KR20120087877A - Phthalocyanine compound - Google Patents

Abstract

Provided is a phthalocyanine compound having high solubility in an ether solvent. In the phthalocyanine compound of the present invention, 2 to 8 of the substituents Z _{1 to} Z ₁₆ in the phthalocyanine skeleton are substituents (a) or substituents (b) of the following formula (2) or (2 '), and the remaining part is a chlorine atom. , At least two of 2 to 8 substituents (a) or (b) are substituents (a).

Description

Phthalocyanine compound

The present invention relates to a phthalocyanine compound and a filter for a flat panel display containing the compound. Specifically, the present invention relates to a phthalocyanine compound having high solubility in an ether solvent and a filter for a flat panel display including the compound.

In recent years, phthalocyanine-based compounds are stable to light, heat, temperature, etc., and are excellent in fastness, and thus, near-infrared absorbing pigments used in optical recording media such as compact disks, laser disks, optical memory disks, and optical cards using semiconductor lasers as light sources. It is used as. In addition, PDP (Plasma Display Panel), which is thin and can be applied to large screens, is attracting attention recently. PDP generates near-infrared light during plasma discharge, and this near-infrared light prevents malfunction of electrical equipment such as TVs, coolers, and video decks for home appliances. It is a problem to induce. In order to solve these problems, the development of phthalocyanine compounds with high visible light transmittance, high near-infrared light cut efficiency, excellent absorption ability in the near infrared region, and excellent heat resistance, light resistance and weather resistance Has been done.

As described above, various phthalocyanine compounds have been studied and developed. However, 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 and methyl. It is known that it is soluble in organic solvents, such as ketones, such as ethyl ketone, chloroform, and toluene, for example (refer patent document 1). However, conventional phthalocyanine compounds did not have sufficient solubility in ether solvents. Therefore, even if the use of an ether solvent is a suitable use, there is a problem that a sufficient amount of the phthalocyanine compound cannot be blended, so that the choice of the solvent to be used and the type of resin to be blended is limited.

In particular, color toner, inkjet ink, household inkjet ink, anti-counterfeiting ink, in particular, anti-counterfeiting barcode ink or anti-counterfeiting offset ink, lenses or shields of goggles, dyeing agents for plastic recycling, optical recording Preheating aids, thermal transfer transfers, photothermal exchangers such as thermal stencils, thermal rewritable recording photothermal exchangers, anti-counterfeiting of ID cards, plastics Selection of solvents for use in light heat exchangers for laser transmission welding (LTW), heat ray shielding agents, near infrared absorption filters, and the like is limited, and there is a limit to the applicable applications. Therefore, there is a high demand for a phthalocyanine compound which has high solubility in ether solvents and is also useful for applications not conventionally applicable.

Patent Document 1: Japanese Patent Application Laid-Open No. 6-107663

Accordingly, an object of the present invention is to provide a phthalocyanine compound having high solubility in an ether solvent.

MEANS TO SOLVE THE PROBLEM As a result of earnestly researching in order to solve the said problem, the present inventors discovered that the phthalocyanine compound which has a specific structure has high solubility with respect to an ether solvent, and came to complete this invention.

That is, the said object is achieved by the phthalocyanine compound represented by following formula (1):

[Formula 1]

In said formula (1), Z <_1> Z <_16> is a chlorine atom, following formula (2) or (2 ') each independently:

[Formula 2]

In said formula (2) and (2 '), R <^1> is a C1-C3 alkylene group, R <^2> is a C1-C8 alkyl group, R <^4> is a C1-C8 alkoxy group or a halogen atom, m is an integer of 1? 4, p is 0 or 1,

Substituent (a) represented by

Formula (3-1) shown below:

(3)

    -X-Ar (3-1)

In said formula (3-1), X is an oxygen atom or a sulfur atom, Ar is a phenyl group or a naphthyl group which may be substituted by R <^3>, and R <^3> is respectively independently a cyano group, a nitro group, COOY, OY, A C1-8 alkyl group which may be substituted with a halogen atom, an aryl group or a halogen atom, where Y is a C1-8 alkyl group,

Substituent (b-1) represented by

Formula (3-2) shown below:

[Formula 4]

-XR ⁷ -COO-R ⁵ (3-2)

In said formula (3-2), X is an oxygen atom or a sulfur atom, R <^7> is a C1-C5 alkylene group, R <^5> may be substituted by the halogen atom or the C1-C8 alkoxy group, It is an alkyl group of 8,

Substituent (b-2) represented by

Formula (3-3) shown below:

[Chemical Formula 5]

-XR ⁷ -Si (R ⁶ ) ₃ (3-3)

In said formula (3-3), X is an oxygen atom or a sulfur atom, R <^7> is a C1-C5 alkylene group, R <^6> is respectively independently a C1-C8 alkoxy group or a C1-C8 alkyl group. to be,

Substituent (b-3) represented by

  Groups derived from 7-hydroxycoumarin (b-4) and

  Group (b-5) derived from 2,3-dihydroxyquinoxane,

Substituent (b) selected from the group consisting of

In this case, 2? 8 of Z ₁ ? Z ₁₆ are a substituent (a) or a substituent (b), and the remaining part is a chlorine atom, and at least two of 2? 8 substituents (a) or a substituent (b) are a substituent. (a),

M represents a metal, metal, metal oxide or metal halide.

The phthalocyanine compound of the present invention can be dissolved in an ether solvent while maintaining high visible light transmittance, high near-infrared cut efficiency, and near-infrared selective absorption in addition to excellent resin compatibility, heat resistance, light resistance, and weather resistance. have. Therefore, it can be used even if it is relatively selectively dissolved in an ether solvent. Moreover, when solvent other than an ether solvent is used, it can also be used for the application of a phthalocyanine pigment | dye on the plastic which may melt | dissolve.

The 1st of this invention relates to the phthalocyanine compound represented by following formula (1):

[Formula 6]

In said formula (1), Z <_1> Z <_16> is a chlorine atom, following formula (2) or (2 ') each independently:

[Formula 7]

In said formula (2) and (2 '), R <^1> is a C1-C3 alkylene group, R <^2> is a C1-C8 alkyl group, R <^4> is a C1-C8 alkoxy group or a halogen atom, m is an integer of 1? 4, p is 0 or 1,

Substituent (a) represented by

Formula (3-1) shown below:

[Formula 8]

    -X-Ar (3-1)

In said formula (3-1), X is an oxygen atom or a sulfur atom, Ar is a phenyl group or naphthyl group which may be substituted by R <^3> , and R <^3> is respectively independently a cyano group, a nitro group, COOY, OY, A C1-8 alkyl group which may be substituted with a halogen atom, an aryl group or a halogen atom, where Y is a C1-8 alkyl group,

Substituent (b-1) represented by

Formula (3-2) shown below:

[Chemical Formula 9]

-XR ⁷ -COO-R ⁵ (3-2)

In said formula (3-2), X is an oxygen atom or a sulfur atom, R <^7> is a C1-C5 alkylene group, R <^5> may be substituted by the halogen atom or the C1-C8 alkoxy group, It is an alkyl group of 8,

Substituent (b-2) represented by

Formula (3-3) shown below:

[Formula 10]

-XR ⁷ -Si (R ⁶ ) ₃ (3-3)

In said formula (3-3), X is an oxygen atom or a sulfur atom, R <^7> is a C1-C5 alkylene group, R <^6> is respectively independently a C1-C8 alkoxy group or a C1-C8 alkyl group. to be,

Substituent (b-3) represented by

  Groups derived from 7-hydroxycoumarin (b-4) and

  Group (b-5) derived from 2,3-dihydroxyquinoxane,

Substituent (b) selected from the group consisting of

In this case, 2? 8 of Z ₁ ? Z ₁₆ are a substituent (a) or a substituent (b), and the remaining part is a chlorine atom, and at least two of 2? 8 substituents (a) or a substituent (b) are a substituent ( a),

M represents a metal, metal, metal oxide or metal halide.

Hereinafter, the phthalocyanine compound represented by said formula (1) is also only called "phthalocyanine compound" or "phthalocyanine compound of this invention."

In the phthalocyanine compound of the present invention, 2 to 8 (preferably 2 to 6) in Z ₁ ? Z ₁₆ are a substituent (a) or a substituent (b), and the remaining part is a chlorine atom. At this time, at least 2 (preferably 2-6) of 2-8 substituents (a) or substituents (b) are substituents (a). Phthalocyanine compounds having such a structure have the following advantages: (i) solubility in ether solvents is improved; (ii) In the near-infrared region, it has a maximum absorption wavelength lambda max in the wavelength region of 640? 750 nm. Among these, (i) high solubility in ether solvents may be used in combination with a resin having high solubility in ether solvents and a pigment, and even in the case of using a plastic which is dissolved in a solvent other than the ether solvent, The pigment | dye can be apply | coated to. And (ii) the maximum absorption wavelength (λ max) in the short wavelength region, which is due to the useless light in the near-infrared region (700? 750 nm) emitted by flat panel displays, especially PDPs and LCDs, or the impure red wavelength (640?) 700 nm) light can be cut, for example, to prevent the malfunction of the optical communication system and at the same time to produce a vivid red color. In particular, since PDP shows extra large light emission near 710 nm, a dye that absorbs 710 nm light and has a high transmittance of visible light such as 520 nm is useful. In addition to the above, each phthalocyanine compound can obtain a spectrum with a relatively sharp peak at the maximum absorption wavelength due to low mobility of the wavelength. Therefore, the phthalocyanine compound of the present invention is easy to obtain a desired wavelength even in the form of a mixture.

Moreover, the phthalocyanine compound of this invention is a substituent (a) or (b) which is a substituent containing an oxygen atom (-OE; E represents arbitrary substituent) or a substituent containing a sulfur atom (-SE; in this case, E Represents an arbitrary substituent) is introduced into the phthalocyanine skeleton. In general, the properties of the phthalocyanine compound vary depending on the kind of substituent, the introduction sites (α positions, β positions), the number of introduction groups, and the like. For example, as a kind of substituent, it is the order of the substituent (-OE) containing an oxygen atom, the substituent (-SE) containing a sulfur atom, and the substituent containing the nitrogen atom (-NE; E represents an arbitrary substituent in this case). The absorption wavelength of the phthalocyanine compound can be shifted to the shorter wavelength side. Therefore, in the phthalocyanine compound of the present invention, since a substituent (-OE) containing an oxygen atom or a substituent (-SE) containing a sulfur atom is introduced, a near infrared wavelength range of 640? 750 nm, more preferably 640? 705 nm, particularly 645? 700 nm is introduced. The selective absorption ability at is increased. In addition, in the phthalocyanine compound in which a substituent (-OE) containing an oxygen atom or a substituent (-SE) containing a sulfur atom is introduced at β, the maximum absorption wavelength is further shifted toward the shorter wavelength than in the case where such a substituent is introduced at α. Therefore, when a large number of substituents (a) or (b) is introduced at β, the maximum absorption wavelength of the resulting phthalocyanine compound is further shifted toward the shorter wavelength.

Moreover, the phthalocyanine compound of this invention is Z <_2> , Z <_3> , Z <_6> , Z <_7> , Z <_10> , Z <_11> , Z <_14> and Z <_15> in this formula (In this specification, it is simply a substituent of "(beta) -position). Or "because it is also referred to as" beta "), it is excellent in heat resistance. In addition, since Z ₁ , Z ₄ , Z ₅ , Z ₈ , Z ₉ , Z ₁₂ , Z ₁₃ and Z ₁₆ (herein, simply referred to as "substituent on α" or "α") have a substituent, ether It is excellent in solubility in the solvent (also referred to simply as "solvent solubility" in the present specification). A phthalocyanine compound aims at the balance of heat resistance and solvent solubility by selecting the number of substituents and the kind of substituents suitably.

EMBODIMENT OF THE INVENTION Hereinafter, preferable embodiment in 1st aspect of this invention is described.

In the present invention, 2 to 8 of the substituent Z ₁ ? Z ₁₆ in the formula (1) are a substituent (a) or a substituent (b). It is preferable that the number of substituents (a) or substituent (b) is small in consideration of the gram absorption coefficient among these, and 2 to 6 of the substituents Z ₁ ? Z ₁₆ in the formula (1) are the substituents (a) or the substituents (b). More preferably the remaining part is a chlorine atom. In consideration of solvent solubility, 3 to 6, more preferably 4 to 8, still more preferably 6 to 8 are substituents (a) or substituents (b), and the remaining portion is preferably a chlorine atom. If the total substitution number of substituents (a) and (b) in Z _{1 to} Z ₁₆ is less than 2, the solvent solubility decreases, which is not preferable. Moreover, when the total substitution number of substituents (a) and (b) exceeds 8, since molecular weight will become large and gram extinction coefficient will become low, it is unpreferable. In addition, the remaining part in which the substituent (a) or the substituent (b) is not introduced in Z ₁ ═Z ₁₆ is a chlorine atom. Thus, heat resistance can be improved by arrange | positioning a chlorine atom to a remainder part.

Further, the introduction position in the phthalocyanine skeleton of the 2 to 8 substituents (a) or the substituents (b) is not particularly limited as long as the total substitution number is in the above range. Therefore, if each structural unit including Z ₁ ? Z ₄ , Z ₅ ? Z ₈ , Z ₉ ? Z ₁₂ , Z ₁₃ ? Z ₁₆ is set to structural units A, B, C, D, respectively, 2? 8 substituents are used. (a) or the substituent (b) may be introduced almost uniformly in the structural unit A? D, or may be introduced unevenly. Preferably, 2-8 substituents (a) or substituents (b) are introduced unevenly in the structural unit A? D. Such a mixture of substituents is preferable in view of achieving a balance of solubility, wavelength control, durability (light resistance, heat resistance), and absorbance per gram in various solvents. In addition, although the detailed mechanism is unclear, the solubility in an ether solvent is improved by the presence of an appropriate number of substituents (a) and (b), and the presence of an appropriate number of chlorine atoms makes the absorption wavelength long, and the durability (light resistance) , Heat resistance) is considered to be improved. In addition, when two or more types of substituents (a) or (b) exist, these substituents (a) and (b) may be same or different, respectively.

Moreover, at least 2, more preferably 2.5 of said 2-8 substituent (a) or substituent (b) are substituents (a). Although the upper limit of the substituent (a) which can occupy in the substituent (a) or the substituent (b) here is eight, Preferably it is seven, More preferably, six. If the substituent (a) is less than two here, since solvent solubility will fall, it is not preferable. Moreover, since the molecular weight becomes large and gram extinction coefficient becomes small when there are more than eight substituents (a), it is unpreferable. In particular, when 6? 8 out of Z ₁ ? Z ₁₆ are substituents (a) or substituents (b), and the remaining part is a chlorine atom, 4? 7 out of 6? 8 substituents (a) or substituents (b) It is preferable that it is a substituent (a). The phthalocyanine compound having such a substituent (a) is excellent in solvent solubility and visible light transmittance of 520 nm. Or two or more and less than six of Z ₁ ? Z ₁₆ are substituents (a) or substituents (b), and the remaining part is a chlorine atom, and two or more and less than six substituents (a) or substituents (b) It is preferable that less than 2-6, More preferably, it is 2-5, Especially preferably, 2.5-5 is a substituent (a). The phthalocyanine compound which has such a substituent (a) is excellent in gram absorption coefficient and heat resistance.

Here, the combination of the introduction positions of the substituents (a) and (b) of the 2 to 8 substituents (a) or the substituents (b) is not particularly limited as long as at least two of them are substituents (a). For example, 4? 8 of Z ₁ ? Z ₁₆ are a substituent (a) or a substituent (b), and the remaining part is a chlorine atom, and at least 4 of 4? 8 substituents (a) or a substituent (b) are In the case of the substituent (a), all 14 combinations may be applied. Similarly, 6? 8 of Z ₁ ? Z ₁₆ are a substituent (a) or a substituent (b), and the remaining part is a chlorine atom, and 4? 7 of 6? 8 substituents (a) or a substituent (b) are a substituent (a ), All 11 combinations can be applied. Among these, considering the above characteristics such as heat resistance and solvent solubility, in particular solvent solubility, as a preferable combination of 6? 8 substituents (a) or (b), 4 substituents (a) and 2 substituents (b), 4 Substituent (a) and 3 substituents (b), 4 substituents (a) and 4 substituents (b), 5 substituents (a) and 2 substituents (b), 6 substituents (a) and 0 substituents (b), six substituents (a) and one substituent (b), or seven substituents (a) and zero substituents (b). In addition, the substituent (a) may be the same in the phthalocyanine frame | skeleton, or may differ, respectively.

In the present invention, the substituent (a) is represented by the formula (2) or (2 '). In addition, as can be seen from the above formula, the substituent (a) has one substituent “-COO (R ¹ O) _m R ² ” and, if necessary, a phenoxy group having one C 1-8 alkoxy group or halogen atom (-R ⁴ ) Or naphthoxy (formula (2 ')) having one substituent "-COO (R ¹ O) _m R ² ".

In the formula (2 '), the oxygen atom (-O-) and the substituent "-COO (R ¹ O) _m R ² " may be substituted with any hydrogen atom of the naphthalene ring. That is, in the formula (2 '), the substituent "-COO (R ¹ O) _m R ² " is present in the benzene ring of the oxygen atom in the two benzene rings, which means that the substituent is present in the position. May be present in the other benzene ring. That is, the substituent (a) of the formula (2 ') includes both the following substituents (a ₁ ) and (a ₂ ).

[Formula 11]

Substituent (a ₁ )

Substituent (a ₂ )

In said formula (2) and (2 '), R <^1> is a C1-C3 alkylene group. Here, as an alkylene group having 1 to 3 carbon atoms, there are a methylene group, an ethylene group, a tetramethylene group, and a propylene group. Among these, in consideration of the above characteristics such as heat resistance and solvent solubility, in particular solvent solubility, R ¹ is preferably an ethylene group or a propylene group, and more preferably an ethylene group.

In the formulas (2) and (2 '), R ² is an alkyl group having 1 to 8 carbon atoms. The alkyl group having 1 to 8 carbon atoms is not particularly limited, and examples thereof include a linear, branched or cyclic alkyl group having 1 to 8 carbon atoms. More specifically, examples of the alkyl group having 1 to 8 carbon atoms include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert-butyl group, n-pentyl group and isopen And linear, branched or cyclic alkyl groups such as a methyl group, neopentyl group, n-hexyl group, cyclohexyl group, n-heptyl group, n-octyl group and 2-ethylhexyl group. Among these, in consideration of the above characteristics such as heat resistance and solvent solubility, in particular solvent solubility, a linear or branched alkyl group having 1 to 5 carbon atoms, particularly a linear or branched alkyl group having 1 to 3 carbon atoms is preferable. In the formulas, m represents the number of repeating unit of the oxyalkylene group (R ¹ O), an integer of 1? 4. Considering the above characteristics such as heat resistance and solvent solubility, in particular solvent solubility, m is preferably 1? 2.

In said formula (2), R <^4> is a C1-C8 alkoxy group or halogen atom. Here, as the alkoxy group having 1 to 8 carbon atoms, straight chains such as methoxy group, ethoxy group, propoxy group, isopropoxy group, butoxy group, pentyloxy group, hexyloxy group, 2-ethylhexyloxy group, octyloxy group, A branched or cyclic alkoxy group is mentioned. Among these, in consideration of the above characteristics such as heat resistance and solvent solubility, especially solvent solubility, a linear or branched alkoxy group having 1 to 5 carbon atoms, particularly a linear or branched alkoxy group having 1 to 3 carbon atoms is preferable. Moreover, a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom are mentioned as a halogen atom. Of these, chlorine atoms are preferred in consideration of heat resistance and solvent solubility. In the above formula, p represents the number of alkoxy groups or halogen atoms (R ⁴ ) bonded to the phenoxy group, and is 0 or 1.

In the substituent (a) of the formula (2), the bonding position of the substituent-COO (R ¹ O) R ^{2 to} the benzene ring is not particularly limited. If for example, p is 0, the substituent (a) is 1 substituent _{^{"-COO (R 1 O) m R}} 2 'is has a structure bonded to a phenoxy group. Here, the substituent "-COO (R ¹ O) _m R ² " is disposed at any position of the ortho position (second position), the meta position (the third position) or the para position (the fourth position) of the phenoxy group. Among these, 2nd and 4th positions are preferable, and 4th position is especially preferable. When the relatively bulky substituent-COO (R ¹ O) R ² is placed in position 4, the resulting phthalocyanine compound absorbs 710 nm of light and has a high transmittance of visible light such as 520 nm, that is, an absorbance ratio [absorbance of = 710 nm]. Absorbance at / 520 nm; also referred to as "Abs (λ710 nm) / Abs (λ520 nm)". In addition, placing a relatively bulky substituent -COO (R ¹ O) R ² above 4, the phthalocyanine compounds obtained can improve the solvent solubility.

In the above formula (2), when p is 1, the substituent (a) is substituted with one substituent "-COO (R ¹ O) _m R ² " and one C 1-8 alkoxy group or halogen atom (-R ⁴ ) has a structure bonded to the phenoxy group. Here, the substituents "-COO (R ¹ O) _m R ² " and "R ⁴ " may each be introduced at any position of the phenoxy group. At this time, in consideration of the above characteristics such as heat resistance, absorbance ratio and solvent solubility, in particular, solvent solubility, second, fourth, second, fifth, second, sixth, third, and fourth positions are preferable in consideration of solvent solubility and absorbance ratio. 2nd, 4th, and 2nd and 6th positions are more preferable.

The position of the bond of the oxygen atom (-O-) to the naphthalene ring in the substituent (a) of the formula (2 ') is not particularly limited, and may be any one derived from 1-naphthol or 2-naphthol. Preferably the substituent (a) is derived from 1-naphthol. Similarly, the bonding position of the substituent-COO (R ¹ O) R ^{2 to} the naphthalene ring is also not particularly limited. The carboxylic acid ester (-COO (R ¹ O) R ² ) is particularly preferred when the solubility tends to improve when adjacent to the oxygen atom (-O-). Therefore, when the substituent (a) is derived from 1-naphthol, the bonding position of the substituent: -COO (R ¹ O) R ^{2 to} the naphthalene ring is 2nd, 3rd, 4th, 5th, 6th, 7th, or Although any of 8th position may be sufficient, considering heat resistance, solvent solubility, etc., 2nd, 3rd, and 4th positions are preferable, and 2nd position is more preferable. When the substituent (a) is derived from 2-naphthol, the bonding position of the substituent: -COO (R ¹ O) R ^{2 to} the naphthalene ring is 1st, 3rd, 4th, 5th, 6th, 7th, or Eighth place may be sufficient, but preferably 1st, 3rd, and 6th positions are preferable, and a 3rd and 6th position is more preferable in consideration of heat resistance, solvent solubility, etc.

That is, it is especially preferable that the substituent (a) has the following six types of structures.

[Chemical Formula 12]

,

,

,

,

,

,

,

,

,

,

.

.

Moreover, in this invention, a substituent (b) is a following formula (3-1):

[Chemical Formula 13]

    -X-Ar (3-1)

Substituent (b-1) represented by following formula (3-2):

[Formula 14]

-XR ⁷ -COO-R ⁵ (3-2)

In said formula (3-2), X is an oxygen atom or a sulfur atom, R <^7> is a C1-C5 alkylene group, R <^5> may be substituted by the halogen atom or the C1-C8 alkoxy group, It is an alkyl group of 8,

Substituent (b-2) represented by following formula (3-3):

[Formula 15]

-XR ⁷ -Si (R ⁶ ) ₃ (3-3)

In said formula (3-3), X is an oxygen atom or a sulfur atom, R <^7> is a C1-C5 alkylene group, R <^6> is respectively independently a C1-C8 alkoxy group or a C1-C8 alkyl group. to be,

Substituent (b-3) represented by

  Groups derived from 7-hydroxycoumarin (b-4) and

  Group (b-5) derived from 2,3-dihydroxyquinoxane,

Substituent (b) chosen from the group which consists of these is shown. In the case where a plurality of substituents (b) are present in the phthalocyanine skeleton, such substituents (b) may be the same or different.

