JP2014031421A - Phthalocyanine compound and infrared cut filter containing the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a phthalocyanine compound showing a feature of absorption wavelengths conforming to the target wavelengths of an infrared cut filter or a light-selective transmission layer.SOLUTION: The phthalocyanine compound includes moieties Zto Zin a phthalocyanine skeleton, in which 6 to 12 of the moieties are a substituent (a-1) defined below and any of (b) to (h), or over 8 to 12 of the moieties are a substituent (a-2) defined below, and the balance is a chlorine atom or a bromine atom. In formula (2), R1 represents an alkylene group having 1 to 3 carbon atoms; R2 represents an alkyl group having 1 to 8 carbon atoms; R4 represents an alkoxy group having 1 to 8 carbon atoms or a halogen atom; m is an integer of 1 to 4; and p is an integer of 0 to 4. The substituent (a-1) is defined when n is an integer of 1 to 3; and the substituent (a-2) is defined when n is 0; and (b) to (h) each represent a specified substituent.

Description

  The present invention relates to a phthalocyanine compound and an infrared cut filter containing the phthalocyanine compound.

  The infrared cut filter is a filter that selectively reduces the transmittance of light of a specific wavelength, and is suitably used as, for example, an optical filter member or an optical member used for mechanical parts, electrical / electronic parts, automobile parts, and the like. Is. For example, in a solid-state imaging device (also referred to as a camera module), which is one of typical optical members, an infrared cut filter (IR cut filter) that blocks infrared light (particularly wavelength> 780 nm) that becomes optical noise is used. Yes.

  As the infrared cut filter, a reflective filter in which metal or the like is vapor-deposited on a base material to form an inorganic multilayer film and the refractive index of each wavelength is controlled is mainly used. For example, the infrared cut filter described in Patent Document 1 is obtained by depositing a reflective IR cut film (dielectric multilayer film) on a base material. The reflection type filter is very excellent in light blocking performance.

  However, such a reflection type filter has an incident angle dependency in which the reflection characteristic changes depending on the incident angle of light, and its reduction has been a problem. In recent years, camera modules have been miniaturized, and such angle dependency is particularly problematic.

  In addition, when a multilayer film is formed on a glass substrate by vapor deposition, it has a high transmittance in a wavelength range (for example, visible region) to be transmitted and a high cut performance in a wavelength region (for example, near-infrared region) to be blocked. If the number of layers of the multilayer film is increased so as to realize the above, there is a possibility that stress is generated between the layers due to heating / cooling in the vapor deposition process and cracks or cracks are generated.

  Examples of the filter other than the reflective filter as described above include an absorption filter in which the transparent base material contains an absorbent that absorbs near infrared light. Absorptive filters are superior to reflective filters in that they are less dependent on incident angle. However, since the absorption characteristics are inferior to those of the reflection type filter, it is necessary to add a large amount of absorbent or increase the film thickness in order to realize sufficient absorption characteristics. In the case where the transparent substrate is glass, if the concentration of the absorbent is increased, cracks are generated and cannot be molded as glass, so the absorbent concentration must be lowered. On the other hand, when the film thickness of the transparent substrate is increased, there may be a problem in terms of downsizing the module.

  In recent years, in optical members and the like, for example, a digital camera module is mounted on a mobile phone, and the miniaturization of optical members has been further demanded. Accordingly, it is desired to reduce the thickness of an infrared cut filter used for a digital camera module or the like. From the viewpoint of thin film and weight reduction, the resin base material is more advantageous than the glass base material, and the glass base material may have problems such as cracks and cracks as described above. An infrared cut filter is being studied. Attempts have been made to reduce the angle dependence of the reflective filter by using such a resin base material and combining the reflective filter and the absorption filter having different characteristics into a reflective absorption filter. . For example, Patent Document 2 and Patent Document 3 describe an infrared cut filter in which a near-infrared reflective film of a dielectric multilayer film is laminated on a base material in which an absorbent is contained in a resin.

  On the other hand, a reflective filter for producing an inorganic multilayer film by vapor deposition is generally high in cost, and when an infrared cut filter is installed on a sensor, the yield may be reduced due to the warping of the filter. Therefore, by providing an infrared cut layer in which a resin composition containing an absorbent that absorbs near infrared light without using an infrared cut filter is applied and cured on a sensor (cover glass on the sensor), a sensor is provided. Studies are also underway to form an infrared cut layer directly on top. For example, Patent Document 4 describes that an infrared cut filter can be removed by imparting an infrared absorption function to a transparent resin upper layer constituting a microlens or a planarization layer formed on a photoelectric conversion element. ing. According to Patent Document 5, such a configuration eliminates the need for an infrared cut filter, so that the distance below the lens is shorter than before without losing color reproducibility.

  Further, Patent Documents 5 and 6 disclose a polymerizable composition using a tungsten compound as an infrared absorber, and it is disclosed that such a polymerizable composition is used as a solder resist layer or an infrared shielding film in a solid-state imaging device. ing.

  Thus, in order to efficiently block light in the infrared region in the camera module, it is very important to study the absorbent. Various near-infrared absorbing dyes have been known so far. Among them, phthalocyanine compounds are near-infrared absorbing dyes having excellent durability such as heat resistance and light resistance (see, for example, Patent Document 7).

JP 2008-181121 A JP 2011-100084 A JP 2012-8532 A International Publication No. 2004/006336 JP 2012-118294 A JP 2012-118295 A JP-A-6-228533

  However, since conventional phthalocyanine compounds are not designed along the spectral curve suitable for infrared cut filters and infrared cut layers used in camera modules, they are not suitable for infrared cut layers used on reflective absorption filters and sensors. Even if it contains, there exists a problem that visible-light transmittance and the light-shielding property of 700-750 nm near-infrared light are inadequate.

  Therefore, the present invention has been made in view of the above circumstances, and an object thereof is to provide a phthalocyanine compound and an infrared cut filter that have high visible light transmittance and high near-infrared light blocking ability of 700 to 750 nm. To do.

  The object of the present invention is to find that a phthalocyanine compound in which a specific number of specific substituents are arranged exhibits high visible light transmittance and near-infrared light blocking ability of 700 to 750 nm, and can solve the above problems. Completed the invention.

  That is, the said subject can be solved by the phthalocyanine compound of following formula (1).

    Following formula (1):

In the above formula (1), Z _{1 to} Z ₁₆ are each independently a fluorine atom, a chlorine atom, a bromine atom, the following formula (2):

In the above formula (2), R ¹ is an alkylene group having 1 to 3 carbon atoms, R ² is an alkyl group having 1 to 8 carbon atoms, and R ⁴ is an alkoxy group having 1 to 8 carbon atoms or A halogen atom, m is an integer of 1 to 4, p is an integer of 0 to 4, and n is an integer of 1 to 3.
A substituent represented by (a-1),
In the above formula (2), R ¹ is an alkylene group having 1 to 3 carbon atoms, R ² is an alkyl group having 1 to 8 carbon atoms, and R ⁴ is an alkoxy group having 1 to 8 carbon atoms or A halogen atom, m is an integer of 1 to 4, p is an integer of 0 to 4, and n is 0.
A substituent (a-2) represented by the following formula (3):

In the formula (3), ^{R 4} and p are the same as defined in the above formula (2), ^{R 3} is a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, or the formula :-( ^R 1 O,) _m R ² , wherein R ¹ , R ² and m have the same definition as in the above formula (2).
Substituent (b) represented by the following formula (4):

In the above formula (5), R ⁴ and p have the same definition as in the above formula (2), and R ³ has the same definition as in the above formula (3).
Substituent (c) represented by the following formula (5):

In the above formula (5), X is an oxygen atom or a sulfur atom, Ar is a phenyl group or a naphthyl group which may be substituted with R ⁵ , and in this case, R ⁵ is each independently cyano. A group, a nitro group, COOY, OY, a halogen atom, an aryl group, or an alkyl group having 1 to 8 carbon atoms which may be substituted with a halogen atom, wherein Y is an alkyl group having 1 to 12 carbon atoms Is,
A substituent (d) represented by the following formula (6):

In the above formula (6), X is an oxygen atom or a sulfur atom, R ⁷ is an alkylene group having 1 to 5 carbon atoms, and R ⁶ is substituted with a halogen atom or an alkoxy group having 1 to 8 carbon atoms. Is an optionally substituted alkyl group having 1 to 8 carbon atoms,
A substituent (e) represented by the following formula (7):

In the above formula (7), X is an oxygen atom or a sulfur atom, ^{R 7} is an alkylene group having 1 to 5 carbon atoms, ^{R 8} are each independently an alkoxy group having 1 to 8 carbon atoms Or an alkyl group having 1 to 8 carbon atoms,
A group represented by (f), a group derived from 7-hydroxycoumarin (g), or a group derived from 2,3-dihydroxyquinoxane (h),
At this time, among Z _{1 to} Z ₁₆ , 6 to 12 are any of the substituents (a-1) and (b) to (h), or more than 8 and 12 or less are substituents (a -2) and the balance is a fluorine atom, a chlorine atom or a bromine atom,
M represents a metal-free, metal, metal oxide, or metal halide.

