same operation as in Example 2-1. Maximum absorption wavelength, gram extinction coefficient, absorbance ratio, and heat resistance were measured, and the result is put together in Table 2.

εg Heat resistance
(ΔE) λmax / nm PGMEA Solubility Abs (λ710 nm) / Abs (λ520 nm) Example 2-1 36  2 687.0 ○ 42.5 Example 2-2 37  4 686.0 ○ 56.0 Example 2-3 47  4 688.0 ○ 63.1 Examples 2-4 36  3 686.0 ○ 39.4 Example 2-5 42 10 692.0 ○ 118.3 Example 2-6 26  5 692.0 ○ 26.2 Example 2-7 27  8 687.0 ○ 33.3 Example 2-8 42  4 684.0 ○ 80.5 Example 2-9 31  3 689.0 ○ 60.3 Example 2-10 25  9 691.0 ○ 56.8 Example 2-11 50  2 681.5 ○ 39.6 Example 2-12 47  6 684.0 ○ 26.4 Example 2-13 84 10 690.0 ○ 52.6 Example 2-14 36  5 688.0 ○ 82.6 Example 2-15 30  7 689.0 ○ 131.6 Example 2-16 40  6 688.0 ○ 65.4 Example 2-17 33  3 687.0 ○ 60.1 Example 2-18 35  4 691.0 ○ 29.8 Example 2-19 32  4 684.0 ○ 24.9 Example 2-20 41  2 685.0 ○ 44.8 Example 2-21 45  2 685.0 ○ 54.8 Example 2-22 41  3 685.0 ○ 64.0 Example 2-23 30  9 689.0 ○ 28.0 Example 2-24 41  3 681.0 ○ 19.1 Example 2-25 24  5 681.0 ○ 63.0 Example 2-26 39  6 686.0 ○ 31.1 Example 2-27 33  3 682.0 ○ 66.8 Example 2-28 29  8 684.0 ○ 54.8 Example 2-29 39  2 684.0 ○ 61.3 Example 2-30 50 10 681.5 ○ 30.4 Example 2-31 26  2 675.0 ○ 35.1 Example 2-32 52  2 686.0 ○ 41.1 Example 2-33 29  3 680.0 ○ 35.0 Example 2-34 30  3 643.0 ○ 31.0 Example 2-35 31  5 679.0 ○ 26.4 Example 2-36 32  5 684.0 ○ 36.6 Example 2-37 28 9 644.0 ○ 20.4 Example 2-38 28 4 686.0 ○ 69.3 Example 2-39 36  3 687.0 ○ 42.5 Example 2-40 47  4 688.0 ○ 63.1 Example 2-41 25  8 691.0 ○ 56.8 Example 2-42 40  7 688.0 ○ 65.4 Example 2-43 45  3 685.0 ○ 54.8 Example 2-44 30  9 689.0 ○ 28.0 Example 2-45 29  9 684.0 ○ 54.8 Example 2-46 29  4 680.0 ○ 35.0 Comparative Example 2-1 48 22 672.0 × (filter clogging) 13.6 Comparative Example 2-2 83 30 681.0 △ (with some melting residue) 12.2

The phthalocyanine compound synthesized in Examples 2-1 to 38 has a gram absorbance coefficient (? G) compared to the β-position 4-substituted phthalocyanine compound synthesized in Comparative Example 2-1 and the β-position 8-substituted phthalocyanine compound synthesized in Comparative Example 2-2. ) Have no predominance, but the heat resistance is improved by 2 times or more compared to the β-position 4-substituted phthalocyanine compound having high heat resistance synthesized in Comparative Example 2-1. In addition, compared with Comparative Examples 2-1 and 2, the phthalocyanine compounds of Examples 2-1 to 38 showed very excellent solvent solubility.

In addition, even when the ratio of absorbance of 710 nm showing extra emission of PDP and 520 nm, which is the wavelength of representative visible light, using the phthalocyanine compound of the present application, the ratio of absorbance was large compared to Comparative Examples 2-1 and 2, so that 710 nm light was efficiently cut. The effect was possible.

In addition, this application is based on Japanese Patent Application No. 2008-222279 for which it applied on August 29, 2008, and Japanese Patent Application No. 2009-100262 for which it applied on April 16, 2009, The indication is referred to It is quoted in its entirety by

Claims (12)

Formula (1-3) shown below:

In the formula, Z ₁ to Z ₁₆ are each independently a hydrogen atom, a halogen atom, the following formula 2:
(2)
-XA ₁
In the formula, X is an oxygen atom or a sulfur atom, A ₁ is a phenyl group, a phenyl group having 1 to 5 substituents R or a naphthyl group having 1 to 7 substituents R, and the substituents R are each independently a nitro group or a COOR ₁ , OR ₂ (R ₂ is an alkyl group having 1 to 8 carbon atoms), a halogen atom, an aryl group, a cyano group or an alkyl group having 1 to 8 carbon atoms that may be substituted with a halogen atom, wherein R ₁ is an alkyl group having 1 to 8 carbon atoms (In this case, the alkyl group may be substituted with an alkyloxy group having 1 to 8 carbon atoms, a halogen atom or an aryl group) or the following general formula 3:
(3)

Wherein R ₃ is an alkylene group having 1 to 3 carbon atoms, R ₄ is an alkyl group having 1 to 8 carbon atoms, and n is an integer of 1 to 4;
Or a group represented by the following formula (2 '):
[Formula 2 ']