The substituent (b) may be a substituent (b-1) of the formula (3-1). In said formula (3-1), X is an oxygen atom (-O-) or a sulfur atom (-S-), Preferably it is an oxygen atom. When X is an oxygen atom, the maximum absorption wavelength of the phthalocyanine compound obtained can be shifted toward a short wavelength side, and therefore the maximum absorption wavelength ((lambda) max) of the obtained phthalocyanine compound can be easily adjusted to the wavelength range of 640 to 750 nm among near-infrared regions.

In said formula (3-1), Ar is a phenyl group or naphthyl group which may be substituted by R <^3> , Preferably it is a phenyl group. In the case where Ar is a phenyl group which may be substituted with R ³ , Ar is a group represented by the following formula.

[Chemical Formula 16]

In said formula, X and R <^3> are the same as the definition in said Formula (3-1), and n is an integer of 1-5.

In formula (3-1), R ³ is a substituent which may be introduced into a phenyl group or a naphthyl group, and is a cyano group (-CN), a nitro group (-NO ₂ ), COOY, OY, a halogen atom, an aryl group or a halogen It is a C1-C8 alkyl group which may be substituted by the atom. When a plurality of R ³ 's are present (the number of substitutions n of R ³ in Formula (3-1) is an integer of 2 to 5), the plurality of R ^{3' s} may be the same or different. Y in the case where R ³ in the R ³ is COOY or OY is an alkyl group having 1 to 8 carbon atoms. Herein, the alkyl group having 1 to 8 carbon atoms is not particularly limited, and examples thereof include a linear, branched or cyclic alkyl group having 1 to 8 carbon atoms, and specific examples thereof are the same as those defined for R ² . Of these, in view of the above characteristics such as heat resistance and solvent solubility, in particular, solvent solubility, a linear or branched alkyl group having 1 to 5 carbon atoms, particularly a linear or branched alkyl group having 1 to 3 carbon atoms is preferable.

Moreover, a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom are mentioned as a halogen atom when said R <^3> is a halogen atom. Of these, chlorine atoms and fluorine atoms are preferable in consideration of heat resistance, solvent solubility and the like. In addition, when R ³ is a chlorine atom or a fluorine atom, the molecular weight of the dye may be reduced and the absorbance per gram may be increased.

Moreover, as said aryl group in the case where said R <^3> is an aryl group, aryl groups, such as a phenyl group, p-methoxyphenyl group, a pt-butylphenyl group, and a p-chlorophenyl group, are mentioned. Especially, since the molecular weight of a pigment | dye becomes small and absorbance per gram becomes high, a phenyl group is preferable.

Moreover, in the case where said R <^3> is a C1-C8 alkyl group which may be substituted by the halogen atom, it does not specifically limit as a C1-C8 alkyl group which is substituted, A C1-C8 linear, branched or cyclic alkyl group is mentioned. number and, more specific example is the same as the definition of R ^2. Among these, in view of the above characteristics such as heat resistance and solvent solubility, in particular solvent solubility, a linear or branched alkyl group having 1 to 5 carbon atoms is preferable. Moreover, as a halogen atom which is a substituent of an 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 a substituent 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 the above formula (3-1), the substitution number n of R ³ in Ar is not particularly limited and appropriately according to the desired effect (gram absorbance coefficient, solvent solubility, heat resistance, 710 nm light absorption, 520 nm visible light transmission, etc.). You can choose. For the number of the example wherein Ar is R in the case may be in a phenyl group substituted with Ar as a R ^{3 3-substituted} (n) is 1? 5 integer, preferably an integer of 1? 3, more preferably 1 or 2 And particularly preferably 1.

In the substituent (b-1) of the formula (3-1), the bonding position of the substituent R ^{3 to} the benzene ring is not particularly limited. Particular preference is given to orthowi (second) and parawi (fourth), fourth. When the substituent R ³ is placed at position 4, the phthalocyanine compound obtained absorbs 710 nm of light and has a high transmittance of visible light such as 520 nm, that is, an absorbance ratio (absorbance of = 710 nm / absorbance of 520 nm; Abs (λ710 nm) / Abs ( λ520 nm)] may be increased. When the substituent R ³ is placed in position 4, the phthalocyanine compound obtained can improve solvent solubility.

When n is 2, two substituents R ³ may be introduced at any position of the benzene ring. In this case, considering the above characteristics such as heat resistance, absorbance ratio and solvent solubility, in particular, solvent solubility, the second, fourth, second, fifth, second, sixth, third, fourth, etc. are preferable in consideration of solvent solubility and absorbance ratio. , 2, 4, 2, 5, 2, 6 are more preferable. In the case where n is 3, the three substituents R ³ may be introduced at any position of the benzene ring. In this case, in consideration of the above characteristics such as heat resistance, absorbance ratio and solvent solubility, in particular, solvent solubility, the second, fourth, sixth, second, fifth, sixth, and the like are preferable, considering the solvent solubility and the absorbance ratio. More preferred.

Also not the expression (3-1) of, Ar may be substituted for R ³ in the case of good-naphthyl group Ar is substituted by R ³ (n) can be substituted also in Fig, R ³ in Ar (n) is not particularly limited It can be suitably selected according to the desired effect (gram absorbance coefficient, solvent solubility, heat resistance, light absorption at 710 nm, visible light transmittance at 520 nm). For the number of the example wherein Ar is R in the even if good naphthyl group substituted Ar in R ^{3 3-substituted} (n) is 1? 5 integer, preferably an integer of 1? 3, more preferably 1 or 2, and particularly preferably 1. Moreover, the bonding position of the substituent R ³ with respect to the naphthalene ring is not specifically limited, It can select suitably according to a desired effect (gram absorbance coefficient, solvent solubility, heat resistance, 710 nm light absorption, 520 nm visible light transmittance, etc.). For example, when n is 1 and Ar is a 1-naphthyl group, the bonding position of R ^{3 to} the naphthalene ring may be any of 2nd, 3rd, 4th, 5th, 6th, 7th or 8th position. Although good heat resistance, solvent solubility, etc. are considered, 2nd, 3rd, and 4th positions are preferable, and 2nd position is more preferable. When the substituent (a) is derived from 2-naphthol, the bonding position of the substituent: -COO (R ¹ O) R ^{2 to} the naphthalene ring is 1st, 3rd, 4th, 5th, 6th, 7th, or Although it may be any 8th position, Preferably 1st, 3rd, and 6th position are preferable, and a 3rd and 6th position is more preferable in consideration of heat resistance, solvent solubility, etc.

In addition, the substituent (b) may be a substituent (b-2) of the formula (3-2). In said formula (3-2), X is an oxygen atom (-O-) or a sulfur atom (-S-), Preferably it is an oxygen atom. R <^7> is a C1-C5 alkylene group. The alkylene group having 1 to 5 carbon atoms is not particularly limited, and examples thereof include a methylene group, an ethylene group, a tetramethylene group, a propylene group, a butylene group and an isobutylene group. Among these, a methylene group, an ethylene group, a tetramethylene group, and a propylene group are preferable. Moreover, in said Formula (3-2), R <^5> is a C1-C8 alkyl group which may be substituted by the halogen atom or the C1-C8 alkoxy group. The alkyl group having 1 to 8 carbon atoms is not particularly limited, and examples thereof include a linear, branched or cyclic alkyl group having 1 to 8 carbon atoms, and more specific examples thereof are the same as defined above for R ² . Among these, in consideration of the above characteristics such as heat resistance and solvent solubility, in particular solvent solubility, a linear or branched alkyl group having 1 to 5 carbon atoms, particularly a linear or branched alkyl group having 1 to 3 carbon atoms is preferable. The alkyl group may be substituted with a halogen atom or an alkoxy group having 1 to 8 carbon atoms. As a halogen atom in the case where an alkyl group is substituted by a halogen atom, a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom are mentioned. Of these, chlorine atoms and fluorine atoms are preferable in consideration of heat resistance, solvent solubility and the like. Examples of the alkoxy group having 1 to 8 carbon atoms when the alkyl group is substituted with an alkoxy group include methoxy group, ethoxy group, propoxy group, isopropoxy group, butoxy group, pentyloxy group, hexyloxy group, 2-ethylhexyloxy group, Linear, branched or cyclic alkoxy groups such as octyloxy group. Among these, in consideration of the above characteristics such as heat resistance and solvent solubility, especially solvent solubility, a linear or branched alkoxy group having 1 to 5 carbon atoms, particularly a linear or branched alkoxy group having 1 to 3 carbon atoms is preferable. The number of substituent introduction of the halogen atom or the alkoxy group to the alkyl group is not particularly limited, but depends on the carbon number of the alkyl group, the desired effect, and the like. 1-8 are preferable and, as for the substituent introduction number of the halogen atom or the alkoxy group with respect to an alkyl group, 1-4 are more preferable.

In addition, the substituent (b) may be a substituent (b-3) of the formula (3-3). In said formula (3-3), X is an oxygen atom (-O-) or a sulfur atom (-S-), Preferably it is an oxygen atom. R <^7> is a C1-C5 alkylene group. There is no restriction | limiting in particular as an alkylene group of C1-C5 here, A more specific example is the same as that of the definition of R <^7> of said Formula (3-2). Preferably, R ⁷ is a methylene group, an ethylene group, a tetramethylene group, and a propylene group. R <^6> is a C1-C8 alkoxy group or a C1-C8 alkyl group. Among these, the alkoxy group having 1 to 8 carbon atoms is not particularly limited, and a more specific example is the same as that of the alkoxy group represented by the formula (3-3), preferably a straight or branched alkoxy group having 1 to 5 carbon atoms, particularly It is a C1-C3 linear or branched alkoxy group. The alkyl group having 1 to 8 carbon atoms is not particularly limited, and a more specific example is the same as defined above for R ² . Among these, in consideration of the above characteristics such as heat resistance and solvent solubility, in particular solvent solubility, a linear or branched alkyl group having 1 to 5 carbon atoms, particularly a linear or branched alkyl group having 1 to 3 carbon atoms is preferable. In addition, although three R <^6> may be same or different, respectively, it is preferable that at least 1 is an alkoxy group, More preferably, it is more preferable that 2 or 3 is an alkoxy group.

The substituent (b) may be a group (b-4) derived from 7-hydroxycoumarin. Or the substituent (b) may be a group (b-5) derived from 2,3-dihydroxyquinoxane.

As described above, the substituent (b) is a substituent (b-1) of Formula (3-1), a substituent (b-2) of Formula (3-2), and a substituent (b-) of Formula (3-3). 3) group (b-4) derived from 7-hydroxycoumarin or group (b-5) derived from 2,3-dihydroxyquinoxane. Of these, considering the above characteristics such as heat resistance and solvent solubility, in particular solvent solubility, the substituent (b) is a substituent (b-1) of the formula (3-1) and a substituent (b- of the formula (3-2) It is preferable that it is 2) and substituent (b-3) of said Formula (3-3), and it is more preferable that substituent (b) is substituent (b-1) of said Formula (3-1).

In Formula (1), M represents a metal free, metal, metal oxide or metal halide. Metal-free here means atoms 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 halide 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, More preferably, it is copper, vanadil, and zinc, More preferably, it is zinc, copper. Since the heat resistance is high, it is especially preferable if the center metal is zinc or copper.

In addition, in the present specification, Z ₁ , Z ₄ , Z ₅ , Z ₈ , Z ₉ , Z ₁₂ , Z _13, and Z ₁₆ represent substituents substituted at 8 positions of α in the phthalocyanine nucleus. The substituent is also referred to as a substituent on α. In the same manner, Z ₂ , Z ₃ , Z ₆ , Z ₇ , Z ₁₀ , Z ₁₁ , Z _14, and Z ₁₅ in Formula (1) represent substituents that are substituted at 8 β positions of the phthalocyanine nucleus. Also called a substituent on (beta). Since the substituent on β has an effect on improving heat resistance and the substituent on α on the solvent solubility, respectively, it is preferable to mix them in a balanced manner.

As an absorption wavelength of the phthalocyanine compound of this invention, it is preferable to have a maximum absorption wavelength ((lambda) max) in the wavelength range of 640 * 750 nm, More preferably, 640 * 705nm, especially 645 * 700nm among near-infrared regions. In addition, the maximum absorption wavelength in the present specification employs the value measured by the method measured in the following Examples. Since the phthalocyanine compound of the present invention exhibits a maximum absorption wavelength near 640? 750 nm, more preferably 640? 705 nm, particularly 645? 700 nm, the useless near-infrared region (700? 750 nm) emitted by flat panel displays, especially PDPs and LCDs. ) And the light of impurity red wavelength (640? 700 nm), called so-called magenta, can be cut, for example, to prevent the malfunction of the optical communication system, and at the same time, to reproduce the vivid red color. The phthalocyanine compound of the present invention absorbs light of 710 nm and has a high visible light transmittance such as 520 nm, that is, a high absorbance ratio. In particular, since PDP shows extra large light emission near 710 nm, the phthalocyanine compound of the present invention absorbs 710 nm light and is a dye having a high visible light transmittance such as 520 nm, and is useful as a filter for PDP, especially a flat panel display.

The phthalocyanine compound of the present invention has high solubility in an ether solvent. This is attributable to the presence of substituents (a) and (b) substituted in the phthalocyanine nucleus and the number of substitutions thereof. When applying the phthalocyanine compound, the solubility in the solvent of the phthalocyanine compound is important because the substrate used as the device should not be dissolved by the solvent and solubility in the resin is also required. 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 used effectively. 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. PGMEA is often used for flat panel display applications. It is preferable that the solubility with respect 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.

The method for producing the phthalocyanine compound of the present invention is not particularly limited and conventionally known methods can be suitably used. Preferably, the method of cyclizing the phthalonitrile compound and the metal salt in a molten state or an organic solvent can be particularly preferably used. . Hereinafter, especially preferable embodiment of a manufacturing method is described about the phthalocyanine compound of this invention. However, the present invention is not limited to the following preferred embodiments.

That is, the following formula (I):

[Chemical Formula 17]

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

[Chemical Formula 18]

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

[Formula 19]

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

[Chemical Formula 20]

The phthalonitrile compound (4) represented by the above is selected from the group consisting of metals, metal oxides, metal carbonyls, metal halides and organic acid metals (also collectively referred to as "metal compounds" in the present specification) and cyclization. The phthalocyanine compound of this invention can be manufactured by making it react. In the above reaction, the phthalonitrile compound (1)? (4) was described in accordance with the structure of the phthalocyanine compound of formula (1), but depending on the structure of the target phthalocyanine compound, 1 to 3 kinds of phthalonitrile compounds Sometimes. Therefore, when the structural units A? D including Z ₁ ? Z ₄ , Z ₅ ? Z ₈ , Z ₉ ? Z ₁₂ , and Z ₁₃ ? Z ₁₆ are the same, one kind of phthalonitrile compound is used as a raw material. Becomes

In addition, of the formulas (I)? (IV), Z 1? Z 16 is defined by the structure of the desired phthalocyanine compound. Specifically, in the above formula (I)? (IV), Z ₁ ? Z ₁₆ is the same as the definition of Z ₁ ? Z ₁₆ in the formula (1), respectively, and the description is omitted here.

In the above aspect, the phthalonitrile compound of formula (I)? (IV), which is a starting material, can be synthesized by conventional methods such as those disclosed in Japanese Patent Laid-Open No. 64-45474. Although a commercial item can also be used, Preferably it is following formula (V):

[Chemical Formula 21]

A phthalonitrile derivative (also referred to simply as a "phthalonitrile derivative" in the present specification) represented by the following formula (2a) or (2'a):

[Formula 22]

Substituent (a) containing precursor (it is also only called "substituent (a) containing precursor" in this specification) represented by this, or following formula (3a-1):

(23)

    H-X-Ar (3a-1)

Substituent (b-1) containing precursor represented by following formula (3a-2):

[Formula 24]

HXR ⁷ -COO-R ⁵ (3a-2)

Substituent (b-2) containing precursor represented by following formula (3a-3):

(25)

HXR ⁷ -Si (R ⁶ ) ₃ (3a-3)

A substituent (b) -containing precursor selected from the group consisting of a substituent (b-3) -containing precursor, 7-hydroxycoumarin, or 2,3-dihydroxyquinoxane (in the present specification, simply referred to as "substituent ( b) containing precursor ”). In addition, below, a substituent (a) containing precursor and a substituent (b) containing precursor are also collectively called "precursor."

In addition, the formula (2a), (2'a) from, R ^1, R ² and R ^4, and m and p are each of the formula (2) and (2 ') of the R ^1, R ² and R ^4, and Since the definition is the same as m and p, the description is omitted here. Like the formula (3a-1)? (3a -3) of the, X, Ar, R ^3, and R ^5? R ⁷ is X, Ar, R in the above formula (3-1)? (3-3), respectively ³ , and R ⁵ ? Same as the definition of R ⁷ , so explanation is omitted here.

In the said reaction, the phthalonitrile derivative of Formula (V) is used as a starting raw material. In said formula (V), X <_1> , X <_2> , X <_3> and X <_4> represent a halogen atom. Here, X <_1> , X <_2> , X <_3> and X <_4> may be same or different. As a halogen atom, a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom are mentioned. Among these, X ₁ , X ₂ , X ₃ and X ₄ preferably represent a fluorine atom or a chlorine atom, and particularly preferably a chlorine atom. In particular, when tetrachlorophthalonitrile is used as a starting material, a substituent (a) -containing precursor or a substituent (b) -containing precursor reacts randomly with the chlorine atoms at positions 3-6 of the tetrachlorophthalonitrile. Therefore, by using tetrachlorophthalonitrile as a starting material, substituents (a) and (b) can be introduced at random on the α and β positions of the phthalocyanine skeleton. Therefore, when tetrachlorophthalonitrile is used as the phthalonitrile derivative, the phthalonitrile compound is obtained in the form of a mixture in which four chlorine atoms of tetrachlorophthalonitrile are optionally substituted with precursors.

Moreover, in reaction of the said phthalonitrile derivative and substituent (a) containing precursor / substituent (b) containing precursor, the ratio of the said precursor is suitably selected by the structure of the phthalonitrile compound made into the objective. Moreover, the total usage-amount of the said precursor will not restrict | limit especially if it is an quantity which can advance the reaction and produce a desired phthalonitrile compound. The lower limit of the number of the substituent (a) -containing precursor / substituent (b) -containing precursor introduced into the phthalonitrile derivative is preferably 0.5, more preferably 0.75. The upper limit of the number of substituent (a) -containing precursor / substituent (b) -containing precursor introduced into the phthalonitrile derivative is preferably three, more preferably 2.5. In view of such a point, the lower limit of the total amount of the substituent (a) -containing precursor / substituent (b) -containing precursor is preferably 0.5 mole, more preferably 0.75 mole to 1 mole of the phthalonitrile derivative. Moreover, the upper limit of the total usage-amount of the said substituent (a) containing precursor / substituent (b) containing precursor becomes like this. Preferably it is 6.0 mol, More preferably, 4.0 mol, Especially preferably, 3.0 mol with respect to 1 mol of phthalonitrile derivatives. .

The reaction of the phthalonitrile derivative and the precursor 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; And polar solvents such as acetone and 2-butanone. Among these, acetonitrile, benzonitrile and acetone are preferable. The usage-amount of the organic solvent at the time of using a solvent is an amount which will make the density | concentration of a phthalonitrile derivative normally 2-40 mass%, Preferably it is 5-30 mass%. In addition, it is preferable to use these trapping agents in the reaction of this phthalonitrile derivative and precursor, in order to remove hydrogen halide (for example, hydrogen chloride, hydrogen fluoride), etc. which generate | occur | produce during reaction. Specific examples of the trapping agent when using the trapping agent include potassium carbonate, sodium carbonate, potassium hydroxide, sodium hydroxide, calcium carbonate, calcium hydroxide, magnesium hydroxide, magnesium chloride, magnesium carbonate, and the like. Calcium hydroxide is preferred. The amount of the trapping agent used when the trapping agent is used is not particularly limited as long as it is an amount capable of efficiently removing hydrogen halide or the like generated during the reaction, but is usually 1.0 to 4.0 moles, preferably 1 mole to 1 mole of the phthalonitrile derivative. Is 1.1? 2.5 moles.

Moreover, the reaction conditions of the said phthalonitrile derivative and a precursor will not be restrict | limited especially if they are conditions which can advance reaction of both and obtain a desired phthalonitrile compound. Specifically, the reaction temperature is usually 20? 150 ° C, preferably 60? 95 ° C. Moreover, reaction time is 0.5 to 60 hours normally, Preferably it is 1 to 50 hours.

By the above reaction, the phthalonitrile compound (1)? (4) of formula (I)? (IV) can be obtained, but after the reaction, crystallization, filtration, washing, drying according to a conventionally known method You may do By such operation, a phthalonitrile compound can be obtained efficiently and in high purity.

Next, the cyclization reaction melts a kind selected from the group consisting of phthalonitrile compound (1)? (4) of formula (I)? (IV) and metal, metal oxide, metal carbonyl, metal halide and organic acid metal. It is preferable to react in a state or 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 of the formula (1) obtained after the reaction can be obtained. Metals such as iron, magnesium, nickel, cobalt, copper, palladium, zinc, vanadium, titanium, indium and tin, and chlorides, bromide and iodide of the metals listed in M in formula (1); And metal oxides such as compounds, metal oxides such as vanadium oxide, titanium oxide and copper oxide, organic acid metals such as acetates, and complex compounds such as acetylacetonate and metal carbonyls such as carbonyl iron. Specifically, vanadium chloride, titanium chloride, copper chloride, zinc chloride, cobalt chloride, nickel chloride, iron chloride, indium chloride, aluminum chloride, tin chloride, germanium chloride, magnesium chloride, copper iodide, zinc iodide, cobalt iodide, indium iodide, Metal halides such as aluminum iodide, copper bromide, zinc bromide, cobalt bromide and aluminum bromide; Vanadium monoxide, vanadium trioxide, vanadium tetraoxide, vanadium pentoxide, titanium dioxide, iron monoxide, iron trioxide, iron trioxide, manganese oxide, nickel monoxide, cobalt monoxide, cobalt dioxide, cobalt dioxide, cuprous oxide, cupric oxide, trioxide Metal oxides such as copper, palladium oxide and zinc oxide; Organic acid metals such as copper acetate, zinc acetate, cobalt acetate, copper benzoate, and zinc benzoate; And complex compounds such as acetylacetonate and metal carbonyl such as cobalt carbonyl, iron carbonyl and nickel carbonyl. Among them, metals, metal oxides and metal halides are preferred, metal halides are more preferred, aluminum iodide, copper chloride and zinc iodide, more preferably copper chloride and zinc iodide, in particular Preferably it is zinc iodide. When zinc iodide is used, the center metal is zinc. The reason for using iodide among metal halides is because it is excellent in the solubility to a solvent and resin, the spectrum of the phthalocyanine compound obtained is sharp, and a desired wavelength can be obtained easily. When the iodide is used in the cyclization reaction, the detailed mechanism of sharpening the spectrum is unclear.However, when the iodide is used, the iodine remaining in the phthalocyanine compound causes a predetermined interaction with the phthalocyanine compound after the reaction. Is assumed to exist. 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 the above aspect, the cyclization reaction can be carried out in the absence of a solvent, but is preferably carried out using an organic solvent. The organic solvent may be any inert solvent having low reactivity with a phthalonitrile compound as a starting material, preferably not showing any 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. Among them, 1-chloronaphthalene, 1-methylnaphthalene, 1-octanol, dichlorobenzene and benzonitrile are used, and 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 (1)? (4) and the metal compound of formula (I)? (IV) in the above aspect are not particularly limited as long as the reaction proceeds. For example, organic solvent 100 The total amount of the phthalonitrile compound (1)? (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 it is 0.8-2.0 mol, More preferably, it is contained in 1.0-1.5 mol. Although it does not specifically limit at the time of cyclization, Preferably it is made to react in the range of reaction temperature of 30-250 degreeC, More preferably, it is 80-200 degreeC. Although reaction time is not specifically limited, Preferably it is 3 to 20 hours. Moreover, although the said reaction may be performed in air | atmosphere, it is preferable to carry out in inert gas atmosphere (for example, under the flow of nitrogen gas, helium gas, argon gas, etc.).