  The problem of the present invention can also be solved by the infrared cut filter containing the phthalocyanine of the present invention.

  The phthalocyanine compound of the present invention has a high visible light transmittance and a blocking property of near infrared light of 700 to 750 nm. Therefore, since the phthalocyanine compound of the present invention exhibits spectral characteristics along the target wavelength of the reflection absorption filter or infrared cut layer, it is particularly useful as a dye used in an infrared cut filter or an infrared cut layer for a camera module.

It is a cross-sectional schematic diagram which shows the structure of a camera module.

  The present invention relates to a phthalocyanine compound represented by the following formula (1).

In the above formula (1), Z _{1 to} Z ₁₆ are each independently a fluorine atom, a chlorine atom, a bromine atom, the following formula (2):

In the above formula (2), R ¹ is an alkylene group having 1 to 3 carbon atoms, R ² is an alkyl group having 1 to 8 carbon atoms, and R ⁴ is an alkoxy group having 1 to 8 carbon atoms or A halogen atom, m is an integer of 1 to 4, p is an integer of 0 to 4, and n is an integer of 1 to 3.
A substituent represented by (a-1),
In the above formula (2), R ¹ is an alkylene group having 1 to 3 carbon atoms, R ² is an alkyl group having 1 to 8 carbon atoms, and R ⁴ is an alkoxy group having 1 to 8 carbon atoms or A halogen atom, m is an integer of 1 to 4, p is an integer of 0 to 4, and n is 0.
A substituent (a-2) represented by the following formula (3):

In the formula (3), ^{R 4} and p are the same as defined in the above formula (2), ^{R 3} is a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, or the formula :-( ^R 1 O,) _m R ² , wherein R ¹ , R ² and m have the same definition as in the above formula (2).
Substituent (b) represented by the following formula (4):

In the above formula (4), R ⁴ and p have the same definition as in the above formula (2), and R ³ has the same definition as in the above formula (3).
Substituent (c) represented by the following formula (5):

In the above formula (5), X is an oxygen atom or a sulfur atom, Ar is a phenyl group or a naphthyl group which may be substituted with R ⁵ , and in this case, R ⁵ is each independently cyano. A group, a nitro group, COOY, OY, a halogen atom, an aryl group, or an alkyl group having 1 to 8 carbon atoms which may be substituted with a halogen atom, wherein Y is an alkyl group having 1 to 12 carbon atoms Is,
A substituent (d) represented by the following formula (6):

In the above formula (6), X is an oxygen atom or a sulfur atom, R ⁷ is an alkylene group having 1 to 5 carbon atoms, and R ⁶ is substituted with a halogen atom or an alkoxy group having 1 to 8 carbon atoms. Is an optionally substituted alkyl group having 1 to 8 carbon atoms,
A substituent (e) represented by the following formula (7):

In the above formula (7), X is an oxygen atom or a sulfur atom, ^{R 7} is an alkylene group having 1 to 5 carbon atoms, ^{R 8} are each independently an alkoxy group having 1 to 8 carbon atoms Or an alkyl group having 1 to 8 carbon atoms,
A group represented by (f), a group derived from 7-hydroxycoumarin (g), or a group derived from 2,3-dihydroxyquinoxane (h),
At this time, among Z _{1 to} Z ₁₆ , 6 to 12 are any of the substituents (a-1) and (b) to (h), or more than 8 and 12 or less are substituents (a -2) and the balance is a chlorine atom or a bromine atom,
M represents metal-free, metal, metal oxide or metal halide.
The phthalocyanine compound of the present invention has 6 to 12 substituents (a-1) and (b) to (h) in the phthalocyanine skeleton (Z _{1 to} Z ₁₆ ) or more than 8 and 12 or less. The substituent (a-2) is introduced, and a fluorine atom, a chlorine atom or a bromine atom is introduced into the remainder. The phthalocyanine compound having such a structure has a high visible light transmittance and a near-infrared light blocking property in the vicinity of 700 to 750 nm (low transmittance at 700 to 750 nm). Specifically, the phthalocyanine compound of the present invention has a maximum absorption wavelength (λmax) of 700 to 760 nm when measured in an acrylic resin by the method described in Examples below, and 50% transmittance at 650 nm. And the transmittance at 550 nm is 85% or more, preferably 90% or more, the transmittance at 700 nm is 40% or less, preferably 38.5% or less, and the maximum absorption wavelength ( The transmittance at λmax) is 30% or less, more preferably 20% or less. Such a balance of transmittance of the phthalocyanine compound (that is, high transmittance at 550 nm, low transmittance at 700 nm and λmax; the same applies hereinafter) is a spectrum along the target wavelength of the reflection absorption filter or infrared cut layer. It is a characteristic. In this specification, “transmittance at 550 nm when adjusted to 50% transmittance at 650 nm” is simply “transmittance at 550 nm” and “50% transmittance at 650 nm”. "Transmittance at 700 nm when adjusted to" is simply "Transmittance at 700 nm", and "Transmission at maximum absorption wavelength (λmax) when adjusted to be 50% transmittance at 650 nm" The “rate” is simply referred to as “transmittance at λmax”, respectively.

  In the phthalocyanine compound of the present invention, the above substituents are usually introduced randomly (that is, the phthalocyanine compound of the present invention exists in the form of a mixture). By introducing the substituents randomly without controlling the number or position, the solvent solubility is excellent as compared with the case of introducing the substituents randomly with the number or position controlled (single compound). The associative property can also be controlled depending on the number of substituents introduced. Here, the phthalocyanine compound of the present invention is excellent in solubility in ether solvents, ester solvents, and ketone solvents. The phthalocyanine compound of the present invention also has high compatibility with the resin. Furthermore, the phthalocyanine compound of the present invention is excellent in heat resistance. For this reason, a resin layer can be formed by heating from a phthalocyanine compound and a resin. In addition to the above-described advantages, the phthalocyanine compound of the present invention is excellent in at least one characteristic of compatibility with a resin, light resistance, and weather resistance.

  The characteristics of the phthalocyanine compound generally vary depending on the type of substituent, the number of introductions, the introduction location (α-position, β-position), and the like. In order to impart solubility, introduction of a substituent is indispensable. For example, as the type of substituent, a substituent containing a nitrogen atom (—NE; where E represents an arbitrary substituent) , The same applies hereinafter), the sulfur-containing substituent (—SE), and the oxygen-containing substituent (—OE) in this order, the absorption wavelength of the phthalocyanine compound is shifted to the longer wavelength side. Also, the greater the number of substituents introduced into the phthalocyanine skeleton, the more the absorption wavelength shifts to the longer wavelength side. Therefore, the phthalocyanine compound of the present invention has excellent transmittance at 550 nm and 700 to 750 nm by introducing an appropriate number of substituents (—OE) containing oxygen atoms or substituents (—SE) containing sulfur atoms. Balance can be achieved. In addition, the phthalocyanine compound in which a substituent containing an oxygen atom (-OE) or a substituent containing a sulfur atom (-SE) is introduced in the β-position is compared with the case where these substituents are introduced in the α-position, The maximum absorption wavelength shifts to the shorter wavelength side.

  Therefore, the phthalocyanine compound of the present invention can be suitably used as an infrared cut filter for a camera module or a dye for an infrared cut layer.

Hereinafter, the present invention will be described in detail. In the present specification, the phthalocyanine compound represented by the above formula (1) is also simply referred to as “phthalocyanine compound” or “phthalocyanine compound according to the present invention”. In the present specification, the substituent of Z ₂ , Z ₃ , Z ₆ , Z ₇ , Z ₁₀ , Z ₁₁ , Z ₁₄ and Z ₁₅ in the above formula (1) is simply referred to as “substituent at the β-position”. Z ₂ , Z ₃ , Z ₆ , Z ₇ , Z ₁₀ , Z ₁₁ , Z ₁₄ and Z ₁₅ are collectively referred to as “β-position”. Similarly, in the above formula (1), the substituents of Z ₁ , Z ₄ , Z ₅ , Z ₈ , Z ₉ , Z ₁₂ , Z ₁₃ and Z ₁₆ are also simply referred to as “substituents at the α-position”, or Z ₁ , Z ₄ , Z ₅ , Z ₈ , Z ₉ , Z ₁₂ , Z ₁₃ and Z ₁₆ are also collectively referred to as “α-position”.