In the formula, R 'is an alkylene group having 1 to 3 carbon atoms, R "is an alkyl group having 1 to 8 carbon atoms, l is an integer of 0 to 4;
In this case, 4 to 10 of Z ₁ ~ Z ₁₆ is a group represented by the formula (2) or (2 '), at least one is a group represented by the formula (2), 3 to 11 is a hydrogen atom, at least one halogen Is an atom,
M represents a nonmetal, metal, metal oxide or metal halide:
Phthalocyanine compound represented by
Formula (1-2) shown below:

In the formula, Z ₁ to Z ₁₆ are each independently a hydrogen atom, the following formula:
(2)
-XA ₁
In the formula, X is an oxygen atom or a sulfur atom, A ₁ is a phenyl group, a phenyl group having 1 to 5 substituents R or a naphthyl group having 1 to 7 substituents R, and the substituents R are each independently a nitro group or a COOR ₁ , OR ₂ (R ₂ is an alkyl group having 1 to 8 carbon atoms), a halogen atom, an aryl group, a cyano group or an alkyl group having 1 to 8 carbon atoms that may be substituted with a halogen atom, wherein R ₁ is an alkyl group having 1 to 8 carbon atoms (In this case, the alkyl group may be substituted with an alkyloxy group having 1 to 8 carbon atoms, a halogen atom or an aryl group) or the following general formula 3:
(3)

In formula, R <_3> is a C1-C3 alkylene group, R <_4> is a C1-C8 alkyl group, n is an integer of 1-4;
Or a group represented by the following formula (2 '):
[Formula 2 ']

Wherein R 'is an alkylene group of 1 to 3 carbon atoms, R "is an alkyl group of 1 to 8 carbon atoms, and l is an integer of 0 to 4:
Which is represented by
In this case, 1 to 3 of Z ₁ , Z ₄ , Z ₅ , Z ₈ , Z ₉ , Z ₁₂ , Z _13, and Z ₁₆ are groups represented by Formula 2 or Formula 2 ′, and Z ₂ , Z ₃ , Z 3 to 1 of ₆ , Z ₇ , Z ₁₀ , Z ₁₁ , Z _14, and Z ₁₅ are groups represented by Formula 2 or 2 ′, and a total of 4 of Z ₁ to Z ₁₆ are represented by Formula 2 or Formula 2 ′. Is a group shown, at least one of Z ₁ to Z ₁₆ is a group represented by the formula (2),
M represents a nonmetal, metal, metal oxide or metal halide:
Phthalocyanine compound represented by. The method of claim 1,
In the phthalocyanine compound represented by said formula (1-3), said A <_1> is a phthalocyanine compound which is a phenyl group which has 1-5 substituents R, or a naphthyl group which has 1-7 substituents R. The method according to claim 1 or 2,
A phthalocyanine compound of 3 to 9 of the Z ₁ to Z ₁₆ is a hydrogen atom. 4. The method according to any one of claims 1 to 3,
4-8 of Z ₁ to Z ₁₆ are groups represented by Formula 2 or 2 ', and 3 to 6 are hydrogen atoms. The method according to any one of claims 1 to 4,
In the phthalocyanine compound represented by Formula (1-3), at least one of the groups represented by Formula 2 is represented by the following formula 4:
[Chemical Formula 4]

In Formula 4, X and R ₁ are as defined in Formula 2, R corresponds to the substituent R, and m and m ₁ are integers of 1 to 5, provided that m ₁ ≦ m:
Group represented by the following formula (4 '):
[Formula 4 ']

In Formula 4 ', X is as defined in Formula 2, R corresponds to substituent R, and m' is an integer from 2 to 5:
The phthalocyanine compound whose group or at least ₁ substituent is represented by the naphthyloxy group or the naphthylthio group which is COOR1. The method of claim 5,
In the phthalocyanine compound represented by the said Formula (1-3), the phthalocyanine compound whose R in 2 and 6 positions in said General formula 4 'is a halogen atom. The method according to any one of claims 1 to 6,
In the phthalocyanine compound represented by Formula (1-3), at least one of the groups represented by Formula 2 is represented by the following Formula 5a:
[Formula 5a]

In formula (5a), X is as defined in formula (1), R corresponds to the substituent, and m is an integer of 1-5:
Phthalocyanine compound represented by. The method according to any one of claims 1 to 7,
In the phthalocyanine compound represented by the formula (1-3), Z ₁ ~ Z groups are present in the case of four or eight represented by the formula (4) of _16, Z ₁ ~ Z ₁ out of ₁₆ at least to the group represented by the formula (4) A phthalocyanine compound other than the group shown by Formula (2) or group represented by Formula (2 '). The method of claim 1,
In the phthalocyanine compound represented by the formula (1-2), Z ₁ to Z ₁₆ each independently represent a hydrogen atom or a group represented by the formula (2). The method according to claim 1 or 9,
The phthalocyanine compound of the phthalocyanine compound represented by the formula (1-2), wherein at least one of the groups represented by the formula (2) is -XA ₁ wherein the substituent is a nitro group, COOR ₁ , a halogen atom or a cyano group. The method according to any one of claims 1, 9 or 10,
In the phthalocyanine compound represented by Formula (1-2), at least one of the groups represented by Formula 2 is represented by the following Formula 5:
[Chemical Formula 5]

In Formula 5, X is the same definition as in Formula 2, R corresponds to the substituent R, and m is an integer of 1 to 5:
[Formula 5 ']

In Formula 5 ', X is the same definition as in Formula 2, R corresponds to the substituent R, and m''is an integer of 1-7:
Phthalocyanine compound represented by. The filter for flat panel displays containing the phthalocyanine compound in any one of Claims 1-11.