After the said cyclization reaction, you may crystallize, filter, wash, and dry according to a conventionally well-known method. By such operation, a phthalocyanine compound can be obtained efficiently and in high purity.

The phthalocyanine compound of the present invention can be used for various purposes because of its excellent compatibility with organic solvents, especially ether solvents.

The phthalocyanine compound of the present invention is semi-transparent, transparent and heat shielding material for the purpose of shielding heat rays, automotive heat radiation absorbing glass, heat shielding film or heat shielding resin glass, plasma having high visible light transmittance and high cut efficiency of near infrared light. Near-infrared absorbers for non-contact fixing toners such as filters for displays, flash fixing, and near-infrared absorbers for heat-retaining heat-retaining fibers, infrared absorbers for textiles having camouflage performance (camouflage performance) for reconnaissance by infrared rays, and semiconductor lasers. Optical recording media, near-infrared absorbing dyes, near-infrared light sensitizers, thermal transfer and thermal stencils for writing or reading in liquid crystal displays, backlights with xenon lamps, optical character readers, etc. Laser melting using heat exchanger and laser beam Photosensitive pigments for tumor treatment that absorb light in the long wavelength region, such as light heat exchanger, near-infrared absorbing filter, stable fatigue inhibitor, or photoconductive material, and color-tube tube-selective absorption filter, color toner, inkjet Ink, 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 molding of PET bottles When used as a preheating aid during processing, it exhibits an excellent effect. In particular, in view of the above characteristics, the phthalocyanine compound of the present invention can be suitably used for a heat ray shielding material, a filter for flat display, and a near infrared absorber.

Since the phthalocyanine compound having the specific structure as described above exhibits the maximum absorption wavelength in a specific wavelength region of 640 占 750 nm, it is possible to selectively cut light in this region. For this reason, when the phthalocyanine compound of this invention is used for a flat panel display, the light of the useless near-infrared region (700-750 nm) which a PDP or LCD emits, for example, or the impure red wavelength (640-700 nm) called what is called a magenta ) Is expected to have the effect of preventing the malfunction of the optical communication system, for example, and at the same time exerting a 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 a phthalocyanine compound. As a use of the filter for flat panel displays, what is used for a plasma display and a liquid crystal display is preferable, and it is especially preferable to use for a plasma display.

Although it is essential for the filter of this invention to contain a phthalocyanine compound, you may further include the pigment | dye which has another maximum absorption wavelength.

Other dyes that can be used in such a case are appropriately selected depending on the maximum absorption wavelength required depending on the application, and examples thereof include dyes absorbing near infrared absorbing dyes of 800? 1000 nm and orange neon light of 570? 600 nm. Can be. Among these, as a near-infrared absorbing pigment of 800-1000 nm, a cyanine pigment | dye, a phthalocyanine pigment | dye, a nickel complex dye, a dimonium pigment | dye, etc. are mentioned.

Although it is essential that the filter of this invention contains a phthalocyanine compound, you may further contain the pigment | dye which has a maximum absorption wavelength in 600-750 nm. As such a pigment | dye, 1-ethyl-2- [3-chloro-5- (1-ethyl-2 (1H) -quinolinylidene) -1, 3-pentadienyl as specifically, shown by a following formula. ] Quinolinium bromide (106-fold; lambda 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-fold; lambda max: 675.6 nm), 3-ethyl-2- [5- (3-ethyl-2-benzothiazolinylidene) And cyanine-based dyes such as) -1,3-pentadienyl] benzothiazolium iodide (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 the maximum absorption wavelength (λ max) is indicated in the parentheses. In addition, the said other pigment | dye may be used independently or 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 simply called "color | dye / phthalocyanine pigment | dye") which can be used by the filter for flat panel displays, and consists of this invention, The inclusion in the base material as used herein means not only contained in the inside of the base material, but also a state applied to the surface of the base material, a state sandwiched between the base material and the base material, and the like. 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 three methods can be used.

That is, (1) a method of kneading a dye / phthalocyanine dye into a resin and heating molding to prepare a resin plate or film; (2) a method of preparing a coating material (liquid to paste material) containing a dye / phthalocyanine dye and coating it 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 the like is applied to a film subjected to antireflection treatment and the like and applied to a PDP panel or a PDP front filter glass.

In the present invention, since the visible light transmittance is lowered in order to cut the near-infrared light emitted from the display, the lower the visible light transmittance, the sharper the image, the higher the visible light transmittance of the filter is good, at least 40%, preferably 60%. More than necessary. The cut region of near-infrared light is 750-1100 nm, preferably 800-1000 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. Therefore, if necessary, you may combine 2 or more types of pigment | dye / phthalocyanine pigment | dye. It is also preferable to add other pigments absorbed in the visible region in order to change the color tone of the filter. Moreover, you may produce the filter containing only the pigment | dye for color tone, and stick together later. In particular, when the electromagnetic wave shielding layer such as sputtering is provided, the color tone is important because the color may be significantly different from the original filter color.

<Examples>

Hereinafter, examples and comparative examples will be described. 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. In the name of the following compound, "α- (substituent A) _a , β- (substituent A) _xa PN (0 <a <x)" or "α- (substituent A) _a , β- (substituent A) _xa Pc ( 0 <a <x) "means that the obtained phthalonitrile compound or the phthalocyanine compound has the average xa substituents A introduced in the a position and (beta) position on (alpha) position, ie, sum x in the α position and (beta) position. It means that two substituents A are introduced. Thus, for example, "α-{(4-CN) C ₆ H ₄ O} _a , β-{(4-CN) C ₆ H ₄ O} _1.5-a Cl _2.5 PN (0≤ in Synthesis Example 2). a <1) "is a phthalonitrile compound in which the average a-cyanophenoxy group in the position corresponded to (alpha) position when it used as a phthalocyanine frame | skeleton has the average 1.5-a 4-cya to the position corresponded to (beta) position It is shown that nophenoxy group has a structure in which a chlorine atom is introduced at the remaining position. Similarly, for example, in Example 1, "ZnPc- {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} _4-x , {β- (4-COOC ₂ H ₄ OCH ₃ ) C ₆ H ₄ O} _{4- y} Cl ₈ (0≤x <2,0≤ y <4) &quot; is a group derived from x 4-cyanophenoxy groups and y p-hydroxybenzoic acid methyl cellosolves on α, and 4-x 4-cyanophenoxy groups on β of the phthalocyanine skeleton. The group derived from -y p-hydroxybenzoic acid methyl cellosolve has the structure which introduce | transduced the chlorine atom in the remaining position. That is, the 16 substituents of the phthalocyanine compound of Example 1 consist of four 4-cyanophenoxy groups, groups derived from four p-hydroxybenzoic acid methylcellosolves, and eight chlorine atoms.

Synthetic example  One: Phthalonitrile  Compound [α-{(4- CN ) C ₆ H ₄ O } _a , β-{(4- CN ) C ₆ H ₄ O } _1-a Cl ₃ PN] (0≤a <1) ( Intermediate 1 ) Synthesis of

15.95 g (0.06 mol) of tetrachlorophthalonitrile (hereinafter abbreviated as "TCPN"), 4-cyanophenol 7.50 g (0.063 mol), potassium carbonate 9.12 g (0.066 mol), acetonitrile 63.82 in a 150 ml flask g was added and reacted for about 7 hours while stirring using a magnetic stirrer at an internal temperature of 80 ° C. After cooling, the solution obtained by suction filtration was distilled off the solvent by evaporation on the conditions of about 110 degreeC x 1 hour. In addition, vacuum drying at about 110 ℃ overnight gave about 20.3g (100.1 mol% yield for TCPN).

Synthetic example  2: Phthalonitrile  Compound [α-{(4- CN ) C ₆ H ₄ O } _a , β-{(4- CN ) C ₆ H ₄ O } _1.5-a Cl _2.5 PN] (0≤a <1.5) ( Intermediate 2 ) Synthesis of

Into a 150 ml flask, 18.61 g (0.07 mole) of TCPN, 12.51 g (0.105 mole) of 4-cyanophenol, 15.96 g (0.116 mole) of potassium carbonate, 74.45 g of acetonitrile were added, and the temperature was 75 ° C. using a magnetic stirrer. The reaction was carried out for about 5 hours while stirring. After cooling, the mixture was treated in the same manner as in Synthesis example 1 to obtain about 26.57 g (yield 97.0 mol% for TCPN).

Synthetic example  3: Phthalonitrile  Compound [α-{(4- CN ) C ₆ H ₄ O } _a , β-{(4- CN ) C ₆ H ₄ O } _2-a Cl ₂ PN] (0≤a <2) ( Intermediate 3 ) Synthesis of

Into a 150 ml flask, 7.98 g (0.03 mole) of TCPN, 7.15 g (0.06 mole) of 4-cyanophenol, 9.92 g (0.066 mole) of potassium carbonate, and 31.91 g of acetonitrile were added to an internal temperature of 85 ° C. using a magnetic stirrer. The reaction was carried out for about 2 hours with stirring. After cooling, the same process as in Synthesis example 1 was carried out, thereby obtaining about 15.12 g (99.2 mol% of TCPN).

Synthetic example  4: Phthalonitrile  Compound [α-{(4- NO ₂ ) C ₆ H ₄ O } _a , β-{(4- NO ₂ ) C ₆ H ₄ O } _1-a Cl ₃ PN] (0≤a <1) ( Intermediate 4 ) Synthesis of

Into a 150 mL flask, 14.63 g (0.055 mole) of TCPN, 7.75 g (0.055 mole) of 4-nitrophenol, 8.36 g (0.061 mole) of potassium carbonate, and 58.50 g of acetonitrile were added and stirred using a magnetic stirrer at 75 ° C. The reaction was carried out for about 1 hour. After cooling, the same process as in Synthesis example 1 was carried out to obtain about 20.17 g (yield 99.5 mol% of TCPN).

Synthetic example  5: Phthalonitrile  Compound [α-{(2,4- Cl ₂ ) C ₆ H ₃ S } _a , β-{(2,4- Cl ₂ ) C ₆ H ₃ S } _1-a Cl ₃ PN] (0≤a <1) ( Intermediate 5 ) Synthesis of

Into a 150 ml flask, 7.00 g (0.0263 mole) of TCPN, 4.71 g (0.0263 mole) of 2,4-dichlorothiophenol, 4.0 g (0.029 mole) of potassium carbonate, and 25 g of acetonitrile were used, and a magnetic stirrer at 70 ° C. was used. It was made to react for about 6 hours, stirring. After cooling, treatment was performed in the same manner as in Synthesis example 1 to obtain about 10.25 g (yield 95.4 mol% of TCPN).

Synthetic example  6: Phthalonitrile  Compound [α-{(2- COOCH ₃ ) C ₆ H ₄ S } _a , β-{(2- COOCH ₃ ) C ₆ H ₄ S } _1-a Cl ₃ PN] (0≤a <1) ( Intermediate 6 ) Synthesis of

Into a 150 ml flask, 10.0 g (0.0376 mole) of TCPN, 6.33 g (0.0376 mole) of methyl thiosalicylate, 5.72 g of potassium carbonate (0.0414 mole), and 36 g of acetone were added and stirred at 65 ° C. with a magnetic stirrer, followed by stirring. The reaction was time. After cooling, the solution obtained by suction filtration was added dropwise into 300 ml of distilled water to precipitate crystals. The crystals obtained after suction filtration were washed in 150 ml of distilled water, followed by further washing with 100 ml of methanol. The crystals obtained after suction filtration were washed again with 80 ml of methanol. Vacuum suction treatment after suction filtration yielded about 12.3 g (82.3 mol% of yield over TCPN).

Synthetic example  7: Phthalonitrile  Compound [α-{(2,4,6- Cl ₃ ) C ₆ H ₂ O } _a , β-{(2,4,6-Cl ₃ C ₆ H ₂ O} _1-a Cl ₃ PN] (0≤a <1) ( Intermediate 7 ) Synthesis of

Into a 150 ml flask, 13.30 g (0.05 mole) of TCPN, 2,4,6-trichlorophenol 9.87 g (0.05 mole), potassium carbonate 7.70 g (0.05 mole), acetonitrile 53.18 g were added and the inner temperature was 85 ° C., magnetic stirrer. The reactor was reacted for about 5 hours while stirring. After cooling, treatment was performed in the same manner as in Synthesis example 1 to obtain about 19.89 g (yield 93.2 mol% of TCPN).

Synthetic example  8: Phthalonitrile  Compound [α-{(4- OCH ₃ ) C ₆ H ₄ O } _a , β-{(4- OCH ₃ ) C ₆ H ₄ O } _1-a Cl ₃ PN] (0≤a <1) ( Intermediate 8 ) Synthesis of

Into a 150 ml flask, 7.98 g (0.03 mole) of TCPN, 4.92 g (0.03 mole) of 4-methoxy phenol, 4.56 g (0.033 mole) of potassium carbonate, and 31.91 g of acetonitrile were used, and a magnetic stirrer at 80 ° C. was used. The reaction was carried out for about 4 hours with stirring. After cooling, treatment was performed in the same manner as in Synthesis example 1 to obtain about 10.5 g (yield 99.0 mol% of TCPN).

Synthetic example  9: Phthalonitrile  Compound [α-{(4-C ( CH ₃ ) ₃ ) C ₆ H ₄ O } _a , β-{(4-C (CH ₃ ) ₃ C ₆ H ₄ O} _1-a Cl ₃ PN] (0≤a <1) ( Intermediate 9 ) Synthesis of

Into a 150 ml flask, 7.98 g (0.03 mole) of TCPN, 4.51 g (0.03 mole) of 4-tert-butylphenol, 4.56 g (0.033 mole) of potassium carbonate, and 31.91 g of acetonitrile were used and a magnetic stirrer at 80 ° C. was used. It was made to react for about 4 hours, stirring. After cooling, the mixture was treated in the same manner as in Synthesis example 1 to obtain about 10.8 g (yield 94.8 mol% of TCPN).

Synthetic example  10: Phthalonitrile  Compound [α-{(4- Cl ) C ₆ H ₄ O } _a , β-{(4- Cl ) C ₆ H ₄ O } _1-a Cl ₃ PN] (0≤a <1) ( Intermediate 10 ) Synthesis of

15.95 g (0.06 mol) of TCPN, 8.10 g (0.063 mol) of 4-chlorophenol, 9.58 g (0.069 mol) of potassium carbonate, and 63.82 g of acetonitrile were added to a 150 ml flask, and stirred using a magnetic stirrer at 85 DEG C. The reaction was carried out for about 3 hours. After cooling, treatment was performed in the same manner as in Synthesis example 1 to obtain about 20.5 g (98.3 mol% of yield over TCPN).

Synthetic example  11: Phthalonitrile  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 11 ) Synthesis of

Into a 150 ml flask, 14.63 g (0.055 mole) of TCPN, 9.91 g (0.058 mole) of 2,6-dichlorophenol, 8.78 g (0.064 mole) of potassium carbonate, and 58.50 g of acetonitrile were used and a magnetic stirrer at 85 ° C. was used. It was made to react for about 3 hours, stirring. After cooling, the same process as in Synthesis Example 1 was performed to obtain about 9.06 g (43.1 mol% of TCPN).

Synthetic example  12: Phthalonitrile  Compound [α-{(2- COOCH ₃ -4- OCH ₃ ) C ₆ H ₃ O } _a , β-{(2-COOCH ₃ -4-OCH ₃ C ₆ H ₃ O} _1-a Cl ₃ PN] (0≤a <1) ( Intermediate 12 ) Synthesis of

4.79 g (0.018 mole) of TCPN, 3.28 g (0.018 mole) of methyl 4-methoxysalicylate, 2.74 g (0.02 mole) of potassium carbonate, and 19.15 g of acetonitrile were added to a 150 ml flask, and a magnetic stirrer was used at 75 ° C. It was made to react for about 2 hours, stirring. After cooling, the same procedure as in Synthesis Example 1 was followed to yield about 7.34 g (99.1 mol% of TCPN).

Synthetic example  13: Phthalonitrile  Compound [α-{(2,6- OCH ₃ ) C ₆ H ₃ O } _a , β-{(2,6-OCH ₃ C ₆ H ₃ O} _1-a Cl ₃ PN] (0≤a <1) ( Intermediate 13 ) Synthesis of

Into a 150 ml flask, 9.84 g (0.037 mole) of TCPN, 5.99 g (0.039 mole) of 2,6-dimethoxyphenol, 5.91 g (0.043 mole) of potassium carbonate, and 39.35 g of acetonitrile were added. It was made to react for about 6 hours, stirring. After cooling, treatment was performed in the same manner as in Synthesis example 1 to obtain about 14.1 g (yield 101.8 mol% of TCPN).

Synthetic example  14: Phthalonitrile  Compound [α- ( C ₆ F ₅ O ) _a , β- ( C ₆ F ₅ O ) _{One- a} Cl ₃ PN ] (0≤a <1) ( Intermediate 14 ) Synthesis of

Into a 150 ml flask, 7.98 g (0.03 mole) of TCPN, 5.52 g (0.03 mole) of pentafluorophenol, 4.56 g (0.033 mole) of potassium carbonate, and 31.91 g of acetonitrile were added and stirred at 85 ° C. in a magnetic stirrer. The reaction was carried out for about 4 hours. After cooling, the treatment was carried out in the same manner as in Synthesis example 1 to obtain about 12.39 g (yield 99.9 mol% of TCPN).

Synthetic example  15: Phthalonitrile  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} _1-a Cl ₃ PN] (0≤a <1) ( Intermediate 15 ) Synthesis of

Into a 150 ml flask, 10.64 g (0.04 mol) of TCPN, 7.85 g (0.04 mol) of p-hydroxybenzoic acid methyl cellosolve, 6.08 g (0.044 mol) of potassium carbonate, and 42.55 g of acetonitrile were added. The reaction was carried out for about 2 hours while stirring using a ler. After cooling, the mixture was treated in the same manner as in Synthesis example 1 to obtain about 16.8 g (98.7 mol% of TCPN).

Synthetic example  16: Phthalonitrile  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} _1.5-a Cl _2.5 PN] (0≤a <1.5) ( Intermediate 16 ) Synthesis of

Into a 150 ml flask, 7.98 g (0.03 mole) of TCPN, 8.83 g (0.045 mole) of p-hydroxybenzoic acid methyl cellosolve, 4.56 g of potassium carbonate (0.033 mole), and 31.91 g of acetonitrile were added. The reaction was carried out for about 2 hours while stirring using a ler. After cooling, treatment was performed in the same manner as in Synthesis example 1 to obtain about 12.78 g (yield 84.3 mol% of TCPN).

Synthetic example  17: Phthalonitrile  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} _1.75-a Cl _2.25 PN] (0≤a <1.75) ( Intermediate 17 ) Synthesis of

Into a 150 ml flask, 10.64 g (0.04 mol) of TCPN, 13.73 g (0.07 mol) of p-hydroxybenzoic acid methyl cellosolve, 10.64 g (0.077 mol) of potassium carbonate, and 42.55 g of acetonitrile were added. The reaction was carried out for about 2 hours while stirring using a ler. After cooling, treatment was performed in the same manner as in Synthesis example 1 to obtain about 22.2 g (yield 101.1 mol% of TCPN).

Synthetic example  18: Phthalonitrile  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 18 ) Synthesis of

Into a 150 ml flask was added 31.38 g (0.118 mole) of TCPN, 46.30 g (0.236 mole) of p-hydroxybenzoic acid methyl cellosolve, 35.88 g (0.260 mole) of potassium carbonate, and 125.51 g of acetonitrile. The reaction was carried out for about 2 hours while stirring using a ler. After cooling, treatment was performed in the same manner as in Synthesis example 1 to obtain about 68.1 g (98.6 mol% of TCPN yield).

Synthetic example  19: Phthalonitrile  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} _2.5-a Cl _1.5 PN] (0≤a <2.5) ( Intermediate 19 ) Synthesis of

Into a 150 ml flask, 7.98 g (0.03 mole) of TCPN, 14.72 g (0.075 mole) of p-hydroxybenzoic acid methyl cellosolve, 4.56 g (0.033 mole) of potassium carbonate, and 31.91 g of acetonitrile were added. The reactor was reacted for about 5 hours while stirring. After cooling, the treatment was carried out in the same manner as in Synthesis example 1 to obtain about 19.6 g (98.4 mol% of TCPN).

Synthetic example  20: Phthalonitrile  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} _1-a Cl ₃ PN] (0≤a <1) ( Intermediate 20 ) Synthesis of

Into a 150 ml flask was added 7.98 g (0.03 mole) of TCPN, 9.69 g (0.032 mole) of 1-hydroxy-2-naphthoate methyl cellosolve, 4.79 g (0.035 mole) of potassium carbonate, and 31.91 g of acetonitrile. It reacted for about 6 hours, stirring using internal temperature 85 degreeC and the magnetic stirrer. After cooling, the mixture was treated in the same manner as in Synthesis example 1 to obtain about 16.0 g (112.1 mol% of TCPN).

Synthetic example  21: Phthalonitrile  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} _1.5-a Cl _2.5 PN] (0≤a <1.5) ( Intermediate 21 ) Synthesis of

Into a 150 ml flask, 3.56 g (0.013 mole) of TCPN, 6.18 g (0.02 mole) of 1-hydroxy-2-naphthoate methyl cellosolve, 3.06 g (0.022 mole) of potassium carbonate, and 14.25 g of acetonitrile were added. It reacted for about 7 hours, stirring using internal temperature 85 degreeC and the magnetic stirrer. After cooling, the treatment was carried out in the same manner as in Synthesis example 1 to obtain about 8.3 g (106.7 mol% of yield over TCPN).

Synthetic example  22: Phthalonitrile  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 22 ) Synthesis of

Into a 150 ml flask was added 7.98 g (0.03 mol) of TCPN, 18.46 g (0.06 mol) of 1-hydroxy-2-naphthoic acid methyl cellosolve, 9.92 g (0.066 mol) of potassium carbonate, and 31.91 g of acetonitrile. It reacted for about 6 hours, stirring using internal temperature 85 degreeC and the magnetic stirrer. After cooling, treatment was performed in the same manner as in Synthesis example 1 to obtain about 23.1 g (112.3 mol% of yield over TCPN).

Synthetic example  23: Phthalonitrile  Compound [α-{(2- CH ₃ O -4- COOC ₂ H ₄ OCH ₃ ) C ₆ H ₄ O } _a , β-{(2-CH ₃ O-4-COOC ₂ H ₄ OCH ₃ C ₆ H ₄ O} _1-a Cl ₃ PN] (0≤a <1) ( Intermediate 23 ) Synthesis of

Into a 150 ml flask, 7.98 g (0.03 mole) of TCPN, 6.91 g (0.03 mole) of methyl vanillate, 4.56 g (0.033 mole) of potassium carbonate, and 31.91 g of acetonitrile. It was made to react for about 2 hours, stirring. After cooling, the mixture was treated in the same manner as in Synthesis example 1 to obtain about 13.7 g (100.2 mol% of yield over TCPN).

Synthetic example  24: Phthalonitrile  Compound [α-{(2- CH ₃ O -4- COOC ₂ H ₄ OCH ₃ ) C ₆ H ₄ O } _a , β-{(2-CH ₃ O-4-COOC ₂ H ₄ OCH ₃ C ₆ H ₄ O} _2-a Cl ₂ PN] (0≤a <2) ( Intermediate 24 ) Synthesis of

4.71 g (0.018 mole) of TCPN, 8.01 g (0.035 mole) of potassium vanillate, 5.38 g (0.039 mole) of potassium carbonate, and 18.83 g of acetonitrile were added to a 150 ml flask, and a magnetic stirrer was used at 75 ° C. It was made to react for about 2 hours, stirring. After cooling, the mixture was treated in the same manner as in Synthesis example 1 to obtain about 11.4 g (yield 99.8 mol% of TCPN).