  In the above formula (1), M represents a metal-free, metal, metal oxide or metal halide. Here, metal-free means an atom other than a metal, for example, two hydrogen atoms. Examples of the metal include iron, magnesium, nickel, cobalt, copper, palladium, zinc, vanadium, titanium, indium, and tin. Examples of the metal oxide include titanyl and vanadyl. Examples of the metal halide include aluminum chloride, indium chloride, germanium chloride, tin (II) chloride, tin (IV) chloride, and silicon chloride. Preferred are copper, zinc, cobalt, nickel, iron, vanadyl, titanyl, indium chloride and tin (II) chloride, more preferred are copper, vanadyl and zinc, and vanadyl and zinc are particularly preferred.

In the above formula (1), among the substituents Z _{1 to} Z ₁₆ , 6 to 12 are any of the substituents (a-1) and (b) to (h), and the balance is a fluorine atom, A chlorine atom or a bromine atom. Here, among Z _{1 to} Z ₁₆ , when the total number of substitutions (total number of introductions) of the substituents (a-1) and (b) to (h) is less than 6, a region of 600 to 700 nm Therefore, it is not suitable as an infrared cut filter for a camera module or a dye for an infrared cut layer. In addition, the solvent and resin solubility is lowered, which is not preferable. On the other hand, when the total number of substitutions (total number of introductions) of the substituents (a-1) and (b) to (h) exceeds 12, the maximum absorption wavelength is shifted to the longer wavelength side, and the association Since the absorption peak derived from sex becomes small, absorption in the wavelength region of 700 nm to λmax is insufficient, and it is not suitable as an infrared cut filter for a camera module or a dye for an infrared cut layer.

Of these, considering the excellent balance of transmittance at 550 nm and 700 to 750 nm, solvent solubility, etc., the total number of substitutions of substituents (a-1) and (b) to (h) (total number of introductions) It is preferable that there are many. For this reason, among the substituents Z _{1 to} Z _{16 in} the above formula (1), 8 to 12 are preferably any of the substituents (a-1) and (b) to (h). Twelve are more preferably any one of the substituents (a-1) and (b) to (h). The balance is a fluorine atom, a chlorine atom or a bromine atom, preferably a fluorine atom or a chlorine atom, and more preferably a chlorine atom in view of transmittance at 550 nm and heat resistance, Considering the transmittance at ˜750 nm, it is more preferably a fluorine atom.

  The smaller the number of fluorine atoms, chlorine atoms or bromine atoms present in the phthalocyanine compound, the smaller the absorption intensity of the sub-peaks. Conversely, the larger the number of fluorine atoms, chlorine atoms or bromine atoms, the larger the absorption intensity of the sub-peaks. For this reason, in order to obtain appropriate spectral characteristics, the total number of substitutions (total number of introductions) of fluorine atoms, chlorine atoms, and bromine atoms must be 4 to 10, preferably 4 to 8. More preferably, it is 4-6.

Moreover, the introduction position in the phthalocyanine skeleton of any of 6 to 12 substituents (a-1) and (b) to (h) is not particularly limited as long as the total number of substitutions is in the above range. Therefore, as described below, each of the structural units including Z _{1 to} Z ₄ , Z _{5 to} Z ₈ , Z _{9 to} Z ₁₂ , and Z _{13 to} Z ₁₆ is represented by structural units A, B, C, and D, respectively. Then, any of 6 to 12 substituents (a-1) and (b) to (h) may be introduced substantially uniformly or non-uniformly in the structural units A to D. Preferably, any of 6 to 12 substituents (a-1) and (b) to (h) are introduced non-uniformly in the structural units A to D. The presence of substituents in this way is preferable in terms of balancing associative control, compatibility with the resin, heat resistance, and the like. Moreover, although a detailed mechanism is unknown, solvent solubility, especially the solvent solubility to an ether solvent improves because a substituent (a-1)-(h) exists in a suitable number heterogeneity, In addition, the presence of fluorine atoms, chlorine atoms, or bromine atoms is considered to increase the absorption wavelength and improve durability (light resistance, heat resistance). In addition, when multiple types of substituent (a-1)-(h) exists, these substituents may be respectively the same or different.

Alternatively, in the above formula (1), among the substituents Z _{1 to} Z ₁₆ , more than 8 and not more than 12 are substituents (a-2) and the remainder is a fluorine atom, a chlorine atom or a bromine atom . Here, among Z _{1 to} Z _{16, if} the number of substitutions (introduction number) of the substituent (a-2) is 8 or less, the absorption derived from the associative properties of phthalocyanine in the region of 600 to 700 nm becomes strong. It is not suitable as an infrared cut filter for a camera module or a dye for an infrared cut layer. In addition, the solvent and resin solubility is lowered, which is not preferable. On the other hand, when the number of substitutions (introduction number) of the substituent (a-2) exceeds 12, the maximum absorption wavelength shifts to the long wavelength side, and the associative-derived absorption peak becomes small. , The absorption in the wavelength region of 700 nm to λmax is insufficient, the transmittance at 700 to 750 nm is increased, and it is not suitable as an infrared cut filter for a camera module or a dye for an infrared cut layer.

Of these, considering the excellent balance of transmittance at 550 nm and 700 to 750 nm, solvent solubility, and the like, it is preferable that the number of substituents (a-2) is large. Thus, the substituents _Z 1 _{to Z 16} in the formula (1), preferably 9 to 12 amino is substituent (a-2), 10 to 12 pieces in the substituent (a-2) More preferably. The balance is a fluorine atom, a chlorine atom or a bromine atom, preferably a chlorine atom or a bromine atom, and more preferably a chlorine atom in view of transmittance at 550 nm and heat resistance, and 700 nm Considering the transmittance at ˜750 nm, it is more preferably a fluorine atom.

  The smaller the number of fluorine, chlorine or bromine atoms present in the phthalocyanine compound, the smaller the absorption intensity of the sub-peak, and vice versa, the greater the number of fluorine, chlorine or bromine atoms, the greater the absorption intensity of the sub-peak. For this reason, in order to obtain appropriate spectral characteristics, the total number of substitutions (total number of introductions) of fluorine atoms, chlorine atoms and bromine atoms must be 4 or more and less than 8, and it should be 4 to 7 Is preferable, and 4 to 6 is preferable.

Moreover, the introduction position in the phthalocyanine skeleton of more than 8 but not more than 12 substituents (a-2) is not particularly limited as long as the total number of substitutions is in the above range. Therefore, as described below, each of the structural units including Z _{1 to} Z ₄ , Z _{5 to} Z ₈ , Z _{9 to} Z ₁₂ , and Z _{13 to} Z ₁₆ is represented by structural units A, B, C, and D, respectively. Then, more than 8 and not more than 12 substituents (a-2) may be introduced substantially uniformly or non-uniformly in the structural units A to D. Preferably, more than 8 but not more than 12 substituents (a-2) are introduced heterogeneously in the structural units A to D. The presence of substituents in this way is preferable in terms of balancing associative control, compatibility with the resin, heat resistance, and the like. Although the detailed mechanism is unknown, the presence of an appropriate number of heterogeneous substituents (a-2) improves solvent solubility, particularly solvent solubility in ether solvents, The presence of chlorine atom or bromine atom is considered to increase the absorption wavelength and improve the durability (light resistance, heat resistance). In addition, when multiple types of substituent (a-2) exists, these substituents may be respectively the same or different.

  Hereinafter, the substituents (a-1), (a-2), and (b) to (h) will be described in detail.

(Substituent (a-1))
In the present invention, the substituent (a-1) has the following formula (2):

It is represented by

In the above formula (2), R ⁴ , p and R ¹ , R ² and m in the group represented by the formula: — (CH ₂ ) _n COO (R ¹ O) _m R ² will be described.

In the above formula (2), R ¹ is an alkylene group having 1 to 3 carbon atoms. Here, examples of the alkylene group having 1 to 3 carbon atoms include a methylene group, an ethylene group, a tetramethylene group, and a propylene group. Among these, R ¹ is preferably an ethylene group or a propylene group, and is preferably an ethylene group in consideration of the above properties such as the balance of transmittance at 550 nm and 700 to 750 nm, solvent solubility, and heat resistance. Is more preferable.