Synthetic example  25: Phthalonitrile  Compound [α-{(2- OCH ₃ -4- COOC ₂ H ₄ OCH ₃ ) C ₆ H ₃ O } _a , β-{(2-OCH ₃ -4-COOC ₂ H ₄ OCH ₃ C ₆ H ₃ O} _1.4-a Cl _2.6 PN] (0≤a <1.4) ( Intermediate 25 ) Synthesis of

Into a 150 ml flask, 13.30 g (0.050 mole) of TCPN, 16.41 g (0.070 mole) of vanillate methyl cellosolve, 10.64 g (0.077 mole) of potassium carbonate, and 53.18 g of acetonitrile were used, and a magnetic stirrer at 75 ° C. was used. It was made to react for about 3 hours, stirring. After cooling, treatment was performed in the same manner as in Synthesis example 1 to obtain about 26.8 g (100.7 mol% of yield over TCPN).

Synthetic example  26: Phthalonitrile  Compound [α-{(2- CH ₃ O -5- NO ₂ ) C ₆ H ₃ O } _a , β-{(2- CH ₃ O -5-NO ₂ C ₆ H ₃ O} _1-a Cl ₃ PN] (0≤a <1) ( Intermediate 26 ) Synthesis of

Into a 150 ml flask, 10.64 g (0.040 mole) of TCPN, 6.7 g (0.040 mole) of 5-nitroguayacol, 6.08 g (0.044 mole) of potassium carbonate, and 42.55 g of acetonitrile were used, and a magnetic stirrer was used at 75 ° C. The mixture was reacted for about 2.5 hours while stirring. After cooling, the mixture was treated in the same manner as in Synthesis example 1 to obtain about 5.4 g (33.9 mol% of yield over TCPN).

Synthetic example  27: Phthalonitrile  Compound [α-{(7- C ₉ H ₅ O ₂ ) O} _a , β-{(7- C ₉ H ₅ O ₂ ) O} _1-a Cl ₃ PN] (0≤a <1) ( Intermediate 27 ) Synthesis of

Into a 150 ml flask, 15.95 g (0.060 mole) of TCPN, 9,3 g (0.060 mole) of 7-hydroxycoumarin, 9.92 g (0.066 mole) of potassium carbonate, 63.82 g of acetonitrile were added and the inner temperature was 75 ° C., using a magnetic stirrer. The reaction was carried out for about 3 hours with stirring. After cooling, treatment was performed in the same manner as in Synthesis example 1 to obtain about 15.9 g (yield 67.7 mol% of TCPN).

Synthetic example  28: Phthalonitrile  Compound [α-{( C ₈ H ₅ N ₂ O ) O} _a , β-{( C ₈ H ₅ N ₂ O ) O} _{One- a} Cl ₃ PN ] (0≤a <1) ( Intermediate 28 ) Synthesis of

6.65 g (0.025 mole) of TCPN, 4.05 g (0.025 mole) of 2,3-dihydroxyquinoxaline, 3.80 g (0.028 mole) of potassium carbonate, and 26.59 g of acetonitrile were added to a 150 ml flask. The reactor was reacted for about 6 hours while stirring. After cooling, the mixture was treated in the same manner as in Synthesis example 1 to obtain about 4.1 g (41.7 mol% of yield over TCPN).

Synthetic example  29: Phthalonitrile  Compound [α-{(2- OCH ₃ -4- COOC ₂ H ₄ OCH ₃ ) C ₆ H ₃ O } _a , β-{(2-OCH ₃ -4-COOC ₂ H ₄ OCH ₃ C ₆ H ₃ O} _1.5-a Cl _2.5 PN] (0≤a <1.5) ( Intermediate 29 ) Synthesis of

Into a 150 ml flask, 10.64 g (0.040 mole) of TCPN, 14.02 g (0.060 mole) of methyl vanillate, 9.22 g (0.066 mole) of potassium carbonate, and 42.55 g of acetonitrile were added, and a magnetic stirrer at 75 ° C. was used. It was made to react for about 4 hours, stirring. After cooling, the treatment was carried out in the same manner as in Synthesis example 1 to obtain about 22.6 g (yield 102.6 mol% of TCPN).

Synthetic example  30: Phthalonitrile  Compound [α-{(2- COOC ₂ H ₄ OCH ₃ ) C ₁₀ H ₈ -6-O} _a , β-{(2-COOC ₂ H ₄ OCH ₃ C ₁₀ H ₈ -6-O} _1-a Cl ₃ PN] (0≤a <1) ( Intermediate 30 ) Synthesis of

9.31 g (0.035 mole) of TCPN, 9.05 g (0.037 mole) of methyl-cellosolve of 6-hydroxy-2-naphthoate, 5.32 g (0.039 mole) of potassium carbonate, and 37.23 g of acetonitrile were added to a 150 ml flask. It reacted for about 4 hours, stirring using internal temperature 75 degreeC and the magnetic stirrer. After cooling, the mixture was treated in the same manner as in Synthesis example 1 to obtain about 16.50 g (yield 99.1 mol% of TCPN).

Synthetic example  31: Phthalonitrile  Compound [α-{(2- COOC ₂ H ₄ OCH ₃ ) C ₁₀ H ₈ -3-O} _a , β-{(2-COOC ₂ H ₄ OCH ₃ C ₁₀ H ₈ -3-O} _1-a Cl ₃ PN] (0≤a <1) ( Intermediate 31 ) Synthesis of

10.64 g (0.040 mol) of TCPN, 10.34 g (0.042 mol) of 3-hydroxy-2-naphthoic acid methyl cellosolve, 6.08 g (0.044 mol) of potassium carbonate, and 42.55 g of acetonitrile were charged into a 150 ml flask. It reacted for about 2 hours, stirring using internal temperature 75 degreeC and the magnetic stirrer. After cooling, the same process as in Synthesis Example 1 was conducted, yielding about 18.42 g (yield 96.8 mol% of TCPN).

Synthetic example  32: Phthalonitrile  Compound [α-{( CH ₃ CH ( OCH ₃ C ₂ H ₄ OOC) C ₂ H ₄ S } _a , β-{(CH ₃ CH (OCH ₃ C ₂ H ₄ OOC) C ₂ H ₄ S} _1-a Cl ₃ PN] (0≤a <1) ( Intermediate 32 ) Synthesis of

Into a 150 ml flask, 10 g (0.0376 mol) of TCPN, 7.23 g (0.0376 mol) of 3-methoxycaptopropionic acid and 35 g of benzonitrile were added, and a magnetic stirrer was used until the internal temperature was stabilized at 100 ° C. After stirring for 30 minutes, potassium carbonate 5.72 g (0.0414 mol) was added thereto and reacted for about 6 hours. After cooling, the mixture was treated in the same manner as in Synthesis example 1 to obtain about 15.5 g (yield 97.7 mol% of TCPN).

Synthetic example  33: Phthalonitrile  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} _0.875-a Cl _3.125 PN] (0≤a <0.875) ( Intermediate 33 ) Synthesis of

Into a 150 ml flask, 7.98 g (0.030 mole) of TCPN, 5.25 g (0.026 mole) of p-hydroxy benzoate, potassium carbonate 3.99 g (0.029 mole), and 31.91 g of acetonitrile were added. The reaction was carried out for about 1 hour while stirring using a ler. After cooling, treatment was performed in the same manner as in Synthesis example 1 to obtain about 12.1 g (yield 99.4 mol% of TCPN).

Synthetic example  34: Phthalonitrile  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} _0.75-a Cl _3.25 PN] (0≤a <0.75) ( Intermediate 34 ) Synthesis of

Into a 150 ml flask, 7.98 g (0.030 mole) of TCPN, 4.41 g (0.023 mole) of p-hydroxybenzoic acid methyl cellosolve, 3.42 g (0.025 mole) of potassium carbonate, and 31.91 g of acetonitrile were added. The reactor was reacted for about 1.5 hours while stirring. After cooling, the treatment was carried out in the same manner as in Synthesis example 1 to obtain about 11.47 g (yield 99.1 mol% of TCPN).

Synthetic example  35: Phthalonitrile  Compound [α-{(4- COOCH ₃ ) C ₆ H ₄ O } _a , β-{(4-COOCH ₃ C ₆ H ₄ O} _1-a Cl ₃ PN] (0≤a <1) ( Intermediate 35 ) Synthesis of

Into a 150 ml flask, 7.98 g (0.030 mole) of TCPN, 4.56 g (0.030 mole) of methyl p-hydroxybenzoate, 4.06 g (0.033 mole) of potassium carbonate, and 31.91 g of acetonitrile were added, and a magnetic stirrer was used at 75 ° C. It was made to react for about 1 hour, stirring. After cooling, the same procedure as in Synthesis Example 1 was conducted to give about 11.67 g (101.9 mol% of yield over TCPN).

Synthetic example  36: Phthalonitrile  Compound [α-{(4- COOC ₂ H ₄ OCH ₃ ) C ₆ H ₄ O } _a , α-{(4-NO ₂ C ₆ H ₄ S} _b , β-{(4- COOC ₂ H ₄ OCH ₃ ) C ₆ H ₄ O } _1-a , β-{(4- NO ₂ ) C ₆ H ₄ S } _{0.25- b} Cl _{2 .75} PN ] (0≤a <1, 0≤b <0.25) (intermediate 36)

5.32 g (0.020 mol) of TCPN, 3.92 g (0.020 mol) of p-hydroxybenzoic acid methyl cellosolve, and 21.27 g of acetonitrile were added to a 150 ml flask, and the magnetic stirrer was used until the temperature was stabilized at 40 ° C. After stirring for about 30 minutes, 3.80 g (0.028 mol) of potassium carbonate was added and reacted for about 2 hours. After the reaction, 0.78 g (0.005 mol) of 4-nitrothiophenol was added to the flask, and the reaction was further performed for about 3 hours. After cooling, treatment was performed in the same manner as in Synthesis example 1 to obtain about 9.1 g (99.5 mol% of yield over TCPN).

Synthetic example  37: Phthalonitrile  Compound [α-{(4- COOC ₂ H ₄ OCH ₃ ) C ₆ H ₄ O } _a , α-{(4-Cl) C ₆ H ₄ S} _b , β-{(4- COOC ₂ H ₄ OCH ₃ ) C ₆ H ₄ O } _1-a , β-{(4- Cl ) C ₆ H ₄ S } _{0.25- b} Cl _{2 .75} PN ] (0≤a <1, 0≤b <0.25) liver Synthesis of Sieve 37

5.32 g (0.020 mol) of TCPN, 3.92 g (0.020 mol) of p-hydroxybenzoic acid methyl cellosolve, and 21.27 g of acetonitrile were added to a 150 ml flask, and the magnetic stirrer was used until the temperature was stabilized at 40 ° C. After stirring for about 30 minutes, 3.80 g (0.028 mol) of potassium carbonate was added and reacted for about 2 hours. After the reaction, 0.72 g (0.005 mol) of 4-chlorothiophenol was added to the flask, followed by further reaction for about 3 hours. After cooling, the mixture was treated in the same manner as in Synthesis example 1 to obtain about 9.3 g (102.5 mol% of yield over TCPN).

Synthetic example  38: Phthalonitrile  Compound [α-{(4- COOC ₂ H ₄ OCH ₃ ) C ₆ H ₄ O } _a , α- ( C ₆ H ₅ S ) _b , β-{(4-COOC ₂ H ₄ OCH ₃ C ₆ H ₄ O} _1-a , β- ( C ₆ H ₅ S ) _{0.25- b} Cl _{2 .75} PN ] (0≤a <1, 0≤b <0.25) ( Intermediate 38 ) Synthesis of

5.32 g (0.020 mol) of TCPN, 3.92 g (0.020 mol) of p-hydroxybenzoic acid methyl cellosolve, and 21.27 g of acetonitrile were added to a 150 ml flask, and the magnetic stirrer was used until the temperature was stabilized at 40 ° C. After stirring for about 30 minutes, 3.80 g (0.028 mol) of potassium carbonate was added and reacted for about 2 hours. After the reaction, 0.55 g (0.005 mol) of thiophenol was added to the flask and allowed to react for about 3 hours. After cooling, the mixture was treated in the same manner as in Synthesis example 1 to obtain about 9.7 g (109.5 mol% of yield over TCPN).

Synthetic example  39: Phthalonitrile  Compound [α-{(4- COOC ₂ H ₄ OCH ₃ ) C ₆ H ₄ O } _a , α- ( C ₆ Cl ₅ S ) _b , β-{(4-COOC ₂ H ₄ OCH ₃ C ₆ H ₄ O} _1-a , β- ( C ₆ Cl ₅ S ) _{0.25- b} Cl _{2 .75} PN ] (0≤a <1, 0≤b <0.25) ( Intermediate 39 ) Synthesis of

5.32 g (0.020 mol) of TCPN, 3.92 g (0.020 mol) of p-hydroxybenzoic acid methyl cellosolve, and 21.27 g of acetonitrile were added to a 150 ml flask, and the magnetic stirrer was used until the temperature was stabilized at 40 ° C. After stirring for about 30 minutes, 3.80 g (0.028 mol) of potassium carbonate was added and reacted for about 2 hours. After the reaction, pentachlorothiophenol 1.41g (0.005 mol) was added to the flask and allowed to react for about 3 hours. After cooling, the treatment was carried out in the same manner as in Synthesis example 1 to obtain about 8.6 g (a yield of 87.9 mol% of TCPN).

Synthetic example  40: Phthalonitrile  Compound [α-{(4- COOC ₂ H ₄ OCH ₃ ) C ₆ H ₄ O } _a , α-{(4-OCH ₃ C ₆ H ₄ S} _b , β-{(4- COOC ₂ H ₄ OCH ₃ ) C ₆ H ₄ O } _1-a , β-{(4- OCH ₃ ) C ₆ H ₄ S } _{0.25- b} Cl _{2 .75} PN ] (0≤a <1, 0≤b <0.25) (intermediate 40)

5.32 g (0.020 mol) of TCPN, 3.92 g (0.020 mol) of p-hydroxybenzoic acid methyl cellosolve, and 21.27 g of acetonitrile were added to a 150 ml flask, and the magnetic stirrer was used until the temperature was stabilized at 40 ° C. After stirring for about 30 minutes, 3.80 g (0.028 mol) of potassium carbonate was added and reacted for about 2 hours. After the reaction, 0.70 g (0.005 mol) of 4-methoxybenzenethiol was added to the flask, and the reaction was further performed for about 3 hours. After cooling, treatment was performed in the same manner as in Synthesis example 1 to obtain about 9.1 g (100.2 mol% of yield over TCPN).

Synthetic example  41: Phthalonitrile  Compound [α-{(4- COOC ₂ H ₄ OCH ₃ ) C ₆ H ₄ O } _a , α-{( C ₁₀ H ₈ ) -2-S} _b , β-{(4- COOC ₂ H ₄ OCH ₃ ) C ₆ H ₄ O } _1-a , β-{( C ₁₀ H ₈ ) -2-S} _{0.25- b} Cl _{2 .75} PN ] (0≤a <1, 0≤b <0.25) ( Intermediate 41 ) Synthesis of

5.32 g (0.020 mol) of TCPN, 3.92 g (0.020 mol) of p-hydroxybenzoic acid methyl cellosolve, and 21.27 g of acetonitrile were added to a 150 ml flask, and the magnetic stirrer was used until the temperature was stabilized at 40 ° C. After stirring for about 30 minutes, 3.80 g (0.028 mol) of potassium carbonate was added and reacted for about 2 hours. After the reaction, 0.80 g (0.005 mol) of β-naphthalene thiol was added to the flask and allowed to react for about 3 hours. After cooling, the mixture was treated in the same manner as in Synthesis example 1 to obtain about 9.4 g (103.0 mol% of TCPN).

Synthetic example  42: Phthalonitrile  Compound [α-{(4- COOC ₂ H ₄ OCH ₃ ) C ₆ H ₄ O } _a , α-{(2,6-Cl ₂ C ₆ H ₃ S} _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 S } _{0.25- b} Cl _{2 .75} PN ] (0≤a <1, 0≤b <0.25) (intermediate 42)

5.32 g (0.020 mol) of TCPN, 3.92 g (0.020 mol) of p-hydroxybenzoic acid methyl cellosolve, and 21.27 g of acetonitrile were added to a 150 ml flask, and the magnetic stirrer was used until the temperature was stabilized at 40 ° C. After stirring for about 30 minutes, 3.80 g (0.028 mol) of potassium carbonate was added and reacted for about 2 hours. After the reaction, 0.90 g (0.005 mol) of 2,6-dichlorothiophenol was added to the flask and allowed to react for about 3 hours. After cooling, the mixture was treated in the same manner as in Synthesis example 1 to obtain about 9.3 g (100.9 mol% of yield over TCPN).

Synthetic example  43: Phthalonitrile  Compound [α-{(2- OCH ₃ -4- COOC ₂ H ₄ OCH ₃ ) C ₆ H ₃ O } _a , α-{(2,6-Cl ₂ C ₆ H ₃ S} _b , β-{(2- OCH ₃ -4- COOC ₂ H ₄ OCH ₃ ) C ₆ H ₃ O } _0.8-a , β-{(2,6- Cl ₂ ) C ₆ H ₃ S } _0.1-b Cl _3.1 PN] (0≤a <0.8, 0≤b <0.1) ( Intermediate 43 ) Synthesis of

5.32 g (0.020 mol) TCPN, 3.89 g (0.016 mol) acetonitrile and 21.27 g of acetonitrile were added to a 150 ml flask. After stirring, 2.7 g (0.020 mol) of potassium carbonate was added thereto and reacted for about 2 hours. After the reaction, 0.36 g (0.002 mol) of 2,6-dichlorothiophenol was added to the flask and allowed to react for about 3 hours. After cooling, treatment was performed in the same manner as in Synthesis example 1 to obtain about 9.1 g (105.1 mol% of yield over TCPN).

Synthetic example  44: Phthalonitrile  Compound [α-{(2- OCH ₃ -4- COOC ₂ H ₄ OCH ₃ ) C ₆ H ₃ O } _a , α-{((OC ₂ H ₅ ) ₃ Si) C ₃ H ₆ S} _b , β-{(2- OCH ₃ -4- COOC ₂ H ₄ OCH ₃ ) C ₆ H ₃ O } _1-a , β-{(( OC ₂ H ₅ ) ₃ Si ) C ₃ H ₆ S } _0.25-b Cl _2.75 PN] (0≤a <1, 0≤b <0.25) ( Intermediate 44 ) Synthesis of

6.65 g (0.025 mole) TCPN, 5.60 g (0.025 mole) acetonitrile and 26.59 g of acetonitrile were added to a 150 ml flask. After stirring, 4.75 g (0.034 mol) of potassium carbonate was added and reacted for about 2 hours. After the reaction, 1.49 g (0.006 mol) of (3-mercaptopropyl) triethoxysilane was added to the flask, followed by further reaction for about 3 hours. After cooling, treatment was performed in the same manner as in Synthesis example 1 to obtain about 12.6 g (99. 9 mol% of yield over TCPN).

Synthetic example  45: Phthalonitrile  Compound [α-{(2- OCH ₃ -4- COOC ₂ H ₄ OCH ₃ ) C ₆ H ₃ O } _a , α-{(CH ₃ (OC ₂ H ₅ ) ₂ Si) C ₃ H ₆ S} _b , β-{(2- OCH ₃ -4- COOC ₂ H ₄ OCH ₃ ) C ₆ H ₃ O } _1-a , β-{(CH ₃ (OC ₂ H ₅ ) ₂ Si) C ₃ H ₆ S} _0.25-b Cl _2.75 PN] (0≤a <1, 0≤b <0.25) ( Intermediate 45 ) Synthesis of

6.65 g (0.025 mole) TCPN, 5.60 g (0.025 mole) acetonitrile and 26.59 g of acetonitrile were added to a 150 ml flask. After stirring, 4.75 g (0.034 mol) of potassium carbonate was added and reacted for about 2 hours. After the reaction, 1.93 g (0.006 mol) of (3-mercaptopropyl) dimethoxymethylsilane was added to the flask, and the reaction was further performed for about 3 hours. After cooling, the mixture was treated in the same manner as in Synthesis example 1 to obtain about 12.0 g (yield 97.5 mol% of TCPN).

Synthetic example  46: Phthalonitrile  Compound [α-{(4- COOC ₂ H ₄ OCH ₃ ) C ₆ H ₄ O } _a , α-{(2,6- (CH ₃ ) ₂ C ₆ H ₃ O} _b , β-{(4- COOC ₂ H ₄ OCH ₃ ) C ₆ H ₄ O } _0.8-a , β-{(2,6- ( CH ₃ ) ₂ ) C ₆ H ₃ O }) _{0.2- b} Cl ₃ PN ] (0≤a <0.8, 0≤b <0.2) ( Intermediate 46 ) Synthesis of

6.65 g (0.025 mole) of TCPN, 4.91 g (0.025 mole) of acetonitrile methyl cellosolve and 26.59 g of acetonitrile were added to a 150 ml flask, and a magnetic stirrer was used until the temperature was stabilized at 40 ° C. After stirring for about 30 minutes, potassium carbonate 3.8g (0.0275mol) was added and reacted for about 2 hours. After the reaction, 0.61 g (0.005 mol) of 2,6-xylenol was added to the flask and allowed to react for about 3 hours. After cooling, the same process as in Synthesis Example 1 was performed to give about 11.1 g (108.2 mol% of yield over TCPN).

Synthetic example  47: Phthalonitrile  Compound [α-{(4- COOC ₂ H ₄ OCH ₃ ) C ₆ H ₄ O } _a , α-{(2-C (CH ₃ ) ₃ C ₆ H ₄ O} _b , β-{(4- COOC ₂ H ₄ OCH ₃ ) C ₆ H ₄ O } _1-a , β-{(2-C ( CH ₃ ) ₃ ) C ₆ H ₄ O } _{0.25- b} Cl _{2 .75} PN ] (0≤a <1, 0≤b <0.25) ( Intermediate 47 ) Synthesis of

6.65 g (0.025 mole) of TCPN, 4.91 g (0.025 mole) of acetonitrile methyl cellosolve and 26.59 g of acetonitrile were added to a 150 ml flask, and a magnetic stirrer was used until the temperature was stabilized at 40 ° C. After stirring for about 30 minutes, 4.75 g (0.0344 mol) of potassium carbonate was added and reacted for about 3.5 hours. After the reaction, 0.94 g (0.006 mol) of 2-tert-butylphenol was added to the flask and reacted for about 4.5 hours. After cooling, treatment was performed in the same manner as in Synthesis example 1 to obtain about 11.3 g (yield 99.6 mol% of TCPN).

Synthetic example  48: Phthalonitrile  Compound [α-{(4- COOC ₂ H ₄ OCH ₃ ) C ₆ H ₄ O } _a , α-{(2,6-Cl ₂ C ₆ H ₃ S} _b , β-{(4- COOC ₂ H ₄ OCH ₃ ) C ₆ H ₄ O } _0.8-a , β-{(2,6- Cl ₂ ) C ₆ H ₃ S } _{0.1- b} Cl _{3 .One} PN ] (0≤a <0.8, 0≤b <0.1) ( Intermediate 48 ) Synthesis of

5.32 g (0.020 mole) of TCPN, 3.14 g (0.016 mole) of acetonitrile methyl cellosolve, and 21.27 g of acetonitrile were added to a 150 ml flask, and the magnetic stirrer was used until the temperature was stabilized at 40 ° C. After stirring for about 30 minutes, 2.74 g (0.02 mol) of potassium carbonate was added thereto and reacted for about 2 hours. After the reaction, 0.36 g (0.002 mol) of 2,6-dichlorothiophenol was added to the flask, followed by further reaction for about 4 hours. After cooling, treatment was performed in the same manner as in Synthesis example 1 to obtain about 8.4 g (yield 102.5 mol% of TCPN).