In the above formula (2), R ² is an alkyl group having 1 to 8 carbon atoms. Here, it does not restrict | limit especially as a C1-C8 alkyl group, A C1-C8 linear, branched or cyclic alkyl group is mentioned. More specifically, examples of the alkyl group having 1 to 8 carbon atoms include methyl group, ethyl group, 2-methylbutyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert. Examples include linear, branched or cyclic alkyl groups such as -butyl group, n-pentyl group, isopentyl group, neopentyl group, n-hexyl group, cyclohexyl group, n-heptyl group, n-octyl group and 2-ethylhexyl group. It is done. Among these, in consideration of the above properties such as transmittance balance at 550 nm and 700 to 750 nm, solvent solubility, heat resistance and the like, a linear or branched alkyl group having 1 to 5 carbon atoms, particularly 1 to 3 carbon atoms. These linear or branched alkyl groups are preferred.

In the above formula (2), m represents the number of repeating units of the oxyalkylene group (R ¹ O) and is an integer of 1 to 4. In consideration of the above properties such as the balance of transmittance at 550 nm and 700 to 750 nm, solvent solubility, and heat resistance, m is preferably 1 or 2.

In the above formula (2), R ⁴ is an alkoxy group having 1 to 8 carbon atoms or a halogen atom. Here, as the alkoxy group having 1 to 8 carbon atoms, methoxy group, ethoxy group, propoxy group, isopropoxy group, butoxy group, pentyloxy group, hexyloxy group, 2-ethylhexyloxy group, octyloxy group, etc. Examples include a chain, branched or cyclic alkoxy group. Among these, in consideration of the above properties such as the balance of transmittance at 550 nm and 700 to 750 nm, solvent solubility, heat resistance and the like, a linear or branched alkoxy group having 1 to 5 carbon atoms, particularly 1 to 3 carbon atoms. These linear or branched alkoxy groups are preferred. Moreover, as a halogen atom, a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom are mentioned. Among these, a chlorine atom or a bromine atom is preferable in consideration of the above properties such as the balance of transmittance at 550 nm and 700 to 750 nm, solvent solubility, and heat resistance. Furthermore, in the above formula, p is represents the number alkoxy group or a halogen atom (R ⁴⁾ is bonded to a phenoxy group, an integer of 0-4. In consideration of the above properties such as transmittance balance at 550 nm and 700 to 750 nm, solvent solubility, and Gram extinction coefficient, preferably p is 0, 1 or 2, more preferably 0 or 1. .

  Moreover, in said formula (2), n is an integer of 1-3. In consideration of the above properties such as the balance of transmittance at 550 nm and 700 to 750 nm, solvent solubility, and heat resistance, n is preferably 1 or 2.

That is, in the substituent (a-1), R ¹ is an ethylene group or a propylene group, R ² is a linear or branched alkyl group having 1 to 3 carbon atoms, and m is 1 or 2. And n is preferably 1 or 2, and is preferably represented by Formula (2).

  More specifically:

Those having the following formula are preferred.

In addition, in the substituent (a-1) of the above formula (2), the bonding position of the substituent — (CH ₂ ) _n COO (R ¹ O) R ^{2 to} the benzene ring is not particularly limited. For example, when p is 0, the substituent (a-1) has a structure in which one substituent “— (CH ₂ ) _n COO (R ¹ O) _m R ² ” is bonded to a phenoxy group. Have. Here, the substituent “— (CH ₂ ) _n COO (R ¹ O) _m R ² ” is any of ortho-position (2-position), meta-position (3-position) or para-position (4-position) of the phenoxy group. It is arranged at such a position. Of these, the 3rd and 4th positions are preferred, and the 4th position is particularly preferred. When the relatively bulky substituent —COO (R ¹ O) R ² is arranged at the 3-position or 4-position, particularly the 4-position, the heat resistance is excellent and fine associability can be controlled by the number of substituents to be introduced. An excellent balance between 550 nm transparency and 700 to 750 nm light shielding properties can be achieved. Moreover, the phthalocyanine compound having such a structure has excellent solubility in ether-based, ester-based, and ketone-based solvents, and also has excellent compatibility with resins. In the above formula (2), when p is 1, the substituent (a-1) is one substituent “— (CH ₂ ) _n COO (R ¹ O) _m R ² ” and It has a structure in which one alkoxy group having 1 to 8 carbon atoms or a halogen atom (—R ⁴ ) is bonded to a phenoxy group. Here, the substituents “— (CH ₂ ) _n COO (R ¹ O) _m R ² ” and “R ⁴ ” may each be introduced at any position of the phenoxy group. In this case, considering the above characteristics such as the balance of transmittance at 550 nm and 700 to 750 nm, solvent solubility, heat resistance and the like, the 2,4, 3,4, 3,5 and the like are preferable. The 3rd and 4th positions are more preferred.

(Substituent (a-2))
In the present invention, the substituent (a-2) is represented by the following formula in which n is 0 in the above formula (2).

In the above formula, substituents R ¹ , R ² , R ⁴ , m and p are the same as defined in the above substituent (a-1).

  That is, the substituent (a-2) preferably has the following structure.

  More preferably, the substituent (a-2) has the following structure.

(Substituent (b))
In the present invention, the substituent (b) has the following formula (3):

It is represented by

In the above formula (3), R ⁴ and p have the same definitions as those in the above formula (2), and thus the description thereof is omitted here. R ³ is a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, or a group represented by the formula: — (R ¹ O) _m R ² . Here, it does not restrict | limit especially as a C1-C8 alkyl group, A C1-C8 linear, branched or cyclic alkyl group is mentioned. 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 Examples include linear, branched or cyclic alkyl groups such as -pentyl group, isopentyl 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 properties such as transmittance balance at 550 nm and 700 to 750 nm, solvent solubility, heat resistance and the like, a linear or branched alkyl group having 1 to 5 carbon atoms, particularly 1 to 3 carbon atoms. These linear or branched alkyl groups are preferred. In addition, R ¹ , R ^2, and m in the group represented by the formula: — (R ¹ O) _m R ² have the same definition as in the above formula (2), and thus the description thereof is omitted here. In consideration of the above properties such as solvent solubility and heat resistance, R ³ is represented by a hydrogen atom, a linear or branched alkyl group having 1 to 3 carbon atoms, or a formula: — (R ¹ O) _m R ^2. It is preferably a group, and more preferably a hydrogen atom, a formula: — (R ¹ O) _m R ² .

That is, in the substituent (b), R ³ is a hydrogen atom, a linear or branched alkyl group having 1 to 3 carbon atoms, or a group represented by the formula: — (R ¹ O) _m R ^2. Wherein R ¹ is an ethylene group or a propylene group, R ² is a linear or branched alkyl group having 1 to 3 carbon atoms, and m is 1 or 2, represented by formula (3) It is preferable. In this case, R ² is preferably a methyl group or an ethyl group, particularly a methyl group.

  More specifically:

Those having the following formula are preferred.

Moreover, in the substituent (b) of the above formula (3), the bonding position of the substituent —SO ₂ NHR ^{3 to} the benzene ring is not particularly limited. For example, when p is 0, the substituent (b) has a structure in which one substituent “—SO ₂ NHR ³ ” is bonded to a phenoxy group. Here, the substituent “—SO ₂ NHR ³ ” is arranged at any position of the phenoxy group in the ortho position (the 2nd position), the meta position (the 3rd position), or the para position (the 4th position). Of these, the 3rd and 4th positions are preferred, and the 4th position is particularly preferred. When the relatively bulky substituent —SO ₂ NHR ³ is arranged at the 3rd or 4th position, particularly the 4th position, the heat resistance is excellent and fine associability can be controlled by the number of substituents to be introduced. And a good balance between light shielding properties of 700 to 750 nm can be achieved. Moreover, the phthalocyanine compound having such a structure has excellent solubility in ether-based, ester-based, and ketone-based solvents, and also has excellent compatibility with resins. In the above formula (3), when p is 1, the substituent (b) is one substituent “—SO ₂ NHR ³ ” and one alkoxy group having 1 to 8 carbon atoms or It has a structure in which a halogen atom (—R ⁴ ) is bonded to a phenoxy group. Here, the substituents “—SO ₂ NHR ³ ” and “R ⁴ ” may each be introduced at any position of the phenoxy group. In this case, considering the above characteristics such as the balance of transmittance at 550 nm and 700 to 750 nm, solvent solubility, heat resistance and the like, the 2,4, 3,4, 3,5 and the like are preferable. The 3rd and 4th positions are more preferred.

(Substituent (c))
In the present invention, the substituent (c) has the following formula (4):

It is represented by

In the above formula (4), R ⁴ and p have the same definition as in the above formula (2), and thus the description thereof is omitted here. R ³ has the same definition as that of the above formula (3), and thus the description thereof is omitted here. In consideration of the above properties such as solvent solubility and heat resistance, R ³ is represented by a hydrogen atom, a linear or branched alkyl group having 1 to 3 carbon atoms, or a formula: — (R ¹ O) _m R ^2. It is preferably a group, more preferably a hydrogen atom or — (R ¹ O) _m R ² .

That is, in the substituent (c), R ³ is a hydrogen atom, a linear or branched alkyl group having 1 to 3 carbon atoms, or a group represented by the formula: — (R ¹ O) _m R ^2. In this case, R ¹ is an ethylene group or a propylene group, R ² is a linear or branched alkyl group having 1 to 3 carbon atoms, and m is 1 or 2, represented by formula (4) It is preferable. In this case, R ² is preferably a methyl group or an ethyl group, particularly a methyl group.

  More specifically:

Those having the following formula are preferred.

Further, in the substituent (c) of the above formula (4), the bonding position of the substituent —CONHR ^{3 to} the benzene ring is not particularly limited. For example, when p is 0, the substituent (c) has a structure in which one substituent “—CONHR ³ ” is bonded to a phenoxy group. Here, the substituent “—CONHR ³ ” is arranged at any position of the phenoxy group in the ortho position (2 position), the meta position (3 position), or the para position (4 position). Of these, the 3rd and 4th positions are preferred, and the 4th position is particularly preferred. When the relatively bulky substituent —CONHR ³ is arranged at the 3rd position or the 4th position, particularly the 4th position, the heat resistance is excellent and fine associability can be controlled by the number of substituents to be introduced. An excellent balance of light shielding properties of 700 to 750 nm can be achieved. Moreover, the phthalocyanine compound having such a structure has excellent solubility in ether-based, ester-based, and ketone-based solvents, and also has excellent compatibility with resins. In the formula (4), when p is 1, the substituent (c) is one substituent “—CONHR ³ ” and one alkoxy group having 1 to 8 carbon atoms or a halogen atom. (—R ⁴ ) has a structure bonded to a phenoxy group. Here, the substituents “—CONHR ³ ” and “R ⁴ ” may each be introduced at any position of the phenoxy group. In this case, considering the above characteristics such as the balance of transmittance at 550 nm and 700 to 750 nm, solvent solubility, heat resistance and the like, the 2,4, 3,4, 3,5 and the like are preferable. The 3rd and 4th positions are more preferred.

(Substituent (d))
In the present invention, the substituent (d) is represented by the following formula (5):

It is represented by

  Here, in said formula (5), 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 obtained phthalocyanine compound can be shifted to the short wavelength side, and thus the obtained phthalocyanine compound has low transmittance at 550 nm and 700 to 750 nm. Moreover, when X is a sulfur atom, the obtained phthalocyanine compound has an advantage of high solvent solubility.

Further, in the above formula (5), Ar, is substituted with R ⁵ is also a phenyl group or naphthyl group, preferably a phenyl group. Here, when Ar is a phenyl group which may be substituted with R ⁵ , Ar is a group represented by the following formula.

In the above formula, X and R ⁵ are the same as defined in the above formula (5), and q is an integer of 0 to 5.

In the above formula (5), R ⁵ 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 an alkyl group having 1 to 8 carbon atoms which may be substituted with a halogen atom. When a plurality of R ⁵ are present (the number of substitutions (q) of R ⁵ in formula (5) is an integer of 2 to 5), the plurality of R ⁵ may be the same or different. It may be. Of the above R ⁵ , Y is an alkyl group having 1 to 12 carbon atoms when R ⁵ is COOY or OY. Here, the alkyl group having 1 to 12 carbon atoms is not particularly limited, and examples thereof include a linear, branched or cyclic alkyl group having 1 to 12 carbon atoms. More specific examples include the definition of R ² above. In addition, nonyl group, decyl group, undecyl group, dodecyl group and the like can be mentioned. Among these, in consideration of the above properties such as solvent solubility and heat resistance, a linear or branched alkyl group having 1 to 10 carbon atoms is preferable, and a linear or branched alkyl group having 1 to 8 carbon atoms is more preferable. A straight-chain or branched alkyl group having 1 to 3 carbon atoms is particularly preferable.

In addition, when R ⁵ is a halogen atom, examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. Among these, a chlorine atom and a bromine atom are preferable in consideration of the above properties such as solvent solubility and heat resistance. Further, when R ⁵ is a chlorine atom or a fluorine atom, the molecular weight of the dye is decreased, and the gram extinction coefficient can be increased.

Further, the aryl group when R ⁵ is an aryl group is not particularly limited, but an aryl group having 6 to 30 carbon atoms is preferable. Specific examples include a phenyl group, a p-methoxyphenyl group, a pt-butylphenyl group, and a p-chlorophenyl group. Among them, a phenyl group is preferable because the molecular weight of the dye is reduced and the gram extinction coefficient is increased.

In addition, when R ⁵ is an alkyl group having 1 to 8 carbon atoms which may be substituted with a halogen atom, the alkyl group having 1 to 8 carbon atoms which may be substituted is not particularly limited, Examples thereof include straight-chain, branched or cyclic alkyl groups having 1 to 8 carbon atoms, and more specific examples are the same as the definition of R ² above. Among these, considering the above properties such as solvent solubility and heat resistance, a linear or branched alkyl group having 1 to 5 carbon atoms is preferable, and a linear or branched alkyl group having 1 to 3 carbon atoms is more preferable. I like it. Examples of the halogen atom that is a substituent of the alkyl group that may be present include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. Among these, a fluorine atom or a chlorine atom is more preferable. There may be a plurality of halogen atoms as substituents for the alkyl group, and when there are a plurality of halogen atoms, they may be the same or different. The number of substituents on the alkyl group is not particularly limited, but is preferably 1 to 3.

In the above formula (5), the number of substitutions (q) of R ⁵ in Ar is not particularly limited, and desired effects (balance of transmittance at 550 nm and 700 to 750 nm, solvent solubility, gram extinction coefficient, heat resistance) For example). For example, when Ar is a phenyl group which may be substituted with ^{R 5,} substitution number of ^{R 5} in Ar (q) is an integer from 1 to 5, preferably an integer of 1 to 3, more preferably Is 1 or 2.

In the substituent (d) of the above formula (5), the bonding position of the substituent R ^{5 to} the benzene ring is not particularly limited. The ortho position (2nd position) and the para position (4th position) are particularly preferable. In the formula (5), when Ar is an optionally substituted phenyl group, the bonding position of -R ^{5 to} the benzene ring is at least one of the para position and the ortho position (position 2). And preferred. In particular, when the substituent R ⁵ is arranged at the 4-position, the resulting phthalocyanine compound can improve the desired effect (balance of transmittance at 550 nm and 700 to 750 nm). Moreover, when the substituent R ⁵ is arranged at the ortho position (position 2), the resulting phthalocyanine compound can improve the solvent solubility.

When q is 2, two substituents R ⁵ may be introduced at any position of the benzene ring. In this case, considering the balance of transmittance at 550 nm and 700 to 750 nm, solvent solubility, heat resistance, and the like, the 2, 4th, 2, 5th, 2, 6th, 3rd, 4th, etc. The 2,4th, 2,5th and 2,6th positions are more preferable, and the 2,5th and 2,6th positions are particularly preferable. When q is 3, the three substituents R ⁵ may be introduced at any position of the benzene ring. In this case, considering the above properties such as the balance of transmittance at 550 nm and 700 to 750 nm, solvent solubility, heat resistance, etc., the 2,3,4th, 2,4,6th, 3,4th, 5th positions Etc. are preferable, and the 2, 4, and 6 positions are more preferable.