Synthetic example  49: Phthalonitrile  Compound [α-{(4- COOC ₂ H ₄ OCH ₃ ) C ₆ H ₄ O } _a , α-{(2,6-Cl ₂ C ₆ H ₃ S} _b , α-{(4- CN ) C ₆ H ₄ O } _c , β-{(4- COOC ₂ H ₄ OCH ₃ ) C ₆ H ₄ O } _0.7-a , β-{(2,6- Cl ₂ ) C ₆ H ₃ S } _0.2-b , β-{(4- CN ) C ₆ H ₄ O } _a } _{0.1- c} Cl ₃ PN } (0≤a <0.7,0≤b <0.2, 0≤c <0.1) ( Intermediate 49 ) Synthesis of

5.32 g (0.020 mol) of TCPN, 2.75 g (0.014 mol) of p-hydroxybenzoic acid methyl cellosolve and 21.27 g of acetonitrile were added to a 150 ml flask, and a magnetic stirrer was used until the temperature was stabilized at 40 ° C. After stirring for about 30 minutes, potassium carbonate 3.04 g (0.022 mol) was added thereto and reacted for about 2 hours. After the reaction, 0.24 g (0.002 mol) of 4-cyanophenol was added to the flask, and the reaction was further performed for about 1 hour. After the reaction, 0.72 g (0.004 mol) of 2,6-dichlorothiophenol was added to the flask, and the reaction was further performed for about 1 hour. After cooling, the treatment was carried out in the same manner as in Synthesis example 1 to obtain about 8.2 g (yield 99.0 mol% of TCPN).

Synthetic example  50: Phthalonitrile  Compound [α-{(4- COOC ₂ H ₄ OCH ₃ ) C ₆ H ₄ O } _a , α-{(2,6-Cl ₂ C ₆ H ₃ S} _b , α-{(2- COOC ₂ H ₄ OCH ₃ ) C ₁₀ H ₈ O } _c , β-{(4- COOC ₂ H ₄ OCH ₃ ) C ₆ H ₄ O } _0.7-a , β-{(2,6-Cl ₂ C ₆ H ₃ S} _0.2-b , β-{(2- COOC ₂ H ₄ OCH ₃ ) C ₁₀ H ₈ O } _{0.1- c} Cl ₃ PN ] (0≤a <0.7, 0≤b <0.2, 0≤c <0.1) ( Intermediate 50 ) Synthesis of

Into a 150 ml flask, 7.45 g (0.028 mole) of TCPN, 3.85 g (0.020 mole) of p-hydroxybenzoic acid methyl cellosolve, and 29.78 g of acetonitrile were added, and a magnetic stirrer was used until the temperature reached 40 ° C. After stirring for about 30 minutes, potassium carbonate 4.26 g (0.031 mol) was added thereto and reacted for about 2 hours. After the reaction, 0.75 g (0.003 mol) of 1-hydroxy-2-naphthoate methyl cellosolve was added to the flask, followed by further reaction for about 2 hours. After the reaction, 1.00 g (0.006 mol) of 2,6-dichlorothiophenol was added to the flask and allowed to react for about 2 hours. After cooling, treatment was performed in the same manner as in Synthesis example 1 to obtain about 11.4 g (yield 95.1 mol% of TCPN).

Synthetic example  51: Phthalonitrile  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} _0.65-a Cl _3.35 PN] (0≤a <0.65) ( Intermediate 51 ) Synthesis of

Into a 150 ml flask was added TCPN22.60 g (0.085 mole), p-hydroxy methyl benzoate 10.95 g (0.015 mole), potassium carbonate 8.40 g (0.061 mole), benzonitrile 70.07 g, temperature 80 ° C., magnetic sterile The reaction was carried out for about 2 hours while stirring using a ler. After cooling, the mixture was treated in the same manner as in Synthesis example 1 to obtain about 31.7 g (100.7 mol% of yield over TCPN).

Synthetic example  52: Phthalonitrile  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} _0.5-a Cl _3.5 PN] (0≤a <0.5) ( Intermediate 52 ) Synthesis of

Into a 150 ml flask, 10.64 g (0.040 mol) of TCPN, 3.96 g (0.020 mol) of p-hydroxybenzoic acid methyl cellosolve, 3.04 g (0.022 mol) of potassium carbonate, 32.97 g of benzonitrile were added and the inner temperature was 80 ° C. It was made to react for about 1 hour, stirring using a stirrer. After cooling, treatment was performed in the same manner as in Synthesis example 1 to obtain about 13.9 g (100.6 mol% of yield over TCPN).

Synthetic example  53: Phthalonitrile  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 53 ) Synthesis of

Into a 150 ml flask, 16.03 g (0.060 mole) of TCPN, 23.87 g (0.120 mole) of methyl salicylate, 18.24 g (0.132 mole) of potassium carbonate and 63.97 g of acetonitrile were added, and a magnetic stirrer was used. The reaction was carried out for about 8 hours with stirring. After cooling, treatment was performed in the same manner as in Synthesis example 1 to obtain about 35.0 g (yield 99.7 mol% of TCPN).

Synthetic example  54: Phthalonitrile  Compound [β-{(2- COOCH ₃ ) C ₆ H ₄ O } PN ] ( Intermediate 54 ) Synthesis of

4-nitrophthalonitrile 25.10 g (0.145 mole), methyl salicylate 30.89 g (0.203 mole), potassium carbonate 22.04 g (0.16 mole), n-tetrabutylammonium bromide 0.93 g (0.003 mole), acetonitrile 100.42 g was added and reacted for about 40 hours with stirring using a magnetic stirrer at 80 ° C. After cooling, a 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. The crystals extracted after suction filtration were vacuum dried at about 60 ° C. overnight to yield about 34.8 g (86.3 mol% of yield for 4-nitrophthalonitrile).

Example  One: Phthalocyanine  compound[ ZnPc -{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 } _4-x , {β- (4- COOC ₂ H ₄ OCH ₃ ) C ₆ H ₄ O } _{4- y} Cl ₈ ] (0≤x <4,0≤y <? S)

2.59 g (0.006 mol) of intermediate 3 obtained in Synthesis Example 3, 3.51 g (0.006 mol) of intermediate 18 obtained in Synthesis Example 18, 1.05 g of zinc iodide and 5.82 g of benzonitrile were charged into a 150 ml flask. It reacted for about 6 hours, stirring using nitrogen flow (10 mL / min), internal temperature 160 degreeC, and a magnetic stirrer.

After cooling, acetone corresponding to the sum (6.1 g) of the weight of the intermediate used in the phthalocyanation reaction was added, followed by stirring to add a crystallization solution. Subsequently, the prepared crystal solution was added dropwise into methanol (122 g) corresponding to 20 times the sum of the weight of the intermediate used in the phthalocyanation reaction, followed by stirring for 30 minutes. Then, distilled water (61 g) of 1 / 2-times amount of methanol was dripped over 30 minutes, and after completion | finish of dripping, it stirred for 30 more minutes to precipitate crystal | crystallization. After the obtained crystals were suction-filtered, 1/2 times methanol (61 g) at the time of crystallization was added again, stirred for 30 minutes, and 1/2 times distilled water (30.5 g) of methanol was dripped over 30 minutes, after completion | finish of dripping Washing and purification were carried out by further stirring for 30 minutes.

The crystals extracted after suction filtration were vacuum dried at about 60 ° C. overnight to yield about 5.00 g (yield 79.4 mol% of Intermediate 3 and Intermediate 18) of the phthalocyanine compound 1.

The phthalocyanine compound 1 thus obtained was measured by the following method for maximum absorption wavelength, gram extinction coefficient and heat resistance, and the results are shown in Table 2 below.

(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 of 0.8 wt% containing methylcellosolve were measured using the spectrophotometer (the U-2910 make from Hitachi, Ltd.). The measuring method was performed as follows.

In a 50 ml flask, 0.04 g of the obtained phthalocyanine compound 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 flask. Subsequently, 1 mL of the prepared solution was aliquoted using a pipette, all the aliquots were added to a 50 mL flask, and diluted with methanol so that the meniscus of the solution coincided with the mark of the 50 mL flask. It prepared. The solution thus prepared was placed in a cube-shaped hard glass cell of 1 cm on one side, and the transmission spectrum was measured using a spectrophotometer. In addition, when the measured absorbance was A, the gram absorbance coefficient was computed with the following formula | equation.

[Equation 1]

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

(Heat resistance evaluation -1)

0.42 g of acrylic binder polymer manufactured by Nippon Catalysts Corporation, and propylene glycol monomethyl ether acetate (hereinafter abbreviated as PGMEA) to 1.225 g of the obtained phthalocyanine compound, 0.112 g of dipentaerythritol hexaacrylate, Ciba Specialty Chemical Co., Ltd. 0.01 g of the company (IRGACURE 369) was added, dissolved and mixed to prepare a resin coating liquid. The obtained resin coating liquid was applied to a glass plate using a bar coater so that the dye concentration in the dry film was 30 wt% and the dry film thickness was 2 μm, and dried at 80 ° C. for 30 minutes. The absorption spectrum of the coated glass plate thus obtained was measured with a spectrophotometer (manufactured by Hitachi, Ltd .: U-2910), and this was taken as the 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 made into the spectrum after heating. In this manner, the absorbances up to 380 nm to 900 nm were integrated in each spectrum after heating, and the difference in absorbance before and after heating was measured. When E1 before the heating, E2 after the heating, and the difference in the measured absorbance were ΔE, ΔE was calculated by the following equation.

[Equation 2]

(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. The preparation was stirred for 1 hour with a magnetic stirrer, and then the whole amount was collected by a syringe and filtered using a membrane filter (φ = 0.45 µm).

If the preparation can pass through without being clogged by the membrane filter, perform a filtration test that determines that the dye is dissolved in the preparation. (Triangle | delta) and the case where clogging of the filter were made were made into x and solubility evaluation was made.

Example  2: Phthalocyanine  compound[ ZnPc -{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 ₁₀ ] (0≤x <2, 0≤y <4)

Into a 150 ml flask was placed 2.44 g (0.007 mol) of intermediate 1, Synthesis 18, 4.10 g (0.007 mol), intermediate 18 obtained in Synthesis Example 1, 1.33 g (0.004 mol) of zinc iodide, and 6.56 g of benzonitrile. It reacted for about 9 hours, stirring using nitrogen flow (10 mL / min), internal temperature 160 degreeC, and a magnetic stirrer.

After cooling, about 5.95 g (87.9 mol% of yields for Intermediate 1 and Intermediate 1) were obtained in the same manner as in Example 1, to thereby obtain a phthalocyanine compound 2.

The phthalocyanine compound 2 thus obtained was measured in the same manner as in Example 1, and the maximum absorption wavelength, gram absorbance coefficient, and heat resistance were measured, and the results are shown in Table 2 below.

Example  3: Phthalocyanine  compound[ ZnPc -{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 } _{5- y} Cl ₉ ] (0≤x <2,0≤y <5)

2.09 g (0.006 mol) of intermediate 1 obtained in Synthesis Example 1, 3.99 g (0.006 mol) of intermediate 19 obtained in Synthesis Example 19, 1.05 g of zinc iodide (2.03 mol), and benzonitrile 2.03 g were added to a 150 ml flask. It reacted for about 5 hours, stirring using nitrogen flow (10 mL / min), internal temperature 160 degreeC, and a magnetic stirrer.

After cooling, about 5.06 g (yield 80.6 mol% of Intermediate 1 and Intermediate 1) of phthalocyanine compound 3 was obtained in the same manner as in Example 1.

The phthalocyanine compound 3 thus obtained was measured in the same manner as in Example 1, and the maximum absorption wavelength, gram absorbance coefficient, and heat resistance were measured, and the results are shown in Table 2 below.

Example  4: Phthalocyanine  compound[ ZnPc -{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 } _3-x , {β- (4- COOC ₂ H ₄ OCH ₃ ) C ₆ H ₄ O } _{4- y} Cl ₉ ] (0≤x <3,0≤y <4)

2.35 g (0.006 mol) of intermediate 2 obtained in Synthesis Example 2, 3.51 g (0.006 mol) of intermediate 18 obtained in Synthesis Example 18, 1.05 g of zinc iodide (1.95 g) and 1.95 g of benzonitrile were charged into a 150 ml flask. It reacted for about 5 hours, stirring using nitrogen flow (10 mL / min), internal temperature 160 degreeC, and a magnetic stirrer.

After cooling, about 4.58 g (75.6 mol% of yield for Intermediate 2 and Intermediate 18) was obtained in the same manner as in Example 1, to obtain a phthalocyanine compound 4.

The phthalocyanine compound 4 thus obtained was measured in the same manner as in Example 1, and the maximum absorption wavelength, gram absorbance coefficient, and heat resistance were measured, and the results are shown in Table 2 below.

Example  5: Phthalocyanine  compound[ ZnPc -{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 } _{6- y} Cl ₉ ] (0≤x <1, 0≤y <6)

Into a 150 mL flask was charged 1, 1.16 g (0.003 mol) of intermediate 1 obtained in Synthesis Example 1, 5.85 g (0.01 mol) of intermediate 18 obtained in Synthesis Example 18, 1.17 g (0.004 mol) of zinc iodide, and 2.34 g of benzonitrile. It reacted for about 7 hours, stirring using nitrogen flow (10 mL / min), internal temperature 160 degreeC, and a magnetic stirrer.

After cooling, the reaction solution was evaporated under the condition of 140 ° C. × 1 hr, and the solvent was distilled off to obtain a solid obtained by subtracting the weight of benzonitrile (2.34 g) from the sum of the intermediate weight (7.0 g) used in the phthalocyanation reaction. Corresponding methyl cellosolve (4.7 g) was added to the solution for stirring to dissolve the crystallized solution. Subsequently, the prepared crystal solution was added dropwise into methanol (70.2 g) corresponding to 10 times the sum of the weight of the intermediate used in the phthalocyanation reaction and stirred for 30 minutes. Then, distilled water (35.1 g) of 1/2 the amount of methanol was dripped over 30 minutes, and after completion | finish of dripping, it stirred for further 30 minutes and precipitated the crystal | crystallization. After the obtained crystals were suction-filtered, 1/2 times methanol (35.1 g) at the time of crystallization was added again, and it stirred for 30 minutes, and 1/2 times distilled water (17.5 g) of methanol was dripped over 30 minutes, and completion | finish of dripping was completed. After 30 minutes, the mixture was further washed and purified. The crystals taken out after suction filtration were vacuum dried at about 60 ° C. overnight to yield about 6.45 g (89.2 mol% of the yields for Intermediate 1 and Intermediate 18) of Phthalocyanine Compound 5.

Thus obtained phthalocyanine compound 5 was measured in the same manner as in Example 1 to measure the maximum absorption wavelength, gram absorption coefficient and heat resistance, and the results are shown in Table 2 below.

Example  6: Phthalocyanine  compound[ ZnPc -{α- (4- CN ) C ₆ H ₄ O } _x , {α- (2-COOC ₂ H ₄ OCH ₃ C ₁₀ H ₈ O} _y , {β- (4- CN ) C ₆ H ₄ O } _2-x , {β- (2- COOC ₂ H ₄ OCH ₃ ) C ₁₀ H ₈ O } _{4- y} Cl ₁₀ ] (0≤x <2, 0≤y <4)

2.70 g (0.008 mol) of intermediate 1 obtained in Synthesis Example 1, 5.14 g (0.008 mol) of intermediate 22 obtained in Synthesis Example 22, 1.32 g of zinc iodide, and 2.61 g of benzonitrile were charged into a 150 ml flask. The reaction was carried out for about 13 hours while stirring using a magnetic stirrer at 160 ° C and an internal temperature under nitrogen flow (10 ml / min).

After cooling, about 7.4 g (yield 92.5 mol% of Intermediate 1 and Intermediate 22) of phthalocyanine compound 6 was obtained in the same manner as in Example 5.

The phthalocyanine compound 6 thus obtained was measured in the same manner as in Example 1, and the maximum absorption wavelength, gram absorbance coefficient, and heat resistance were measured, and the results are shown in Table 2 below.

Example  7: Phthalocyanine  compound[ ZnPc -{α- (4- NO ₂ ) C ₆ H ₄ O } _x , {α- (4-COOC ₂ H ₄ OCH ₃ C ₆ H ₄ O} _y , {β- (4- NO ₂ ) C ₆ H ₄ O } _2-x , {β- (4- COOC ₂ H ₄ OCH ₃ ) C ₆ H ₄ O } _{4- y} Cl ₁₀ ] (0≤x <2, 0≤y <4)

2.95 g (0.008 mol) of the intermediate 4 obtained in Synthesis Example 4, 4.68 g (0.008 mol) of the intermediate 18 obtained in Synthesis Example 18, 1.40 g of zinc iodide (0.004 mol), and 7.49 g of benzonitrile were charged into a 150 ml flask. It reacted for about 8 hours, stirring using nitrogen flow (10 mL / min), internal temperature 160 degreeC, and a magnetic stirrer.

After cooling, about 6.85 g (86.8 mol% of yields for Intermediate 4 and Intermediate 18) were obtained in the same manner as in Example 1, to obtain a phthalocyanine compound 7.

The phthalocyanine compound 7 thus obtained was measured in the same manner as in Example 1, and the maximum absorption wavelength, gram absorbance coefficient, and heat resistance were measured, and the results are shown in Table 2 below.

Example  8: Phthalocyanine  compound[ ZnPc -{α- (2,4- Cl ₂ ) C ₆ H ₃ S } _x , {α- (4-COOC ₂ H ₄ OCH ₃ C ₆ H ₄ O} _y , {β- (2,4- Cl2 ) C ₆ H ₄ S } _2-x , {β- (4- COOC ₂ H ₄ OCH ₃ ) C ₆ H ₄ O } _{4- y} Cl ₁₀ ] (0≤x <2, 0≤y <4)

Into a 150 ml flask was placed 5, 4.00 g (0.01 mol) of intermediate 5 obtained in Synthesis Example 5, 5.73 g (0.01 mol) of intermediate 18 obtained in Synthesis Example 18, 1.72 g of zinc iodide (3.24 mol), and 3.24 g of benzonitrile. It reacted for about 6 hours, stirring using nitrogen flow (10 mL / min), internal temperature 160 degreeC, and a magnetic stirrer.

After cooling, about 8.50 g (85.0 mol% of yields for Intermediate 5 and Intermediate 18) were obtained in the same manner as in Example 5 to obtain a phthalocyanine compound 8.

The phthalocyanine compound 8 thus obtained was measured in the same manner as in Example 1, and the maximum absorption wavelength, gram absorbance coefficient, and heat resistance were measured, and the results are shown in Table 2 below.

Example  9: Phthalocyanine  compound[ ZnPc -{α- (2- COOCH ₃ ) C ₆ H ₄ S } _x , {α- (4-COOC ₂ H ₄ OCH ₃ C ₆ H ₄ O} _y , {β- (2- COOCH ₃ ) C ₆ H ₄ S } _2-x , {β- (4- COOC ₂ H ₄ OCH ₃ ) C ₆ H ₄ O } _{4- y} Cl ₁₀ ] (0≤x <2, 0≤y <4)

Into a 150 ml flask was charged 3.98 g (0.01 mol) of intermediate 6 obtained in Synthesis Example 6, 5.85 g (0.01 mol) of intermediate 18 obtained in Synthesis Example 18, 1.28 g of zinc iodide, and 3.28 g of benzonitrile. It reacted for about 6 hours, stirring using nitrogen flow (10 mL / min), internal temperature 160 degreeC, and a magnetic stirrer.

After cooling, about 8.9 g (87.6 mol% of the yields of the intermediate 6 and the intermediate 18) of the phthalocyanine compound 9 were obtained in the same manner as in Example 5.

Thus obtained phthalocyanine compound 9 was measured in the same manner as in Example 1 to measure the maximum absorption wavelength, gram absorption coefficient and heat resistance, and the results are shown in Table 2 below.

Example  10: Phthalocyanine  compound[ ZnPc -{α- (2,4,6- Cl ₃ ) C ₆ H ₂ O } _x , {α- (4-COOC ₂ H ₄ OCH ₃ C ₆ H ₄ O} _y , {β- (2,4,6- Cl ₃ ) C ₆ H ₂ O } _2-x , {β- (4- COOC ₂ H ₄ OCH ₃ ) C ₆ H ₄ O } _{4- y} Cl ₁₀ ] (0≤x <2, 0≤y <4)

Into a 150 ml flask was placed 4.79 g (0.01 mol) of intermediate 7 obtained in Synthesis Example 7, 18.5 g (0.01 mol) of intermediate 18 obtained in Synthesis Example 18, 1.76 g (0.006 mol) of zinc iodide, and 3.37 g of benzonitrile. It reacted for about 6 hours, stirring using nitrogen flow (10 mL / min), internal temperature 160 degreeC, and a magnetic stirrer.

After cooling, about 10.1 g (yield 96.7 mol% of intermediate 7 and intermediate 18) of the phthalocyanine compound 10 was obtained by operation similar to Example 5.

The phthalocyanine compound 10 thus obtained was measured in the same manner as in Example 1, and the maximum absorption wavelength, gram absorbance coefficient, and heat resistance were measured, and the results are shown in Table 2 below.

Example  11: Phthalocyanine  compound[ ZnPc -{α- (2,4,6- Cl ₃ ) C ₆ H ₂ O } _x , {α- (2-COOC ₂ H ₄ OCH ₃ C ₁₀ H ₈ O} _y , {β- (2,4,6- Cl ₃ ) C ₆ H ₂ O } _2-x , {β- (2- COOC ₂ H ₄ OCH ₃ ) C ₁₀ H ₈ O } _{4- y} Cl ₁₀ ] (0≤x <2, 0≤y <4)

Into a 150 ml flask was placed 3.70 g (0.008 mol) of intermediate 7 obtained in Synthesis Example 7, 5.22 g (0.008 mol) of intermediate 22 obtained in Synthesis Example 22, 1.32 g of zinc iodide, and 2.78 g of benzonitrile. It was made to react for about 10 hours, stirring using nitrogen flow (10 mL / min), internal temperature 160 degreeC, and a magnetic stirrer.

After cooling, the same procedure as in Example 5 was carried out to obtain about 6.0 g (yield 93.2 mol% of Intermediate 7 and Intermediate 22) of the phthalocyanine compound 11.

Thus obtained phthalocyanine compound 11 was measured in the same manner as in Example 1 to measure the maximum absorption wavelength, gram absorption coefficient and heat resistance, and the results are shown in Table 2 below.

Example  12: Phthalocyanine  compound[ ZnPc -{α- (4- OCH ₃ ) C ₆ H ₄ O } _x , {α- (4-COOC ₂ H ₄ OCH ₃ C ₆ H ₄ O} _y , {β- (4- OCH ₃ ) C ₆ H ₄ O } _2-x , {β- (4- COOC ₂ H ₄ OCH ₃ ) C ₆ H ₄ O } _{4- y} Cl ₁₀ ] (0≤x <2, 0≤y <4)

Into a 150 ml flask was charged the intermediate 8 obtained in Synthesis Example 8, 3.54 g (0.01 mol), the intermediate 18 obtained in Synthesis Example 18, 5.85 g (0.01 mol), zinc iodide 1.76 g (0.006 mol), and 3.13 g of benzonitrile. It reacted for about 8 hours, stirring using nitrogen flow (10 mL / min), internal temperature 160 degreeC, and a magnetic stirrer.

After cooling, about 9.35 g (yield 96.2 mol% of the intermediates 8 and 18) of the phthalocyanine compound 12 was obtained by operation similar to Example 5.

Thus obtained phthalocyanine compound 12 was measured in the same manner as in Example 1 to measure the maximum absorption wavelength, gram absorption coefficient and heat resistance, and the results are shown in Table 2 below.