Further, in the above formula (5), when Ar is a naphthyl group optionally substituted by ^{R 5,} substitution number of ^{R 5} in Ar (q) also substitution number of ^{R 5} in Ar (q ) Is not particularly limited, and can be appropriately selected depending on desired effects (balance of transmittance at 550 nm and 700 to 750 nm), solvent solubility, heat resistance, gram extinction coefficient, and the like. For example, when Ar is a naphthyl group optionally substituted by ^{R 5,} substitution number of ^{R 5} in Ar (q) is an integer from 1 to 5, preferably an integer of 1 to 3, more preferably Is 1 or 2, particularly preferably 1. Further, the bonding position of the substituent R ^{5 to} the naphthalene ring is not particularly limited, and depends on the desired effect (balance of transmittance at 550 nm and 700 to 750 nm), solvent solubility, heat resistance, gram extinction coefficient, etc. It can be selected as appropriate. For example, when q is 1 and Ar is a 1-naphthyl group, the bonding position of R ^{5 to} the naphthalene ring is the 2nd, 3rd, 4th, 5th, 6th, 7th or 8th position. In consideration of the above characteristics such as transmittance balance at 550 nm and 700 to 750 nm, solvent solubility, heat resistance, etc., the 2nd, 3rd and 4th positions are preferable, and the 2nd position is more preferable. . When the substituent (d) is derived from 2-naphthol, the bonding position of the substituent: —COO (R ¹ O) R ^{2 to} the naphthalene ring is 1, 3, 4, 5, , 6-position, 7-position, or 8-position, but preferably 1-position, 3-position, and 6-position, and the above properties such as balance of transmittance at 550 nm and 700 to 750 nm, solvent solubility, and heat resistance In view of the above, the 3rd or 6th position is more preferable.

  More specifically, the substituent (d) preferably has the following. In the following examples, a is 1 or 2.

(Substituent (e))
In the present invention, the substituent (e) is
Following formula (6):

In the above formula (6), X is an oxygen atom or a sulfur atom, R ⁷ is an alkylene group having 1 to 5 carbon atoms, and R ⁶ is substituted with a halogen atom or an alkoxy group having 1 to 8 carbon atoms. It is an alkyl group having 1 to 8 carbon atoms which may be used.

In said formula (6), X is an oxygen atom (-O-) or a sulfur atom (-S-), Preferably it is an oxygen atom. R ⁷ is an alkylene group having 1 to 5 carbon atoms. Here, 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. Of these, a methylene group, an ethylene group, a tetramethylene group, and a propylene group are preferable. Moreover, in said formula (6), R < ⁶ > is a C1-C8 alkyl group which may be substituted by the halogen atom or the C1-C8 alkoxy group. Here, the alkyl group having 1 to 8 carbon atoms is not particularly limited, and examples thereof include straight-chain, branched or cyclic alkyl groups having 1 to 8 carbon atoms. More specific examples include the definition of R ² above. It is the same. Among these, in consideration of the above properties such as solvent solubility and heat resistance, 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. Here, the alkyl group may be substituted with a halogen atom or an alkoxy group having 1 to 8 carbon atoms. Examples of the halogen atom in the case where the alkyl group is substituted with a halogen atom include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom. Among these, a chlorine atom and a fluorine atom are preferable in consideration of the above properties such as solvent solubility and heat resistance. In addition, when the alkyl group is substituted with an alkoxy group, the alkoxy group having 1 to 8 carbon atoms includes methoxy group, ethoxy group, propoxy group, isopropoxy group, butoxy group, pentyloxy group, hexyloxy group, 2 -Linear, branched or cyclic alkoxy groups such as ethylhexyloxy group and octyloxy group. Among these, in consideration of the above properties such as solvent solubility and heat resistance, 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. Further, the number of halogen atoms or alkoxy group substituents introduced into the alkyl group is not particularly limited, but varies depending on the number of carbon atoms of the alkyl group, a desired effect, and the like. The number of halogen atom or alkoxy group substituents introduced into the alkyl group is preferably 1-8, more preferably 1-4.

(Substituent (f))
In the present invention, the substituent (f) is
Following formula (7):

In the above formula (7), X is an oxygen atom or a sulfur atom, ^{R 7} is an alkylene group having 1 to 5 carbon atoms, ^{R 8} are each independently an alkoxy group having 1 to 8 carbon atoms Or an alkyl group having 1 to 8 carbon atoms.

Here, in said formula (7), X is an oxygen atom (-O-) or a sulfur atom (-S-), Preferably it is an oxygen atom. R ⁷ is an alkylene group having 1 to 5 carbon atoms. Here, as the alkylene group having 1 to 5 carbon atoms is not particularly limited, a more specific example is the same as the definition of R ⁷ in the formula (6). R ⁷ is preferably a methylene group, an ethylene group, a tetramethylene group, or a propylene group. R ⁸ is an alkoxy group having 1 to 8 carbon atoms or an alkyl group having 1 to 8 carbon atoms. Among these, the alkoxy group having 1 to 8 carbon atoms is not particularly limited, and more specific examples are the same as the definition of the alkoxy group of the above formula (7), preferably a straight chain having 1 to 5 carbon atoms. A chain or branched alkoxy group, particularly a linear or branched alkoxy group having 1 to 3 carbon atoms. In addition, the alkyl group having 1 to 8 carbon atoms is not particularly limited, and more specific examples are the same as the definition of R ² above. Among these, in consideration of the above properties such as solvent solubility and heat resistance, 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 three R ⁸ groups may be the same or different from each other, but at least one is preferably an alkoxy group, more preferably two or three are alkoxy groups. It is more preferable that

(Substituent (g))
In the present invention, the substituent (g) is a group (g) derived from 7-hydroxycoumarin.

(Substituent (h))
In the present invention, the substituent (h) is a group (h) derived from 2,3-dihydroxyquinoxane.

  Of the above substituents, considering the excellent balance of transmittance at 550 nm and 700 to 750 nm, solvent solubility, heat resistance, etc., the substituents (b), (c) or (d) or the substituents (a- 2) is preferably introduced into the phthalocyanine skeleton, more preferably the substituent (b) or (d), or the substituent (a-2) is introduced into the phthalocyanine skeleton, and the substituent (d) is More preferably, it is introduced into the phthalocyanine skeleton.

  The phthalocyanine compound according to the present invention has a heterogeneous structure when viewed as a whole compound. Usually, in the phthalocyanine compound, the substituents constituting each unit are often the same from the viewpoint of the purpose of designing to have a sharp absorption wavelength in order to appropriately absorb the target wavelength and the productivity. That is, phthalonitrile having the same substituent at the α-position and β-position is often used. However, in the present application, as a result of earnest study to obtain a phthalocyanine compound having a shape of a spectral curve along the target wavelength of a reflection absorption type infrared cut filter or an infrared cut layer, the substituents are assumed to be different for each unit. From the viewpoint of the whole phthalocyanine compound, it has been found that a phthalocyanine compound having a desired spectral curve can be obtained by adopting a structure in which substituents are introduced non-uniformly.

  As the target spectrum of the absorption filter used for the infrared cut filter for the camera module, the balance between the transmittance at 550 nm (transparency in the visible light region) and the transmittance at 700 to 750 nm is considered. Specifically, the maximum absorption wavelength (λmax) measured in the acrylic resin by the method described in Examples below is adjusted to 700 to 760 nm, and the transmittance is adjusted to 50% transmittance at 650 nm. In this case, the transmittance at 550 nm is preferably 85% or more, and more preferably 90% or more. Moreover, it is preferable that the transmittance at λmax is 30% or less when the transmittance measured in the acrylic resin by the method described in Examples below is adjusted to be 50% transmittance at 650 nm. More preferably, it is 20% or less. Further, it is more preferable that the transmittance as high as possible is maintained up to around 650 nm, and the transmittance rapidly decreases around 650 nm. From this viewpoint, specifically, when the transmittance measured in the acrylic resin by the method described in Examples below is adjusted so that the transmittance is 50% at 650 nm, the transmittance at 700 nm is 40. % Or less, more preferably 38.5% or less, even more preferably 35% or less, and particularly preferably 30% or less. As the target spectrum of the infrared cut filter, it is desirable to cut the wavelength in the infrared region exceeding 700 nm as much as possible. Therefore, the maximum absorption wavelength (λmax) measured in the acrylic resin by the method described in the examples of the phthalocyanine compound is It is preferable that it is 700-750 nm, and it is more preferable that it is 705-745 nm.