Example  13: Phthalocyanine  compound[ ZnPc -{α- (4-C ( CH ₃ ) ₃ ) C ₆ H ₄ O } _x , {α- (4-COOC ₂ H ₄ OCH ₃ C ₆ H ₄ O} _y , {β- (4-C ( CH ₃ ) ₃ ) C ₆ H ₄ O } _2-x , {β- (4- COOC ₂ H ₄ OCH ₃ ) C ₆ H ₄ O } _{4- y} Cl ₁₀ ] (0≤x <2, 0≤y <4)

Into a 150 ml flask was placed the intermediate 9 obtained in Synthesis Example 9, 3.80 g (0.01 mol), the intermediate 18 obtained in Synthesis Example 18, 5.85 g (0.01 mol), zinc iodide 1.76 g (0.006 mol), and 3.22 g of benzonitrile. It reacted for about 8 hours, stirring using nitrogen flow (10 mL / min), internal temperature 160 degreeC, and a magnetic stirrer.

After cooling, about 9.6 g (yield of 96.2 mol% of intermediates 9 and 18) of phthalocyanine compound 13 were obtained in the same manner as in Example 5.

Thus obtained phthalocyanine compound 13 was measured in the same manner as in Example 1 to measure the maximum absorption wavelength, gram absorption coefficient and heat resistance, and the results are shown in Table 2 below.

Example  14: Phthalocyanine  compound[ ZnPc -{α- (4- Cl ) C ₆ H ₄ O } _x , {α- (4-COOC ₂ H ₄ OCH ₃ C ₆ H ₄ O} _y , {β- (4- Cl ) C ₆ H ₄ O } _2-x , {β- (4- COOC ₂ H ₄ OCH ₃ ) C ₆ H ₄ O } _{4- y} Cl ₁₀ ] (0≤x <2, 0≤y <4)

Into a 150 mL flask was placed 10, 2.43 g (0.007 mol) of intermediate 10 obtained in Synthesis Example 10, 4.10 g (0.007 mol) of intermediate 18 obtained in Synthesis Example 18, 1.23 g (0.004 mol) of zinc iodide, and 2.18 g of benzonitrile. It reacted for about 6 hours, stirring using nitrogen flow (10 mL / min), internal temperature 160 degreeC, and a magnetic stirrer.

About 6.0 g (yield 88.8 mol% of the intermediates 10 and 18) of the phthalocyanine compound 14 was obtained by the same operation as in Example 5 after cooling.

Thus obtained phthalocyanine compound 14 was measured in the same manner as in Example 1 to measure the maximum absorption wavelength, gram absorption coefficient and heat resistance, and the results are shown in Table 2 below.

Example  15: Phthalocyanine  compound[ ZnPc -{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 } _{4- y} Cl ₁₀ ] (0≤x <2, 0≤y <4)

Into a 150 ml flask was placed 11.11 g (0.007 mole) of intermediate 11, 2.67 g (0.007 mole) obtained in Synthesis Example 11, 1.23 g (0.004 mole) of zinc iodide, and 2.26 g of benzonitrile. It reacted for about 7 hours, stirring using nitrogen flow (10 mL / min), internal temperature 160 degreeC, and a magnetic stirrer.

After cooling, about 6.37 g (yield 91.0 mol% of intermediates 11 and 18) of phthalocyanine compound 15 were obtained in the same manner as in Example 5.

Thus obtained phthalocyanine compound 15 was measured in the same manner as in Example 1 to measure the maximum absorption wavelength, gram absorption coefficient and heat resistance, and the results are shown in Table 2 below.

Example  16: Phthalocyanine  compound[ ZnPc -{α- (2- COOCH ₃ -4- OCH ₃ ) C ₆ H ₃ O } _x , {α- (4-COOC ₂ H ₄ OCH ₃ C ₆ H ₄ O} _y , {β- (2- COOCH ₃ -4- OCH ₃ ) C ₆ H ₃ O } _2-x , {β- (4- COOC ₂ H ₄ OCH ₃ ) C ₆ H ₄ O } _{4- y} Cl ₁₀ ] (0≤x <2, 0≤y <4)

Into a 150 mL flask was charged 4.12 g (0.010 mol) of intermediate 12 obtained in Synthesis Example 12, 5.85 g (0.010 mol) of intermediate 18 obtained in Synthesis Example 18, 1.76 g (0.006 mol) of zinc iodide, and 3.32 g of benzonitrile. It reacted for about 5 hours, stirring using nitrogen flow (10 mL / min), internal temperature 160 degreeC, and a magnetic stirrer.

After cooling, about 9.7 g (yield 94.2 mol% of intermediate 12 and intermediate 18) of the phthalocyanine compound 16 were obtained by operation similar to Example 5.

The phthalocyanine compound 16 thus obtained was measured in the same manner as in Example 1, and the maximum absorption wavelength, gram absorbance coefficient, and heat resistance were measured, and the results are shown in Table 2 below.

Example  17: Phthalocyanine  compound[ ZnPc -{α- (2,6- ( OCH ₃ ) ₂ ) C ₆ H ₃ O } _x , {α- (4-COOC ₂ H ₄ OCH ₃ C ₆ H ₄ O} _y , {β- (2,6- ( OCH ₃ ) ₂ ) C ₆ H ₃ O } _2-x , {β- (4- COOC ₂ H ₄ OCH ₃ ) C ₆ H ₄ O } _{4- y} Cl ₁₀ ] (0≤x <2, 0≤y <4)

Into a 150 ml flask was placed 3.13 g (0.01 mol) of intermediate 13, Synthesis 18, 5.85 g (0.01 mol), intermediate 1.18, 1.73 g (0.006 mol) of zinc iodide, and 3.23 g of benzonitrile. It reacted for about 8 hours, stirring using nitrogen flow (10 mL / min), internal temperature 160 degreeC, and a magnetic stirrer.

After cooling, about 9.65 g (yield 96.3 mol% of intermediate 13 and intermediate 18) of phthalocyanine compound 17 was obtained by operation similar to Example 5.

Thus obtained phthalocyanine compound 17 was measured in the same manner as in Example 1 to measure the maximum absorption wavelength, gram absorption coefficient and heat resistance, and the results are shown in Table 2 below.

Example  18: Phthalocyanine  compound[ ZnPc -{α- C ₆ F ₅ O } _x , {α- (4-COOC ₂ H ₄ OCH ₃ C ₆ H ₄ O} _y , {β- C ₆ F ₅ O } _2-x , {β- (4- COOC ₂ H ₄ OCH ₃ ) C ₆ H ₄ O } _{4- y} Cl ₁₀ ] (0≤x <2, 0≤y <4)

Into a 150 ml flask was charged 4.14 g (0.01 mol) of intermediate 14 obtained in Synthesis Example 14, 5.85 g (0.01 mol) of intermediate 18 obtained in Synthesis Example 18, 1.76 g (0.006 mol) of zinc iodide, and 3.33 g of benzonitrile. It reacted for about 8 hours, stirring using nitrogen flow (10 mL / min), internal temperature 160 degreeC, and a magnetic stirrer.

After cooling, about 9.95 g (yield of 96.5 mol% of intermediates 14 and 18) of phthalocyanine compound 18 was obtained in the same manner as in Example 5.

Thus obtained phthalocyanine compound 18 was measured in the same manner as in Example 1 to measure the maximum absorption wavelength, gram absorption coefficient and heat resistance, and the results are shown in Table 2 below.

Example  19: Phthalocyanine  compound[ ZnPc -{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 ₁₀ ] (0≤x <6)

Into a 150 mL flask was charged 15, 3.58 g (0.008 mol) of intermediate 15 obtained in Synthesis Example 15, 4.92 g (0.008 mol) of intermediate 18 obtained in Synthesis Example 18, 1.47 g (0.005 mol) of zinc iodide, and 7.87 g of benzonitrile. It reacted for about 9 hours, stirring using nitrogen flow (10 mL / min), internal temperature 160 degreeC, and a magnetic stirrer.

After cooling, the same procedure as in Example 1 was carried out to obtain about 8.0 g (yield of 91.2 mol% of Intermediate 15 and Intermediate 18) phthalocyanine compound 19.

Thus obtained phthalocyanine compound 19 was measured in the same manner as in Example 1 to measure the maximum absorption wavelength, gram absorption coefficient and heat resistance, and the results are shown in Table 2 below.

Example  20: Phthalocyanine  compound[ ZnPc -{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} _7-x Cl ₉ ] (0≤x <7)

Into a 150 ml flask was placed 15, 2.13 g (0.005 mol) of intermediate 15 obtained in Synthesis Example 15, 3.33 g (0.005 mol) of intermediate 19 obtained in Synthesis Example 19, 0.88 g (0.003 mol) of zinc iodide, and 1.82 g of benzonitrile. It reacted for about 5 hours, stirring using nitrogen flow (10 mL / min), internal temperature 160 degreeC, and a magnetic stirrer.

After cooling, about 4.78 g (85.1 mol% of the yields for the intermediate 15 and the intermediate 19) of the phthalocyanine compound 20 were obtained by operation similar to Example 5.

The phthalocyanine compound 20 thus obtained was measured in the same manner as in Example 1, and the maximum absorption wavelength, gram absorbance coefficient, and heat resistance were measured, and the results are shown in Table 2 below.

Example  21: Phthalocyanine  compound[ ZnPc -{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} _7-x Cl ₉ ] (0≤x <7)

Into a 150 mL flask was placed 2.16 g (0.005 mol) of intermediate 16 obtained in Synthesis Example 16, 2.93 g (0.005 mol) of intermediate 18 obtained in Synthesis Example 18, 0.88 g (0.003 mol) of zinc iodide, and 1.82 g of benzonitrile. It reacted for about 5 hours, stirring using nitrogen flow (10 mL / min), internal temperature 160 degreeC, and a magnetic stirrer.

After cooling, about 4.62 g (82.2 mol% of yields for Intermediate 16 and Intermediate 18) were obtained in the same manner as in Example 5 to obtain a phthalocyanine compound 21.

Thus obtained phthalocyanine compound 21 was measured in the same manner as in Example 1 to measure the maximum absorption wavelength, gram absorption coefficient and heat resistance, and the results are shown in Table 2 below.

Example  22: Phthalocyanine  compound[ ZnPc -{α- (2- COOC ₂ H ₄ OCH ₃ ) C ₁₀ H ₈ O } _x , {β- (2-COOC ₂ H ₄ OCH ₃ C ₁₀ H ₈ O} _6-x Cl ₁₀ ] (0≤x <6)

Into a 150 mL flask was charged 20, 4.76 g (0.01 mol) of intermediate 20 obtained in Synthesis Example 20, 6.86 g (0.01 mol) of intermediate 22 obtained in Synthesis Example 22, 1.76 g (0.006 mol) of zinc iodide, and 3.87 g of benzonitrile. It reacted for about 5 hours, stirring using nitrogen flow (10 mL / min), internal temperature 160 degreeC, and a magnetic stirrer.

After cooling, about 9.3 g (yield 77.9 mol% of Intermediate 20 and Intermediate 22) of phthalocyanine compound 22 was obtained in the same manner as in Example 5.

Thus obtained phthalocyanine compound 22 was measured in the same manner as in Example 1 to measure the maximum absorption wavelength, gram absorption coefficient and heat resistance, and the results are shown in Table 2 below.

Example  23: Phthalocyanine  compound[ ZnPc -{α- (4- COOC ₂ H ₄ OCH ₃ ) C ₁₀ H ₈ O } _x , {α- (4-COOC ₂ H ₄ OCH ₃ C ₆ H ₄ O} _y , {β- (4- COOC ₂ H ₄ OCH ₃ ) C ₁₀ H ₈ O } _2-x , {β- (4- COOC ₂ H ₄ OCH ₃ ) C ₆ H ₄ O } _{4- y} Cl ₁₀ ] (0≤x <2, 0≤y <4)

Into a 150 ml flask was charged 20, 4.76 g (0.01 mol) of intermediate 20 obtained in Synthesis Example 20, 5.85 g (0.01 mol) of intermediate 18 obtained in Synthesis Example 18, 1.76 g (0.006 mol) of zinc iodide, and 3.54 g of benzonitrile. It reacted for about 5 hours, stirring using nitrogen flow (10 mL / min), internal temperature 160 degreeC, and a magnetic stirrer.

After cooling, about 10.25 g (yield 93.7 mol% of Intermediate 20 and Intermediate 18) of the phthalocyanine compound 23 was obtained in the same manner as in Example 5.

Thus obtained phthalocyanine compound 23 was measured in the same manner as in Example 1 to measure the maximum absorption wavelength, gram absorption coefficient and heat resistance, and the results are shown in Table 2 below.

Example  24: Phthalocyanine  compound[ ZnPc -{α- (4- COOC ₂ H ₄ OCH ₃ ) C ₁₀ H ₈ O } _x , {α- (4-COOC ₂ H ₄ OCH ₃ C ₆ H ₄ O} _y , {β- (4- COOC ₂ H ₄ OCH ₃ ) C ₁₀ H ₈ O } _3-x , {β- (4- COOC ₂ H ₄ OCH ₃ ) C ₆ H ₄ O } _{4- y} Cl ₉ ] (0≤x <3, 0≤y <4)

Into a 150 ml flask was placed 3.21 g (0.006 mol) of intermediate 21 obtained in Synthesis Example 21, 3.22 g (0.006 mol) of intermediate 18 obtained in Synthesis Example 18, 0.99 g (0.003 mol) of zinc iodide, and 2.14 g of benzonitrile. It reacted for about 5 hours, stirring using nitrogen flow (10 mL / min), internal temperature 160 degreeC, and a magnetic stirrer.

After cooling, about 5.22 g (yield 79.2 mol% of intermediate 21 and intermediate 18) of phthalocyanine compound 24 were obtained by the same operation as Example 5.

Thus obtained phthalocyanine compound 24 was measured in the same manner as in Example 1 to measure the maximum absorption wavelength, gram absorption coefficient and heat resistance, and the results are shown in Table 2 below.

Example  25: Phthalocyanine  compound[ ZnPc -{α- (4- COOC ₂ H ₄ OCH ₃ ) C ₁₀ H ₈ O } _x , {α- (4-COOC ₂ H ₄ OCH ₃ C ₆ H ₄ O} _y , {β- (4- COOC ₂ H ₄ OCH ₃ ) C ₁₀ H ₈ O } _3-x , {β- (4- COOC ₂ H ₄ OCH ₃ ) C ₆ H ₄ O } _{3- y} Cl ₁₀ ] (0≤x <3, 0≤y <3)

Into a 150 mL flask was charged 3.21 g (0.006 mol) of intermediate 21 obtained in Synthesis Example 21, 3.03 g (0.006 mol) of intermediate 16 obtained in Synthesis Example 16, 1.05 g of zinc iodide (2.17 g), and 2.17 g of benzonitrile. It reacted for about 5 hours, stirring using nitrogen flow (10 mL / min), internal temperature 160 degreeC, and a magnetic stirrer.

After cooling, about 5.59 g (83.3 mol% of yields for Intermediate 21 and Intermediate 16) of phthalocyanine compound 25 was obtained in the same manner as in Example 5.

Thus obtained phthalocyanine compound 25 was measured in the same manner as in Example 1 to measure the maximum absorption wavelength, gram absorption coefficient and heat resistance, and the results are shown in Table 2 below.

Example  26: Phthalocyanine  compound[ ZnPc -{α- (2- CH ₃ O -4- COOC ₂ H ₄ OCH ₃ ) C ₆ H ₄ O } _x , {α- (4-COOC ₂ H ₄ OCH ₃ C ₆ H ₄ O} _y , {β- (2- CH ₃ O -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-y Cl ₁₀ ] (0≤x <2, 0≤y <4)

3.65 g (0.008 mol) of intermediate 23 obtained in Synthesis Example 23, 4.92 g (0.008 mol) of intermediate 18 obtained in Synthesis Example 18, 1.40 g of zinc iodide (0.004 mol) and 2.78 g of benzonitrile were charged into a 150 ml flask. It reacted for about 6 hours, stirring using nitrogen flow (10 mL / min), internal temperature 160 degreeC, and a magnetic stirrer.

After cooling, about 7.9 g (yield 92.0 mol% of intermediate 18 and intermediate 23) of the phthalocyanine compound 26 were obtained by operation similar to Example 5.

Thus obtained phthalocyanine compound 26 was measured in the same manner as in Example 1 to measure the maximum absorption wavelength, gram absorption coefficient and heat resistance, and the results are shown in Table 2 below.

Example  27: Phthalocyanine  compound[ ZnPc -{α- (2- CH ₃ O -4- COOC ₂ H ₄ OCH ₃ ) C ₆ H ₄ O } _x , {β- (2-CH ₃ O-4-COOC ₂ H ₄ OCH ₃ C ₆ H ₄ O} _6-x Cl ₁₀ ] (0≤x <6)

2.73 g (0.006 mol) of intermediate 23 obtained in Synthesis Example 23, 3.87 g (0.006 mol) of intermediate 24 obtained in Synthesis Example 24, 1.05 g of zinc iodide, and 2.20 g of benzonitrile were charged into a 150 ml flask. It reacted for about 6 hours, stirring using nitrogen flow (10 mL / min), internal temperature 160 degreeC, and a magnetic stirrer.

After cooling, about 6.35 g (yield 93.3 mol% of intermediate 23 and intermediate 24) of the phthalocyanine compound 27 were obtained by operation similar to Example 5.

Thus obtained phthalocyanine compound 27 was measured in the same manner as in Example 1 to measure the maximum absorption wavelength, gram absorption coefficient and heat resistance, and the results are shown in Table 2 below.

Example  28: Phthalocyanine  compound[ ZnPc -{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 ₁₀ ] (0≤x <6)

7.58 g (0.015 mol) of intermediate 16 obtained in Synthesis Example 16, 1.32 g (0.004 mol) of zinc iodide, and 1.90 g of benzonitrile were added to a 150 ml flask, under nitrogen flow (10 ml / min), and an internal temperature of 160 ° C. It was made to react for about 6 hours, stirring using a stirrer.

About 6.9 g (yield 88.8 mol% with respect to intermediate 16) phthalocyanine compound 28 was obtained by operation similar to Example 1 after cooling.

Thus obtained phthalocyanine compound 28 was measured in the same manner as in Example 1 to measure the maximum absorption wavelength, gram absorption coefficient and heat resistance, and the results are shown in Table 2 below.

Example  29: Phthalocyanine  compound[ ZnPc -{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} _7-x Cl ₉ ] (0≤x <7)

7.64 g (0.014 mol) of intermediate 17 obtained in Synthesis Example 17, 1.23 g (0.004 mol) of zinc iodide, and 1.91 g of benzonitrile were added to a 150 ml flask, under nitrogen flow (10 ml / min), and an internal temperature of 160 ° C. was used. It was made to react for about 4 hours, stirring using a stirrer.

After cooling, the same procedure as in Example 1 was carried out to obtain about 7.07 g (89.5 mol% of yield relative to intermediate 17) of the phthalocyanine compound 29.

Thus obtained phthalocyanine compound 29 was measured in the same manner as in Example 1 to measure the maximum absorption wavelength, gram absorption coefficient and heat resistance, and the results are shown in Table 2 below.

In Example 1? 29 of the phthalocyanine compound 1? 29, shown in the configuration of (Z _1? Z ₁₆ in the formula (1)), substituents in Table 1.

[Table 1]

Example 30

About the phthalocyanine compound 2 obtained in Example 2, heat resistance was evaluated in accordance with the method of the following heat resistance evaluation-2. In addition, the method of the following heat resistance evaluation-2 is the same as the method of the said heat resistance evaluation-1 except having changed the dry film thickness from 0.2 micrometer to 0.1 micrometer. The results are shown in Table 2 below. In addition, Table 2 below describes the maximum absorption wavelength and gram absorption coefficient of the phthalocyanine compound 2, which are the same results as in Example 2.

(Heat resistance evaluation -2)

0.42 g of acrylic binder polymers and the propylene glycol monomethyl ether acetate (hereinafter abbreviated to PGMEA) 20.0 g, dipentaerythritol hexaacrylate (0.112 g), Ciba Specialty Chemicals Co., Ltd. ) 0.01g (IRGACURE 369) was added, melt | dissolved, and mixed, and the resin coating liquid was prepared. The obtained resin coating liquid was applied to a glass plate using a bar coater so that the dye concentration in the dry film was 30 wt% and the dry film thickness was 0.1 μm, and dried at 80 ° C. for 30 minutes. Thus, the absorption spectrum of the coated glass plate obtained was measured with the spectrophotometer (The Hitachi, Ltd. make: U-2910), and made this the spectrum before heating. Next, the coating film glass plate which measured the spectrum before heating was heat-processed at 220 degreeC for 20 minutes. The absorption spectrum of this heat-processed coated glass plate was measured with the spectrophotometer, and this was made into the spectrum after heating. The absorbance up to 380 nm-900 nm was integrated in each spectrum after heating measured in this way, and the difference of the absorbance before and after heating was measured. When E1 before the heating, E2 after the heating, and the difference in the measured absorbance were ΔE, ΔE was calculated by the following equation.

[Equation 3]

Example  31

In Example 30, the heat resistance was evaluated in the same manner as in Example 30 except that the phthalocyanine compound 9 obtained in Example 9 was used instead of the phthalocyanine compound 2 obtained in Example 2. The results are shown in Table 2 below. In addition, Table 2 below describes the maximum absorption wavelength and gram absorption coefficient of the phthalocyanine compound 9, which are the same results as in Example 9.

Example  32

In Example 30, the heat resistance was evaluated in the same manner as in Example 30 except that the phthalocyanine compound 11 obtained in Example 11 was used instead of the phthalocyanine compound 2 obtained in Example 2. The results are shown in Table 2 below. In addition, Table 2 below describes the maximum absorption wavelength and gram absorption coefficient of the phthalocyanine compound 11, which are the same results as in Example 11.

Example  33

In Example 30, the heat resistance was evaluated in the same manner as in Example 30 except that the phthalocyanine compound 19 obtained in Example 19 was used instead of the phthalocyanine compound 2 obtained in Example 2. The results are shown in Table 2 below. In addition, Table 2 below describes the maximum absorption wavelength and gram absorption coefficient of the phthalocyanine compound 19, which are the same results as in Example 19.

Example  34

In Example 30, the heat resistance was evaluated in the same manner as in Example 30 except that the phthalocyanine compound 26 obtained in Example 26 was used instead of the phthalocyanine compound 2 obtained in Example 2. The results are shown in Table 2 below. In addition, Table 2 below describes the maximum absorption wavelength and gram absorption coefficient of the phthalocyanine compound 26, which are the same results as in Example 26.

Example  35

In Example 30, the heat resistance was evaluated in the same manner as in Example 30 except that the phthalocyanine compound 27 obtained in Example 27 was used instead of the phthalocyanine compound 2 obtained in Example 2. The results are shown in Table 2 below. In addition, Table 2 below describes the maximum absorption wavelength and gram absorption coefficient of the phthalocyanine compound 27, which are the same results as in Example 27.

Comparative example  One: Phthalocyanine  compound[ ZnPc -{β- (2- COOCH ₃ ) C ₆ H ₄ O } ₄ H ₁₂ Synthesis

Into a 150 ml flask was placed the intermediate 54 obtained in Synthesis Example 54, 4.17 g (0.015 mol), zinc iodide 1.32 g (0.004 mol), and benzonitrile 30.94 g, under nitrogen flow (10 ml / min), internal temperature 185 ° C., magnetic It was made to react for about 5 hours, stirring using a stirrer. About 3.8 g (84.9 mol% of yield with respect to intermediate 54) of the comparative phthalocyanine compound 1 was obtained by operation similar to Example 5 after cooling.

The comparative phthalocyanine compound 1 thus obtained was measured in the same manner as described in Example 1, and the maximum absorption wavelength, gram absorbance coefficient, and heat resistance were measured, and the results are shown in Table 2 below.

Comparative example  2

Comparative phthalocyanine compound 2 {ZnPc (3-COOCH ₃ PhO) ₆ (3-COOHPhO) ₂ F ₈ } was synthesized in the same manner as in Example 18 of JP-A 2008-50599.

The comparative phthalocyanine compound 2 thus obtained was measured in the same manner as in Example 1, and the maximum absorption wavelength, gram absorbance coefficient, and heat resistance were measured, and the results are shown in Table 2 below.

[Table 2]

The phthalocyanine compound synthesize | combined in Example 1? 29 is compared with the comparative phthalocyanine compound 1 ((beta-position 4-substituted phthalocyanine compound) synthesize | combined in the comparative example 1, and the comparative phthalocyanine compound 2 ((beta-position 8 substituted phthalocyanine compound) synthesize | combined in Comparative Example 2). Compared with the gram extinction coefficient (? G), no superiority was observed, but the heat resistance was improved by 2 times or more compared to the β-position 4-substituted phthalocyanine compound having high heat resistance synthesized in Comparative Example 1. Moreover, the phthalocyanine compound 1-35 of Example 1-35 showed the outstanding solvent solubility significantly compared with the comparative phthalocyanine compound 1, 2 of the comparative example 1,2.

In addition, even when the ratio of absorbance of 710 nm showing the 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 is more than twice as large as that of Comparative Examples 1 and 2, so that 710 nm light is efficiently cut. The effect was possible.

Example  36: Phthalocyanine  compound[ ZnPc -{α- (4- OCH ₃ ) C ₆ H ₄ O } _x , {α- (2- OCH ₃ -4-COOC ₂ H ₄ OCH ₃ C ₆ H ₃ O} _y , {β- (4- OCH ₃ ) C ₆ H ₄ O } _0.8-x , {β- (2- OCH ₃ -4- COOC ₂ H ₄ OCH ₃ ) C ₆ H ₃ O } _4.48-y Cl _10.72 ] (0≤x <0.8, 0≤y <4.48)

Into a 150 ml flask was placed 8.06 g (0.003 mol) of intermediate 8 obtained in Synthesis Example 8, 6.38 g (0.012 mol) of intermediate 25 obtained in Synthesis Example 25, 1.32 g of zinc iodide (0.004 mol), and 2.48 g of benzonitrile. Then, the mixture was allowed to react for about 7.5 hours while stirring using a magnetic stirrer at 160 ° C and an internal temperature under nitrogen flow (10 ml / min). About 7.3 g (yield 95.0 mol% with respect to intermediate 8 and intermediate 25) were obtained by operation similar to Example 5 after cooling.

The phthalocyanine compound 30 thus obtained was measured in the same manner as in Example 1, and the maximum absorption wavelength, gram absorbance coefficient, and heat resistance were measured, and the results are shown in Table 4 below.

Example  37: Phthalocyanine  compound[ ZnPc -{α- (4- NO ₂ ) C ₆ H ₄ O } _x , {α- (2- OCH ₃ -4-COOC ₂ H ₄ OCH ₃ C ₆ H ₃ O} _y , {β- (4- NO ₂ ) C ₆ H ₄ O } _0.8-x , {β- (2- OCH ₃ -4- COOC ₂ H ₄ OCH ₃ ) C ₆ H ₃ O } _4.48-y Cl _10.72 ] (0≤x <0.8, 0≤y <4.48)

Into a 150 mL flask was charged 4.11 g (0.003 mol) of intermediate 4 obtained in Synthesis Example 4, 6.38 g (0.012 mol) of intermediate 25 obtained in Synthesis Example 25, and 2.49 g of zinc iodide (1.34 g) and 2.49 g of benzonitrile. It reacted for about 8 hours, stirring using nitrogen flow (10 mL / min), internal temperature 160 degreeC, and a magnetic stirrer. About 7.3 g (yield 94.4 mol% with respect to intermediate 4 and intermediate 25) were obtained by operation similar to Example 5 after cooling.

The phthalocyanine compound 31 thus obtained was measured in the same manner as in Example 1, and the maximum absorption wavelength, gram absorbance coefficient, and heat resistance were measured, and the results are shown in Table 4 below.

Example  38: Phthalocyanine  compound[ ZnPc -{α- (2- OCH ₃ -5- NO ₂ ) C ₆ H ₃ O } _x , {α- (4-COOC ₂ H ₄ OCH ₃ C ₆ H ₄ O} _y , {β- (2- OCH ₃ -5- NO ₂ ) C ₆ H ₃ O } _2-x , {β- (4- COOC ₂ H ₄ OCH ₃ ) C ₆ H ₄ O } _{4- y} Cl ₁₀ ] (0≤x <2, 0≤y <4)

Into a 150 ml flask was placed 2.26 g (0.006 mol) of intermediate 26 obtained in Synthesis Example 26, 3.51 g (0.006 mol) of intermediate 18 obtained in Synthesis Example 18, 1.05 g of zinc iodide (1.97 g), and 1.97 g of benzonitrile. It reacted for about 6 hours, stirring using nitrogen flow (10 mL / min), internal temperature 160 degreeC, and a magnetic stirrer. About 5.9 g (yield 96.7 mol% with respect to intermediate 26 and intermediate 18) were obtained by operation similar to Example 5 after cooling.

Thus obtained phthalocyanine compound 32 was measured in the same manner as in Example 1 to measure the maximum absorption wavelength, gram absorption coefficient and heat resistance, and the results are shown in Table 4 below.

Example  39: Phthalocyanine  compound[ ZnPc -{α- (7- ( C ₉ H ₅ O ₂ )) O} _x , {α- (4-COOC ₂ H ₄ OCH ₃ C ₆ H ₄ O} _y , {β- (7- ( C ₉ H ₅ O ₂ )) O} _2-x , {β- (4- COOC ₂ H ₄ OCH ₃ ) C ₆ H ₄ O } _{4- y} Cl ₁₀ ] (0≤x <2, 0≤y <4)

Into a 150 ml flask was placed 3.27 g (0.010 mol) of intermediate 27 obtained in Synthesis Example 27, 5.85 g (0.010 mol) of intermediate 18 obtained in Synthesis Example 18, 1.76 g (0.006 mol) of zinc iodide, and 3.11 g of benzonitrile. It reacted for about 8 hours, stirring using nitrogen flow (10 mL / min), internal temperature 160 degreeC, and a magnetic stirrer. About 9.1 g (yield of 94.1 mol% with respect to intermediate 27 and intermediate 18) were obtained by operation similar to Example 5 after cooling.

Thus obtained phthalocyanine compound 33 was measured in the same manner as in Example 1 to measure the maximum absorption wavelength, gram absorption coefficient and heat resistance, and the results are shown in Table 4 below.

Example  40: Phthalocyanine  compound[ ZnPc -{α- ( C ₈ H ₅ N ₂ O ) O} _x , {α- (4-COOC ₂ H ₄ OCH ₃ C ₆ H ₄ O} _y , {β- ( C ₈ H ₅ N ₂ O ) O} _1-x , {β- (4- COOC ₂ H ₄ OCH ₃ ) C ₆ H ₄ O } _{4.5- y} Cl _{10 .5} ] (0≤x <1, 0≤y <4.5)

Into a 150 ml flask was charged 1.28 g (0.003 mol) of intermediate 28 obtained in Synthesis Example 28, 5.51 g (0.010 mol) of intermediate 29 obtained in Synthesis Example 29, 1.17 g (0.004 mol) of zinc iodide, and 2.27 g of benzonitrile. It reacted for about 8 hours, stirring using nitrogen flow (10 mL / min), internal temperature 160 degreeC, and a magnetic stirrer. About 6.55 g (yield 93.2 mol% with respect to intermediate 28 and intermediate 29) were obtained by operation similar to Example 5 after cooling.

Thus obtained phthalocyanine compound 34 was measured in the same manner as in Example 1 to measure the maximum absorption wavelength, gram absorption coefficient and heat resistance, and the results are shown in Table 4 below.

Example  41: Phthalocyanine  compound[ ZnPc -{α- (2- COOC ₂ H ₄ OCH ₃ ) C ₁₀ H ₈ -6-O} _x , {α- (4-COOC ₂ H ₄ OCH ₃ C ₆ H ₄ O} _y , {β- (2- COOC ₂ H ₄ OCH ₃ ) C ₁₀ H ₈ -6-O} _2-x , {β- (4- COOC ₂ H ₄ OCH ₃ ) C ₆ H ₄ O } _4-y Cl ₁₀ ] (0≤x <2, 0≤y <4)

Into a 150 ml flask was charged 3.30 g (0.007 mol) of intermediate 30 obtained in Synthesis Example 30, 4.10 g (0.007 mol) of intermediate 18 obtained in Synthesis Example 18, 1.23 g (0.004 mol) of zinc iodide, and 2.48 g of benzonitrile. It was made to react for about 5.5 hours, stirring by using a magnetic stirrer at 160 degreeC, internal temperature under nitrogen flow (10 mL / min). About 6.85 g (yield 89.5 mol% with respect to intermediate 30 and the intermediate 18) were obtained by operation similar to Example 5 after cooling.

Thus obtained phthalocyanine compound 35 was measured in the same manner as in Example 1, the maximum absorption wavelength, gram absorption coefficient and heat resistance and the results are shown in Table 4 below.

Example  42: Phthalocyanine  compound[ ZnPc -{α- (2- COOC ₂ H ₄ OCH ₃ ) C ₁₀ H ₈ -3-O} _x , {α- (4-COOC ₂ H ₄ OCH ₃ C ₆ H ₄ O} _y , {β- (2- COOC ₂ H ₄ OCH ₃ ) C ₁₀ H ₈ -3-O} _2-x , {β- (4- COOC ₂ H ₄ OCH ₃ ) C ₆ H ₄ O } _4-y Cl ₁₀ ] (0≤x <2, 0≤y <4)

Into a 150 mL flask was charged 3.31 g (0.008 mol) of intermediate 31 obtained in Synthesis Example 31, 4.68 g (0.008 mol) of intermediate 18 obtained in Synthesis Example 18, 1.40 g (0.004 mol) of zinc iodide, and 2.83 g of benzonitrile. It reacted for about 6 hours, stirring using nitrogen flow (10 mL / min), internal temperature 160 degreeC, and a magnetic stirrer. About 8.45 g (yield 96.6 mol% with respect to intermediate 31 and intermediate 18) was obtained by operation similar to Example 5 after cooling.

Thus obtained phthalocyanine compound 36 was measured in the same manner as in Example 1 to measure the maximum absorption wavelength, gram absorption coefficient and heat resistance, and the results are shown in Table 4 below.

Example  43: Phthalocyanine  compound[ ZnPc -{α- ( CH ₃ CH ( OCH ₃ C ₂ H ₄ OOC) C ₂ H ₄ S } _x , {α- (4-COOC ₂ H ₄ OCH ₃ C ₆ H ₄ O} _y , {β- ( CH ₃ CH ( OCH ₃ C ₂ H ₄ OOC) C ₂ H ₄ S } _2-x , {β- (4- COOC ₂ H ₄ OCH ₃ ) C ₆ H ₄ O } _4-y Cl ₁₀ ] (0≤x <2, 0≤y <4)

Into a 150 ml flask was placed 3.37 g (0.008 mol) of intermediate 32 obtained in Synthesis Example 32, 4.68 g (0.008 mol) of intermediate 18 obtained in Synthesis Example 18, 1.40 g (0.004 mol) of zinc iodide, and 2.69 g of benzonitrile. It reacted for about 6 hours, stirring using nitrogen flow (10 mL / min), internal temperature 160 degreeC, and a magnetic stirrer. About 6.70 g (yield 80.5 mol% of the intermediates 32 and 18) were obtained by operation similar to Example 5 after cooling.

Thus obtained phthalocyanine compound 37 was measured in the same manner as in Example 1, the maximum absorption wavelength, the gram absorption coefficient and the heat resistance and the results are shown in Table 4 below.

Example  44: Phthalocyanine  compound[ ZnPc -{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} _4-x Cl ₁₂ ] (0≤x <4)

An intermediate 15, 11.92 g (0.028 mole), zinc iodide 2.46 g (0.008 mole), and benzonitrile 3.97 g were added to a 150 ml flask, under nitrogen flow (10 ml / min), internal temperature 160 ° C., and magnetic It was made to react for about 8 hours, stirring using a stirrer. About 12.35 g (yield 99.8 mol% of intermediates 15) were obtained by operation similar to Example 5 after cooling.

Thus obtained phthalocyanine compound 38 was measured in the same manner as in Example 1 to measure the maximum absorption wavelength, gram absorption coefficient and heat resistance, and the results are shown in Table 4 below.

Example  45: Phthalocyanine  compound[ ZnPc -{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} _3.5-x Cl _12.5 ] (0≤x <3.5)

6.49 g (0.016 mol) of intermediate 33 obtained in Synthesis Example 33, 1.40 g (0.004 mol) of zinc iodide, and 2.16 g of benzonitrile were added to a 150 ml flask, and under nitrogen flow (10 ml / min), an internal temperature of 160 DEG C and a magnetic It was made to react for about 6 hours, stirring using a stirrer. About 6.75 g (yield of 100.0 mol% with respect to intermediate 33) were obtained by operation similar to Example 5 after cooling.

Thus obtained phthalocyanine compound 39 was measured in the same manner as in Example 1 to measure the maximum absorption wavelength, gram absorption coefficient and heat resistance, and the results are shown in Table 4 below.

Example  46: Phthalocyanine  compound[ ZnPc -{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} _3-x Cl ₁₃ ] (0≤x <3)

6.17 g (0.016 mol) of intermediate 34 obtained in Synthesis Example 34, 1.40 g (0.004 mol) of zinc iodide, and 2.06 g of benzonitrile were added to a 150 ml flask, and under nitrogen flow (10 ml / min), an internal temperature of 160 ° C. was applied. It was made to react for about 6 hours, stirring using a stirrer. About 6.4 g (yield 99.5 mol% with respect to intermediate 34) were obtained by operation similar to Example 5 after cooling.

The phthalocyanine compound 40 thus obtained was measured in the same manner as in Example 1, and the maximum absorption wavelength, gram absorbance coefficient, and heat resistance were measured, and the results are shown in Table 4 below.

Example  47: Phthalocyanine  compound[ ZnPc -{α- (4- COOC ₂ H ₄ OCH ₃ ) C ₆ H ₄ O } _x , {α- (4-COOCH ₃ C ₆ H ₄ O} _y , {β- (4- COOC ₂ H ₄ OCH ₃ ) C ₆ H ₄ O } _3-x , {β- (4- COOCH ₃ ) C ₆ H ₄ O } _{One- y} Cl ₁₂ ] (0≤x <3, 0≤y <1)

Into a 150 ml flask was placed 15, 5.11 g (0.012 mol) of intermediate 15 obtained in Synthesis Example 15, 1.53 g (0.004 mol) of intermediate 35 obtained in Synthesis Example 35, 1.40 g (0.004 mol) of zinc iodide, and 2.06 g of benzonitrile. It reacted for about 7 hours, stirring using nitrogen flow (10 mL / min), internal temperature 160 degreeC, and a magnetic stirrer. About 6.39 g (yield 92.7 mol% of the intermediates 15 and 35) were obtained by operation similar to Example 5 after cooling.

Thus obtained phthalocyanine compound 41 was measured in the same manner as in Example 1 to measure the maximum absorption wavelength, gram absorption coefficient and heat resistance, and the results are shown in Table 4 below.

Example  48: Phthalocyanine  compound[ ZnPc -{α- (4- COOC ₂ H ₄ OCH ₃ ) C ₆ H ₄ O } _x , {α- (4-NO ₂ C ₆ H ₄ S} _y , {β- (4- COOC ₂ H ₄ OCH ₃ ) C ₆ H ₄ O } _4-x , {β- (4- NO ₂ ) C ₆ H ₄ S } _{One- y} Cl ₁₁ ] (0≤x <4,0≤y <1)

7.29 g (0.016 mol) of intermediate 36 obtained in Synthesis Example 36, 1.40 g (0.004 mol) of zinc iodide, and 2.43 g of benzonitrile were added to a 150 ml flask, and under nitrogen flow (10 ml / min), an internal temperature of 160 ° C. was applied. It was made to react for about 8 hours, stirring using a stirrer. About 7.4 g (yield of 98.1 mol% with respect to intermediate body 36) were obtained by operation similar to Example 5 after cooling.

Thus obtained phthalocyanine compound 42 was measured in the same manner as in Example 1 to measure the maximum absorption wavelength, gram absorption coefficient and heat resistance, and the results are shown in Table 4 below.

Example  49: Phthalocyanine  compound[ ZnPc -{α- (4- COOC ₂ H ₄ OCH ₃ ) C ₆ H ₄ O } _x , (α- (4-Cl) C ₆ H ₄ S} _y , {β- (4- COOC ₂ H ₄ OCH ₃ ) C ₆ H ₄ O } _4-x , {β- (4- Cl ) C ₆ H ₄ S } _{One- y} Cl ₁₁ ] (0≤x <4,0≤y <1)

Into a 150 ml flask was placed the intermediate 37 obtained in Synthesis Example 37, 7.24 g (0.016 mole), zinc iodide 1.40 g (0.004 mole), and benzonitrile 2.41 g. It was made to react for about 8 hours, stirring using a stirrer. About 7.35 g (yield of 97.9 mol% of intermediates 37) were obtained by operation similar to Example 5 after cooling.

Thus obtained phthalocyanine compound 43 was measured in the same manner as in Example 1, the maximum absorption wavelength, gram absorption coefficient and heat resistance and the results are shown in Table 4 below.

Example  50: Phthalocyanine  compound[ ZnPc -{α- (4- COOC ₂ H ₄ OCH ₃ ) C ₆ H ₄ O } _x , (α-C ₆ H ₅ S) _y , {β- (4- COOC ₂ H ₄ OCH ₃ ) C ₆ H ₄ O } _4-x , (β- C ₆ H ₅ S ) _{One- y} Cl ₁₁ ] (0≤x <4, 0≤y <1)

Into a 150 ml flask was placed the intermediate 38 obtained in Synthesis Example 38, 7.11 g (0.016 mole), zinc iodide 1.40 g (0.004 mole), and benzonitrile 2.37 g. It was made to react for about 8 hours, stirring using a stirrer. About 7.25 g (yield 98.4 mol% of the intermediates 38) were obtained by operation similar to Example 5 after cooling.

Thus obtained phthalocyanine compound 44 was measured in the same manner as in Example 1 to measure the maximum absorption wavelength, gram absorption coefficient and heat resistance, and the results are shown in Table 4 below.

Example  51: Phthalocyanine  compound[ ZnPc -{α- (4- COOC ₂ H ₄ OCH ₃ ) C ₆ H ₄ O } _x , (α-C ₆ Cl ₅ S) _y , {β- (4- COOC ₂ H ₄ OCH ₃ ) C ₆ H ₄ O } _4-x , (β- C ₆ Cl ₅ S ) _{One- y} Cl ₁₁ ] (0≤x <4, 0≤y <1)

6.82 g (0.014 mol) of intermediate 39 obtained in Synthesis Example 39, 1.23 g (0.004 mol) of zinc iodide, and 2.27 g of benzonitrile were added to a 150 ml flask, and under nitrogen flow (10 ml / min), an internal temperature of 160 ° C. was used. It was made to react for about 8 hours using a stirrer and stirring. About 6.8 g (yield of 96.5 mol% with respect to intermediate 39) were obtained by operation similar to Example 5 after cooling.

Thus obtained phthalocyanine compound 45 was measured in the same manner as in Example 1 to measure the maximum absorption wavelength, gram absorption coefficient and heat resistance, and the results are shown in Table 4 below.

Example  52: Phthalocyanine  compound[ ZnPc -{α- (4- COOC ₂ H ₄ OCH ₃ ) C ₆ H ₄ O } _x , {α- (4-OCH ₃ C ₆ H ₄ S} _y , {β- (4- COOC ₂ H ₄ OCH ₃ ) C ₆ H ₄ O } _4-x , {β- (4- OCH ₃ ) C ₆ H ₄ S } _{One- y} Cl ₁₁ ] (0≤x <4, 0≤y <1)

Into a 150 ml flask was placed the intermediate 40 obtained in Synthesis Example 40, 7.23 g (0.016 mole), zinc iodide 1.40 g (0.004 mole), and benzonitrile 2.41 g. It was made to react for about 8 hours, stirring using a stirrer. About 7.35 g (yield 98.2 mol% with respect to intermediate 40) were obtained by operation similar to Example 5 after cooling.

Thus obtained phthalocyanine compound 46 was measured in the same manner as in Example 1 to measure the maximum absorption wavelength, gram absorption coefficient and heat resistance, and the results are shown in Table 4 below.

Example  53: Phthalocyanine  compound[ ZnPc -{α- (4- COOC ₂ H ₄ OCH ₃ ) C ₆ H ₄ O } _x , {α- C ₁₀ H ₈ -2-S} _y , {β- (4- COOC ₂ H ₄ OCH ₃ ) C ₆ H ₄ O } _4-x , {β- C ₁₀ H ₈ -2-S} _{One- y} Cl ₁₁ ] (0≤x <4, 0≤y <1)

6.39 g (0.014 mol) of intermediate 41 obtained in Synthesis Example 41, 1.23 g (0.004 mol) of zinc iodide, and 2.13 g of benzonitrile were added to a 150 ml flask, and under nitrogen flow (10 ml / min), an internal temperature of 160 ° C. was used. It was made to react for about 8 hours, stirring using a stirrer. About 6.45 g (yield 97.4 mol% with respect to intermediate body 41) were obtained by operation similar to Example 5 after cooling.

Thus obtained phthalocyanine compound 47 was measured in the same manner as in Example 1 to measure the maximum absorption wavelength, gram absorption coefficient and heat resistance, and the results are shown in Table 4 below.

Example  54: Phthalocyanine  compound[ ZnPc -{α- (4- COOC ₂ H ₄ OCH ₃ ) C ₆ H ₄ O } _x , {α- (2,6-Cl ₂ C ₆ H ₃ S} _y , {β- (4- COOC ₂ H ₄ OCH ₃ ) C ₆ H ₄ O } _4-x , {β- (2,6- Cl ₂ ) C ₆ H ₃ S } _{One- y} Cl ₁₁ ] (0≤x <4, 0≤y <1)

Into a 150 ml flask was placed the intermediate 42 obtained in Synthesis Example 42, 7.38 g (0.016 mole), zinc iodide 1.40 g (0.004 mole), and benzonitrile 2.46 g, under nitrogen flow (10 ml / min), temperature 160 ° C., magnetic It was made to react for about 8 hours, stirring using a stirrer. About 7.45 g (yield of 97.5 mol% with respect to intermediate 42) were obtained by operation similar to Example 5 after cooling.

Thus obtained phthalocyanine compound 48 was measured in the same manner as in Example 1 to measure the maximum absorption wavelength, gram absorption coefficient and heat resistance, and the results are shown in Table 4 below.

Example  55: Phthalocyanine  compound[ ZnPc -{α- (2- OCH ₃ -4- COOC ₂ H ₄ OCH ₃ ) C ₆ H ₃ O } _x , {α- (2,6-Cl ₂ C ₆ H ₃ S} _y , {β- (2- OCH ₃ -4- COOC ₂ H ₄ OCH ₃ ) C ₆ H ₃ O } _3.2-x , {β- (2,6- Cl ₂ ) C ₆ H ₃ S } _0.4-y Cl _12.4 ] (0≤x <3.2, 0≤y <0.4)

6.91 g (0.016 mol) of intermediate 43 obtained in Synthesis Example 43, 1.40 g (0.004 mol) of zinc iodide, and 2.30 g of benzonitrile were added to a 150 ml flask, under nitrogen flow (10 ml / min), internal temperature of 160 ° C., and magnetic It was made to react for about 8 hours, stirring using a stirrer. After cooling, about 6.5 g (99.6 mol% of yield for Intermediate 43) was obtained in the same manner as in Example 5.