  The phthalocyanine compound according to the present invention is preferentially composed of a fluorine atom, a chlorine atom or a bromine atom (a larger amount of fluorine atom, chlorine atom or bromine atom is introduced). It is preferentially composed of a high unit (unit A) and any one of the substituents (a-1) and (b) to (h) or the substituent (a-2) (substituent (a-1) and (B) to (h) or a unit (unit B) having a low molecular association in the resin due to introduction of a larger amount of substituent (a-2). Due to such a difference in associative properties, a plurality of peaks appear in the wavelength-transmittance spectral curve of the phthalocyanine compound. In the phthalocyanine compound composed only of the unit B, the transmittance between the sub-peak of the transmittance and the main peak is decreased between 650 and 700 nm, and the absorption characteristic between 650 and 700 nm is decreased. On the other hand, due to the presence of unit A having high molecular associability, a sub-peak of transmittance appears between 650 and 700 nm, and this sub-peak forms a smooth transmittance curve leading to the main peak near 700 nm. It becomes a characteristic.

  Conventionally, the spectral characteristics of phthalocyanine compounds have been demanded to have a single peak and a sharp width for the purpose of improving solubility in a solvent. However, in the present invention, a phthalocyanine compound having spectral characteristics having two peaks is intentionally designed to be suitable for a dye used in an infrared cut filter. Here, the magnitude of the two peaks of the phthalocyanine compound of the present invention is not particularly limited, and can be appropriately selected according to desired spectral characteristics. Specifically, the absorbance at the sub-peak relative to the absorbance at the main peak is preferably greater than 0.20, more preferably greater than 0.22, and even more preferably greater than 0.25. The “sub-peak” refers to a peak at a wavelength with the highest absorbance after the main peak at the maximum absorption wavelength. In addition, based on the spectral curve when determining the maximum absorption wavelength of each compound, the maximum absorption wavelength and the absorbance value for the main peak of the sub-peaks in the phthalocyanine compound are determined. The spectral curve obtained in the acrylic resin by the method described in the following examples is used.

  As the pigment for the infrared cut filter, the center metal of the phthalocyanine compound represented by the formula (1) is preferably vanadyl because a target spectral curve is obtained.

  On the other hand, as a pigment used for the infrared cut layer disposed on the sensor, the transmittance in the visible light region is excellent (the transmittance at 550 nm is high), and an absorption rise occurs in the vicinity of 650 to 700 nm. Those having low transmittance at ˜760 nm are preferable. The maximum absorption wavelength becomes a long wavelength region due to the presence of the unit B. However, if only the unit B is used, an absorption peak occurs below 650 nm as described above, so that it is not suitable for the dye used for the infrared cut layer. . On the other hand, if only unit A is used, absorption occurs in the visible light region, which is also unsuitable for the dye used for the infrared cut layer. By mixing the unit A and the unit B, the target spectrum of the dye used for the infrared cut layer is close.

  Thus, as a pigment | dye used by an infrared cut layer, it is preferable that the central metal of the phthalocyanine compound of Formula (1) is zinc (Zn), copper (Cu), and vanadyl (VO).

  In addition, when manufacturing the "phthalocyanine compound" of the present invention, raw materials (phthalonitrile derivatives) are mixed in a desired ratio. At this time, the produced “phthalocyanine compound” is in the form of a mixture having various structures. Therefore, the whole mixture is analyzed, or theoretically, the number of introduction (substitution) of the substituents (a-1), (a-2), (b) to (h) is the decimal point as in the following examples. It is represented by

Preferable examples of the phthalocyanine compound (1) include the following. In the following, M is described as being metal free. Pc represents a phthalocyanine nucleus, a substituent substituted at the α-position immediately after Pc, and a substituent substituted at the β-position after the substituent substituted at the α-position. “{Α- (Substituent (b)) _A F _8-A }” is described as follows. The obtained phthalocyanine compound has an average of A substituents b introduced at the α-position, and the average number of fluorine atoms. It means that 8-A exists.
_{· [Pc- (2,5-Cl 2} C 6 H 3 O) 6 Cl 10]
_{· [Pc- (2,5-Cl 2} C 6 H 3 O) 8 Cl 8]
_{· [Pc- (2,5-Cl 2} C 6 H 3 O) 10 Cl 6]
_{· [Pc- (2,5-Cl 2} C 6 H 3 O) 12 Cl 4]
_{· [Pc- (2,5-Cl 2} C 6 H 3 O) 4 (2,6- (CH 3) 2 PhO) 4 Cl 8]
_{· [Pc- (4-CH 3} COC 6 H 4 O) 4 (2,6- (CH 3) 2 PhO) 4 Cl 8]
_{· [Pc- (4-CH 3} OCH 2 CH 2 OCOC 6 H 4 O) 10 Cl 6]
_{· [Pc- (2-CH 3} COC 6 H 4 O) 10 Cl 6]
_{· [Pc- (4-NOC 6} H 4 O) 10 Cl 6]
_{· [Pc- (C 10 H 7} O) 8 Cl 8]
[Pc- (4-CNC ₆ H ₄ O) ₈ Cl ₈ ]
_{· [Pc- (2-PhC 6} H 4 O) 6 Cl 10]
_{· [Pc- (2-PhC 6} H 4 O) 10 Cl 6]
_{· [Pc- (2,5-Cl 2} C 6 H 3 O) 6 F 10]
_{· [Pc- (2,5-Cl 2} C 6 H 3 O) 8 F 8]
_{· [Pc- (2,5-Cl 2} C 6 H 3 O) 10 F 6]
_{· [Pc- (2,5-Cl 2} C 6 H 3 O) 12 F 4]
_{· [Pc- (2,5-Cl 2} C 6 H 3 O) 4 (2,6- (CH 3) 2 PhO) 4 F 8]
_{· [Pc- (4-CH 3} COOC 6 H 4 O) 4 (2,6- (CH 3) 2 PhO) 4 F 8]
_{· [Pc- (4-CH 3} OCH 2 CH 2 OCOC 6 H 4 O) 10 F 6]
_{· [Pc- (2-CH 3} COOC 6 H 4 O) 10 F 6]
_{· [Pc- (4-NO 2} C 6 H 4 O) 10 F 6]
_{· [Pc- (C 10 H 7} O) 8 F 8]
[Pc- (4-CNC ₆ H ₄ O) ₈ F ₈ ]
_{· [Pc- (2-PhC 6} H 4 O) 6 F 10]
_{· [Pc- (2-PhC 6} H 4 O) 10 F 6]
_{· [Pc- (2,6-Cl 2} C 6 H 3 O) 8 Cl 10]
_{· [Pc- (2-ClC 6} H 4 O) 8 Cl 8]
_{· [Pc- (4-ClC 6} H 4 O) 10 Cl 6]
[Pc- (4-FC ₆ H ₄ O) ₁₀ Cl ₆ ]
_{· [Pc- (4-BrC 6} H 4 O) 9 Cl 7]
_{· [Pc- (4-COOCH 3} C 6 H 4 O) 10 Cl 6]
_{· [Pc- {4-COO (} CH 2 CH 2 OCH 3) C 6 H 4 O} 10 Cl 6]
_{· [Pc- (2-COOCH 3} C 6 H 4 O) 6 Cl 10]
_{· [Pc- (4-NO 2} C 6 H 4 O) 10 Cl 6]
[Pc- (4-CNC ₆ H ₄ O) ₄ (2-CH ₃ OPhO) ₄ Cl ₈ ]
[Pc- (4-CNC ₆ H ₄ O) ₄ (2-CH ₃ OPhO) ₈ Cl ₄ ]
_{· [Pc- (2,5-Cl 2} C 6 H 3 O) 6 F 10]
_{· [Pc- (2,5-Cl 2} C 6 H 3 O) 8 F 8]
_{· [Pc- (2-ClC 6} H 4 O) 8 F 8]
_{· [Pc- (4-ClC 6} H 4 O) 10 F 6]
[Pc- (4-FC ₆ H ₄ O) ₁₀ F ₆ ]
_{· [Pc- (4-BrC 6} H 4 O) 9 F 7]
_{· [Pc- (4-COOCH 3} C 6 H 4 O) 10 F 6]
_{· [Pc- (2-COOCH 3} C 6 H 4 O) 6 F 10]
[Pc- (4-CNC ₆ H ₄ O) ₈ F ₈ ]
_{· [Pc- (2-PhC 6} H 4 O) 6 F 10]
[Pc- (4-CNC ₆ H ₄ O) ₄ (2-CH ₃ OPhO) ₄ F ₈ ]
[Pc- (4-CNC ₆ H ₄ O) ₄ (2-CH ₃ OPhO) ₈ F ₄ ]
_{· [Pc- (4-CH 3} OCH 2 CH 2 NHCOC 6 H 4 O) 10 Cl 6]
_{· [Pc- (4-CH 3} OCH 2 CH 2 NHCOC 6 H 4 O) 10 F 6]
_{· [Pc- (4-NH 2} SO 2 C 6 H 4 O) 10 Cl 6]
_{· [Pc- (4-NH 2} SO 2 C 6 H 4 O) 10 F 6].