Thus obtained phthalocyanine compound 49 was measured in the same manner as in Example 1 to measure the maximum absorption wavelength, gram absorption coefficient and heat resistance, and the results are shown in Table 4 below.

Example  56: Phthalocyanine  compound[ ZnPc -{α- (2- OCH ₃ -4- COOC ₂ H ₄ OCH ₃ ) C ₆ H ₃ O } _x , {α-((OC ₂ H ₅ ) ₃ Si) C ₃ H ₆ S} _y , {β- (2- OCH ₃ -4- COOC ₂ H ₄ OCH ₃ ) C ₆ H ₃ O } _4-x , {β-(( OC ₂ H ₅ ) ₃ Si ) C ₃ H ₆ S } _1-y Cl ₁₁ ] (0≤x <4, 0≤y <1)

8.10 g (0.016 mol) of intermediate 44 obtained in Synthesis Example 44, 1.40 g (0.004 mol) of zinc iodide, and 2.80 g of benzonitrile were added to a 150 ml flask, and under nitrogen flow (10 ml / min), 160 ° C, magnetic temperature It was made to react for about 8 hours, stirring using a stirrer. About 7.43 g (yield 88.9 mol% of the intermediates 44) were obtained by operation similar to Example 5 after cooling.

The phthalocyanine compound 50 thus obtained was measured in the same manner as in Example 1, and the maximum absorption wavelength, gram absorbance coefficient, and heat resistance were measured, and the results are shown in Table 4 below.

Example  57: Phthalocyanine  compound[ ZnPc -{α- (2- OCH ₃ -4- COOC ₂ H ₄ OCH ₃ ) C ₆ H ₃ O } _x , {α- (CH ₃ (OC ₂ H ₅ ) ₂ Si) C ₃ H ₆ S} _y , {β- (2- OCH ₃ -4- COOC ₂ H ₄ OCH ₃ ) C ₆ H ₃ O } _4-x , {β- (CH ₃ (OC ₂ H ₅ ) ₂ Si) C ₃ H ₆ S} _1-y Cl ₁₁ ] (0≤x <4, 0≤y <1)

Into a 150 ml flask was charged the intermediate 45 obtained in Synthesis Example 45, 7.87 g (0.016 mole), zinc iodide 1.40 g (0.004 mole), and benzonitrile 2.62 g, under nitrogen flow (10 ml / min), temperature 160 ° C., magnetic It was made to react for about 8 hours, stirring using a stirrer. About 7.38 g (yield 90.8 mol% with respect to intermediate 45) were obtained by operation similar to Example 5 after cooling.

The phthalocyanine compound 51 thus obtained was measured in the same manner as in Example 1, and the maximum absorption wavelength, gram absorbance coefficient, and heat resistance were measured, and the results are shown in Table 4 below.

Example  58: Phthalocyanine  compound[ ZnPc -{α- (4- COOC ₂ H ₄ OCH ₃ ) C ₆ H ₄ O } _x , {α- (2,6- (CH ₃ ) ₂ C ₆ H ₃ O} _y , {β- (4- COOC ₂ H ₄ OCH ₃ ) C ₆ H ₄ O } _3.2-x , {β- (2,6- ( CH ₃ ) ₂ ) C ₆ H ₃ O } _{0.8- y} Cl ₁₂ ] (0≤x <3.2, 0≤y <0.8)

6.46 g (0.016 mol) of intermediate 46 obtained in Synthesis Example 46, 1.40 g (0.004 mol) of zinc iodide, and 2.19 g of benzonitrile were added to a 150 ml flask, under nitrogen flow (10 ml / min), internal temperature of 160 ° C., and magnetic It was made to react for about 8 hours, stirring using a stirrer. About 6.24 g (yield 91.3 mol% for intermediate 46) were obtained by operation similar to Example 5 after cooling.

Thus obtained phthalocyanine compound 52 was measured in the same manner as in Example 1 to measure the maximum absorption wavelength, gram absorption coefficient and heat resistance, and the results are shown in Table 4 below.

Example  59: Phthalocyanine  compound[ ZnPc -{α- (4- COOC ₂ H ₄ OCH ₃ ) C ₆ H ₄ O } _x , {α- (2-C (CH ₃ ) ₃ C ₆ H ₄ O} _y , {β- (4- COOC ₂ H ₄ OCH ₃ ) C ₆ H ₄ O } _4-x , {β- (2-C ( CH ₃ ) ₃ ) C ₆ H ₄ O } _{One- y} Cl ₁₁ ] (0≤x <4, 0≤y <1)

7.26 g (0.016 mol) of intermediate 47 obtained in Synthesis Example 47, 1.40 g (0.004 mol) of zinc iodide, and 2.42 g of benzonitrile were added to a 150 ml flask, under nitrogen flow (10 ml / min), and an internal temperature of 160 ° C., magnetic The reaction was carried out for about 8.5 hours while stirring using a stirrer. About 7.16 g (yield of 95.1 mol% of intermediates 47) were obtained by operation similar to Example 5 after cooling.

Thus obtained phthalocyanine compound 53 was measured in the same manner as in Example 1 to measure the maximum absorption wavelength, gram absorption coefficient and heat resistance, and the results are shown in Table 4 below.

Example  60: Phthalocyanine  compound[ ZnPc -{α- (4- COOC ₂ H ₄ OCH ₃ ) C ₆ H ₄ O } _x , {α- (2,6-Cl ₂ C ₆ H ₃ S} _y , {β- (4- COOC ₂ H ₄ OCH ₃ ) C ₆ H ₄ O } _3.2-x , {β- (2,6- Cl ₂ ) C ₆ H ₃ S } _{0.4- y} Cl _{12 .4} ] (0≤x <3.2,0≤y <0.4)

Into a 150 ml flask was charged Intermediate 48, 5.71 g (0.014 mol) obtained in Synthesis Example 48, 1.23 g (0.004 mol) of zinc iodide, and 1.90 g of benzonitrile, under nitrogen flow (10 ml / min), temperature 160 ° C., magnetic It was made to react for about 8 hours, stirring using a stirrer. About 5.85 g (yield 98.5 mol% of the intermediates 48) were obtained by operation similar to Example 5 after cooling.

The phthalocyanine compound 54 thus obtained was measured in the same manner as in Example 1, and the maximum absorption wavelength, gram absorbance coefficient, and heat resistance were measured, and the results are shown in Table 4 below.

Example  61: Phthalocyanine  compound[ ZnPc -{α- (4- COOC ₂ H ₄ OCH ₃ ) C ₆ H ₄ O } _x , {α- (2,6-Cl ₂ C ₆ H ₃ S} _y , {α- (4- CN ) C ₆ H ₄ O } _z , {β- (4- COOC ₂ H ₄ OCH ₃ ) C ₆ H ₄ O } _3.2-x , {β- (2,6- Cl ₂ ) C ₆ H ₃ S } _0.8-y , {β- (4- CN ) C ₆ H ₄ O } _{0.4- z} Cl ₁₂ ] (0≤x <2.8, 0≤y <0.8, 0≤z <0.4)

6.63 g (0.016 mol) of intermediate 49 obtained in Synthesis Example 49, 1.40 g of zinc iodide (0.004 mol) and 2.21 g of benzonitrile were added to a 150 ml flask, under nitrogen flow (10 ml / min), temperature 160 ° C, magnetic It was made to react for about 8 hours, stirring using a stirrer. About 6.8 g (98.6 mol% of the yield with respect to intermediate 49) were obtained by operation similar to Example 5 after cooling.

Thus obtained phthalocyanine compound 55 was measured in the same manner as in Example 1, the maximum absorption wavelength, the gram absorption coefficient and the heat resistance and the results are shown in Table 4 below.

Example  62: Phthalocyanine  compound[ ZnPc -{α- (4- COOC ₂ H ₄ OCH ₃ ) C ₆ H ₄ O } _x , {α- (2,6-Cl ₂ C ₆ H ₃ S} _y , {α- (2- COOC ₂ H ₄ OCH ₃ ) C ₁₀ H ₈ O } _z , {β- (4- COOC ₂ H ₄ OCH ₃ ) C ₆ H ₄ O } _3.2-x , {β- (2,6-Cl ₂ C ₆ H ₃ S} _0.8-y , {β- (2- COOC ₂ H ₄ OCH ₃ ) C ₁₀ H ₈ O } _{0.4- z} Cl ₁₂ ] (0≤x <2.8, 0≤y <0.8, 0≤z <0.4)

Into a 150 ml flask was placed the intermediate 50 obtained in Synthesis Example 50, 10.47 g (0.025 mole), zinc iodide 2.15 g (0.007 mole), and benzonitrile 3.49 g, under nitrogen flow (10 ml / min), temperature 160 ° C., magnetic It was made to react for about 8 hours, stirring using a stirrer. About 10.8 g (yield of 99.4 mol% with respect to intermediate 50) was obtained by operation similar to Example 5 after cooling.

Thus obtained phthalocyanine compound 56 was measured in the same manner as in Example 1 to measure the maximum absorption wavelength, gram absorption coefficient and heat resistance, and the results are shown in Table 4 below.

Example  63: Phthalocyanine  compound[ ZnPc -{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 } _3-x , {β- (4- CN ) C ₆ H ₄ O } _{One- y} Cl ₁₂ ] (0≤x <3, 0≤y <1)

Into a 150 ml flask was charged Intermediate 14, 1.39 g (0.004 mol) obtained in Synthesis Example 1, Intermediate 15 obtained in Synthesis Example 15, 5.49 g (0.012 mol), Zinc iodide 1.40 g (0.004 mol) and 2.3 g of benzonitrile. It reacted for about 6 hours, stirring using nitrogen flow (10 mL / min), internal temperature 160 degreeC, and a magnetic stirrer. About 7.05 g (yield 98.6 mol% with respect to intermediate 1 and intermediate 15) was obtained by operation similar to Example 5 after cooling.

Thus obtained phthalocyanine compound 57 was measured in the same manner as in Example 1, the maximum absorption wavelength, the gram absorbance coefficient and the heat resistance and the results are shown in Table 4 below.

In the example 36? 63 of the phthalocyanine compound 30? 57, the third substituent; to the configuration of (formula (1) in the Z _1? Z ₁₆₎ table.

TABLE 3

Example  64

In Example 30, the heat resistance was evaluated in the same manner as in Example 30 except that the phthalocyanine compound 30 obtained in Example 36 was used instead of the phthalocyanine compound 2 obtained in Example 2. The results are shown in Table 4 below. In addition, Table 4 below describes the maximum absorption wavelength and gram absorption coefficient of the phthalocyanine compound 30, which are the same results as in Example 36.

Example  65

In Example 30, the heat resistance was evaluated in the same manner as in Example 30 except that the phthalocyanine compound 31 obtained in Example 37 was used instead of the phthalocyanine compound 2 obtained in Example 2. The results are shown in Table 4 below. In addition, Table 4 below describes the maximum absorption wavelength and gram absorption coefficient of the phthalocyanine compound 31, which are the same results as in Example 37.

Example  66

In Example 30, the heat resistance was evaluated in the same manner as in Example 30 except that the phthalocyanine compound 32 obtained in Example 38 was used instead of the phthalocyanine compound 2 obtained in Example 2. The results are shown in Table 4 below. In addition, Table 4 below describes the maximum absorption wavelength and gram absorption coefficient of the phthalocyanine compound 32, which are the same results as in Example 38.

Example  67

In Example 30, the heat resistance was evaluated in the same manner as in Example 30 except that the phthalocyanine compound 33 obtained in Example 39 was used instead of the phthalocyanine compound 2 obtained in Example 2. The results are shown in Table 4 below. In addition, Table 4 below describes the maximum absorption wavelength and gram absorption coefficient of the phthalocyanine compound 33, which are the same results as in Example 39.

Example  68

In Example 30, the heat resistance was evaluated in the same manner as in Example 30 except that the phthalocyanine compound 36 obtained in Example 42 was used instead of the phthalocyanine compound 2 obtained in Example 2. The results are shown in Table 4 below. In addition, Table 4 below describes the maximum absorption wavelength and gram absorption coefficient of the phthalocyanine compound 36, which are the same results as in Example 42.

Example  69

In Example 30, the heat resistance was evaluated in the same manner as in Example 30 except that the phthalocyanine compound 38 obtained in Example 44 was used instead of the phthalocyanine compound 2 obtained in Example 2. The results are shown in Table 4 below. In addition, Table 4 below describes the maximum absorption wavelength and gram absorption coefficient of the phthalocyanine compound 38, which are the same results as in Example 44.

Example  70

In Example 30, the heat resistance was evaluated in the same manner as in Example 30 except that the phthalocyanine compound 39 obtained in Example 45 was used instead of the phthalocyanine compound 2 obtained in Example 2. The results are shown in Table 4 below. In addition, Table 4 below describes the maximum absorption wavelength and gram absorption coefficient of the phthalocyanine compound 39, which are the same results as in Example 45.

Example  71

In Example 30, the heat resistance was evaluated in the same manner as in Example 30 except that the phthalocyanine compound 45 obtained in Example 51 was used instead of the phthalocyanine compound 2 obtained in Example 2. The results are shown in Table 4 below. In addition, Table 4 below describes the maximum absorption wavelength and gram absorption coefficient of the phthalocyanine compound 45, which are the same results as in Example 51.

Example  72

In Example 30, the heat resistance was evaluated in the same manner as in Example 30 except that the phthalocyanine compound 49 obtained in Example 55 was used instead of the phthalocyanine compound 2 obtained in Example 2. The results are shown in Table 4 below. In addition, Table 4 below describes the maximum absorption wavelength and gram absorption coefficient of the phthalocyanine compound 49, which are the same results as in Example 55.

Example  73

In Example 30, the heat resistance was evaluated in the same manner as in Example 30 except that the phthalocyanine compound 50 obtained in Example 56 was used instead of the phthalocyanine compound 2 obtained in Example 2. The results are shown in Table 4 below. In addition, Table 4 below describes the maximum absorption wavelength and gram absorption coefficient of the phthalocyanine compound 50, which are the same results as in Example 56.

Example  74

In Example 30, the heat resistance was evaluated in the same manner as in Example 30 except that the phthalocyanine compound 55 obtained in Example 61 was used instead of the phthalocyanine compound 2 obtained in Example 2. The results are shown in Table 4 below. In addition, Table 4 below describes the maximum absorption wavelength and gram absorption coefficient of the phthalocyanine compound 55, which are the same results as in Example 61.

TABLE 4

The phthalocyanine compound synthesize | combined in Example 36? 63 is compared with the comparative phthalocyanine compound 1 ((beta-position 4-substituted phthalocyanine compound) synthesize | combined in Comparative Example 1, and the comparative phthalocyanine compound 2 ((beta-position 8 substituted phthalocyanine compound) synthesize | combined in Comparative Example 2). Compared with the gram extinction coefficient (? G), no superiority was observed, but the heat resistance was improved by 2 times or more compared with the β-position 4-substituted phthalocyanine compound having high heat resistance synthesized in Comparative Example 1. Moreover, the phthalocyanine compound 30-57 of Example 36-74 showed the outstanding solvent solubility significantly compared with the comparative phthalocyanine compound 1, 2 of the comparative example 1,2.

In addition, even when the ratio of absorbance of 710 nm showing extra luminescence of PDP and 520 nm, which is a representative wavelength of visible light, using the phthalocyanine compound of the present application, the ratio of absorbance is three times or more compared with Comparative Examples 1 and 2, so that 710 nm light can be efficiently obtained. It showed an effect that can be cut.

In addition, as shown in Table 2, compared to the phthalocyanine compound synthesized from a single intermediate synthesized in Examples 28,29, compared to other intermediate mixed phthalocyanine synthesized in Examples 19,20 having the same substituent and number of substitution As can be seen from the fact that the heat resistance and the absorbance ratio between 710 nm and 520 nm are improved, the number of substituents is 5 to 8, and the phthalocyanine compound having excellent solubility is obtained by mixing intermediates of other substituent groups among the phthalocyanine compounds having the same composition. It shows a desirable effect.

On the other hand, since the phthalocyanine compound obtained by this invention leads to high solubility by making the substituent introduction position of the intermediate used for synthesis uneven, for example, the number of substituents of Example 46 etc. is less than 3-5, and there are few substituents. In the phthalocyanine compound, even when synthesized from a single intermediate, the phthalocyanine compound is characterized by having excellent heat resistance and absorbance ratio between 710 nm and 520 nm.

Example  75: Phthalocyanine  compound[ ZnPc -{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} _2.6-x Cl _13.4 ] (0≤x <2.6)

Into a 150 mL flask was charged the intermediate 51,9.98 g (0.027 mole), zinc iodide 2.37 g (0.007 mole), and benzonitrile 3.33 g in a 150 mL flask, under nitrogen flow (10 mL / min), at 160 ° C., magnetic temperature. The reaction was carried out for about 12 hours while stirring using a stirrer. About 10.41 g (yield 99.9 mol% of the intermediates 51) were obtained by operation similar to Example 5 after cooling.

Thus obtained phthalocyanine compound 58 was measured in the same manner as in Example 1 to measure the maximum absorption wavelength, gram absorption coefficient and heat resistance, and the results are shown in Table 6 below.

Example  76: Phthalocyanine  compound[ ZnPc -{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} _2-x Cl ₁₄ ] (0≤x <2)

Into a 150 mL flask was charged the intermediate 52 obtained in Synthesis Example 52, 12.83 g (0.037 mol), zinc iodide 3.26 g (0.010 mol), and benzonitrile 4.28 g, under nitrogen flow (10 ml / min), internal temperature 160 ° C., magnetic The reaction was carried out for about 12 hours while stirring using a stirrer. About 13.50 g (yield of 100.5 mol% with respect to intermediate 52) was obtained by operation similar to Example 5 after cooling.

Thus obtained phthalocyanine compound 59 was measured in the same manner as in Example 1, and the maximum absorption wavelength, gram absorption coefficient and heat resistance were measured, and the results are shown in Table 6 below.

Example  77: Phthalocyanine  compound[ CuPc -{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} _8-x Cl ₆ ] (0≤x <8)

Into a 150 ml flask was placed the intermediate 53 obtained in Synthesis Example 53, 8.78 g (0.0150 mol), 0.41 g (0.0041 mol) of copper chloride (I), 0.81 g (0.0062 mol) of n-octanol, and 2.12 g of 2-chlorotoluene. Then, the mixture was reacted for about 10 hours while stirring using a magnetic stirrer at 160 ° C, internal temperature under nitrogen flow (10 ml / min). Then, the solution obtained by suction filtration was dripped at 21.2 g of 2-chlorotoluene, and it stirred for 30 minutes. Further, 28.2 g of distilled water was added dropwise thereto, followed by stirring for 1 hour to precipitate crystals. The obtained crystals were filtered off with suction, and then washed with 14.1 g of methanol and 14.1 g of distilled water, followed by stirring and washing. The crystals taken out after suction filtration were vacuum dried at about 60 ° C. overnight to yield about 7.05 g (yield 78.0 mol% for Intermediate 53).

The phthalocyanine compound 60 thus obtained was measured in the same manner as in Example 1, and the maximum absorption wavelength, gram absorbance coefficient, and heat resistance were measured, and the results are shown in Table 6 below.

Moreover, the structure of the substituent (Z <_1> Z <_16> in Formula (1)) of the phthalocyanine compound 58-60 of the said Example 75? 77 is shown in Table 5 below.

[Table 5]

Example  78

In Example 30, the heat resistance was evaluated in the same manner as in Example 30 except that the phthalocyanine compound 58 obtained in Example 75 was used instead of the phthalocyanine compound 2 obtained in Example 2. The results are shown in Table 6 below. In addition, Table 6 below describes the maximum absorption wavelength and gram absorption coefficient of the phthalocyanine compound 58, which are the same results as in Example 75.

Example  79

In Example 30, the heat resistance was evaluated in the same manner as in Example 30 except that the phthalocyanine compound 60 obtained in Example 77 was used instead of the phthalocyanine compound 2 obtained in Example 2. The results are shown in Table 6 below. In addition, Table 6 below describes the maximum absorption wavelength and gram absorption coefficient of the phthalocyanine compound 60, which are the same results as in Example 77.

TABLE 6

The phthalocyanine compound synthesized in Example 75? 77 is compared to Comparative Phthalocyanine Compound 1 (β-substituted phthalocyanine compound) synthesized in Comparative Example 1 or Comparative Phthalocyanine Compound 2 (β-substituted 8-substituted phthalocyanine compound) synthesized in Comparative Example 2. Compared with the gram extinction coefficient εg, no superiority was observed, but the heat resistance was improved by two times or more compared with the β-position 4-substituted phthalocyanine compound having high heat resistance synthesized in Comparative Example 1. Moreover, compared with the comparative phthalocyanine compounds 1 and 2 of the comparative examples 1 and 2, the phthalocyanine compounds 58 and 60 of Examples 75-77 showed the outstanding solvent solubility significantly.

In addition, even when the ratio of absorbance of 710 nm showing extra luminescence of PDP and 520 nm, which is a representative wavelength of visible light, using the phthalocyanine compound of the present application, the ratio of absorbance is three times or more compared with Comparative Examples 1 and 2, so that 710 nm light can be efficiently obtained. It showed an effect that can be cut.

The present application is also based on Japanese Patent Application No. 2009-172973, filed July 24, 2009 and Japanese Patent Application No. 2010-043398, filed February 26, 2010, the disclosures of which are incorporated by reference in their entirety. It is.

Claims (4)

Phthalocyanine compound represented by following formula (1):
[Formula 1]

In said formula (1), Z <_1> Z <_16> is a chlorine atom, following formula (2) or (2 ') each independently:
(2)

In said formula (2) and (2 '), R <^1> is a C1-C3 alkylene group, R <^2> is a C1-C8 alkyl group, R <^4> is a C1-C8 alkoxy group or a halogen atom, m is an integer of 1? 4, p is 0 or 1,
Substituent (a) represented by
Formula (3-1) shown below:
(3)
-X-Ar (3-1)
In said formula (3-1), X is an oxygen atom or a sulfur atom, Ar is a phenyl group or naphthyl group which may be substituted by R <^3> , and R <^3> is respectively independently a cyano group, a nitro group, COOY, OY, A C1-8 alkyl group which may be substituted with a halogen atom, an aryl group or a halogen atom, where Y is a C1-8 alkyl group,
Substituent (b-1) represented by
Formula (3-2) shown below:
[Chemical Formula 4]
-XR ⁷ -COO-R ⁵ (3-2)
In said formula (3-2), X is an oxygen atom or a sulfur atom, R <^7> is a C1-C5 alkylene group, R <^5> may be substituted by the halogen atom or the C1-C8 alkoxy group, It is an alkyl group of 8,
Substituent (b-2) represented by
Formula (3-3) shown below:
[Chemical Formula 5]
-XR ⁷ -Si (R ⁶ ) ₃ (3-3)
In said formula (3-3), X is an oxygen atom or a sulfur atom, R <^7> is a C1-C5 alkylene group, R <^6> is respectively independently a C1-C8 alkoxy group or a C1-C8 alkyl group. to be,
Substituent (b-3) represented by
Group (b-4) derived from 7-hydroxycoumarin, and
Group (b-5) derived from 2,3-dihydroxyquinoxane,
Substituent (b) selected from the group consisting of
In this case, 2? 8 of Z ₁ ? Z ₁₆ are a substituent (a) or a substituent (b), and the remaining part is a chlorine atom, and at least two of 2? 8 substituents (a) or a substituent (b) are a substituent. (a),
M represents a metal, metal, metal oxide or metal halide. The phthalocyanine compound according to claim 1, wherein in formula (1), 2 to 8 substituents (a) or 2 to 7 of the substituents (b) in Z _{1 to} Z ₁₆ are a substituent (a). The phthalocyanine compound according to claim 1 or 2, wherein the substituent (a) is represented as follows:
[Chemical Formula 6]

,

,

,

,

or

. The filter for flat panel displays containing the phthalocyanine compound in any one of Claims 1-3.