  The phthalocyanine compound of the present invention has a high transmittance at 550 nm and a low transmittance at 700 nm, and has an excellent balance. In addition, the phthalocyanine compound of the present invention is excellent in compatibility with organic solvents, particularly ether solvents, ester solvents, and ketone solvents. As the ether solvent, branched or linear ethers and cyclic ethers are effectively used. Specifically, tetrahydrofuran, 1,4-dioxane, 1,3-dioxolane, diethyl ether, diisopropyl ether, 1,2-dimethoxyethane, cyclopentyl methyl ether, propylene glycol monomethyl ether acetate (PGMEA), ethylene glycol monoethyl ether Examples include acetate, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, and the like. Of these, PGMEA is often used for infrared cut filter applications. Examples of the ester solvent include ethyl acetate, methyl acetate, butyl acetate, methoxybutyl acetate, cellosolve acetate, amyl acetate, normal propyl acetate, isopropyl acetate, methyl lactate, ethyl lactate, butyl lactate and the like. Examples of the ketone solvent include acetone, methyl ethyl ketone, methyl isobutyl ketone, diisobutyl ketone, cyclohexanone, diacetone alcohol and the like. The solubility of the phthalocyanine compound of the present invention in PGMEA, which is an ether solvent, is preferably 10% by weight or more, and more preferably 20% by weight or more. The upper limit of solubility is not particularly limited, but is usually about 30% by weight or less.

  The method for producing the phthalocyanine compound of the present invention is not particularly limited, and a conventionally known method can be appropriately used. Preferably, the phthalonitrile compound and the metal salt are used in a molten state or in an organic solvent. A method of cyclization reaction is particularly preferably used. Hereinafter, particularly preferred embodiments of the production method for the phthalocyanine compound of the present invention will be described. However, the present invention is not limited to the following preferred embodiments.

  That is, the following formula (I):

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

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

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

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 this specification). The phthalocyanine compound of the present invention can be produced by cyclization reaction with one kind. In the above reaction, the phthalonitrile compounds (1) to (4) are described according to the structure of the phthalocyanine compound of the formula (1). Sometimes it becomes. For this reason, for example, when the structural units A to D including Z _{1 to} Z ₄ , Z _{5 to} Z ₈ , Z _{9 to} Z ₁₂ , and Z _{13 to} Z ₁₆ are the same, the phthalonitrile compound used as a raw material is One type. Alternatively, during the reaction, a phthalonitrile derivative of the following formula (V) (particularly, tetrachlorophthalonitrile or tetrabromophthalonitrile) is substituted with any of the phthalonitrile compounds of the above formulas (I) to (IV), A reaction may be performed. By using such a phthalonitrile derivative in the reaction, the number of chlorine atoms or bromine atoms introduced into the phthalocyanine skeleton is appropriately adjusted, and the substituents (a-1) and (b) to (h) Or the phthalocyanine compound which introduce | transduced substituent (a-2) by the appropriate number of substituents and substituent seed | species can be manufactured.

In the above formulas (I) to (IV), Z _{1 to} Z ₁₆ are defined by the structure of the desired phthalocyanine compound. Specifically, in the above formulas (I) to (IV), Z _{1 to} Z ₁₆ are the same as the definitions of Z _{1 to} Z _{16 in} the above formula (1), respectively, and thus description thereof is omitted here. To do.

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

A phthalonitrile derivative represented by the following (in this specification, simply referred to as “phthalonitrile derivative”) is represented by the following formula (2a):

A substituent (a-1) -containing precursor represented by the following (in this specification, simply referred to as “substituent (a-1) -containing precursor”), the following formula (2b):

A substituent (a-2) -containing precursor represented by the following (in this specification, simply referred to as “substituent (a-2) -containing precursor”), the following formula (3a):

A substituent (b) -containing precursor represented by the following (in this specification, simply referred to as “substituent (b) -containing precursor”), the following formula (4a):

A substituent (c) -containing precursor represented by the following (in this specification, simply referred to as “substituent (c) -containing precursor”), the following formula (5a):

A substituent (d) -containing precursor represented by the following (in this specification, simply referred to as “substituent (d) -containing precursor”), the following formula (6a):

A substituent (e) -containing precursor represented by the following (in this specification, simply referred to as “substituent (e) -containing precursor”), the following formula (7a):

A group consisting of a substituent (f) -containing precursor represented by the formula (also referred to herein as “substituent (f) -containing precursor”), 7-hydroxycoumarin, or 2,3-dihydroxyquinoxane It is obtained by reacting with a substituent selected from more. In the following, the precursors are collectively referred to as “precursors”.

In the above formulas (2a) and (2b), R ¹ , R ² and R ⁴ , and n, m and p are R ¹ , R ² and R ⁴ in the above formula (2), and n, respectively. , M and p are the same as those defined here, and the description is omitted here. Similarly, in the above formulas (3a) to (5a), R ¹ , R ² , R ³ , R ⁴ and R ⁵ , and m and p are the same as R in the above formulas (3) to (5), respectively. ^{1, R 2, R 3,} R 4 and for ^{R 5,} and is similar to the definition of m and p, the description thereof is omitted here. In the above formulas (6a) to (7a), R ⁶ , R ⁷ and R ⁸ are the same as defined for R ⁶ , R ⁷ and R ^{8 in} the above formulas (6) to (7), respectively. Therefore, the description is omitted here.

In the above reaction, a phthalonitrile derivative of the formula (V) is used as a starting material. In the above 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 the same or different. Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. Among these, X ₁ , X ₂ , X ₃ and X ₄ preferably represent a fluorine atom, a chlorine atom or a bromine atom, and particularly preferably represent a chlorine atom or a bromine atom. In particular, when tetrachlorophthalonitrile or tetrabromophthalonitrile is used as a starting material, the precursor reacts with a chlorine atom or bromine atom at the 3-6 position of the tetrachlorophthalonitrile or tetrabromophthalonitrile at random. . For this reason, by using tetrachlorophthalonitrile or tetrabromophthalonitrile as a starting material, the substituents (a-1), (a-2), (b) to (h) are substituted with the α-position of the phthalocyanine skeleton and Can be introduced randomly at the β-position. Therefore, when tetrachlorophthalonitrile or tetrabromophthalonitrile is used as a phthalonitrile derivative, the phthalonitrile compound is optionally pre-cursed by four chlorine atoms or bromine atoms of tetrachlorophthalonitrile or tetrabromophthalonitrile. Obtained in the form of a body-substituted mixture. On the other hand, when tetrafluorophthalonitrile is used as a starting material, the precursor reacts preferentially with the fluorine atoms at the 4- and 5-positions of the tetrafluorophthalonitrile. For this reason, by using tetrafluorophthalonitrile as a starting material, the substituents (a-1), (a-2), and (b) to (h) can be selectively introduced into the β-position of the phthalocyanine skeleton. .

  In the reaction between the phthalonitrile derivative and the precursor, the proportion of the precursor is appropriately selected depending on the structure of the target phthalonitrile compound. The total amount of the precursor used is not particularly limited as long as these reactions can proceed to produce a desired phthalonitrile compound, and can be appropriately selected according to the structure of the desired phthalonitrile compound. The number of the substituents (a-1), (a-2), (b) to (h) -containing precursors introduced into the phthalonitrile derivative is as described above. Considering such points, the amount of the substituent (a-1), (a-2), (b) to (h) -containing precursor is not particularly limited, and is appropriately determined depending on the number of substituents introduced. You can choose.

  The reaction between the phthalonitrile derivative and the precursor may be performed in the absence of a solvent or in an organic solvent, but is preferably performed in an organic solvent. Examples of the organic solvent that can be used in this case include nitriles such as acetonitrile and benzonitrile; polar solvents such as acetone and 2-butanone. Of these, acetonitrile, benzonitrile and acetone are preferred. The amount of the organic solvent used when the solvent is used is such an amount that the concentration of the phthalonitrile derivative is usually 2 to 50% by weight, preferably 10 to 40% by weight. Further, in the reaction of the phthalonitrile derivative and the precursor, it is preferable to use these trapping agents in order to remove hydrogen halide (for example, hydrogen chloride or hydrogen fluoride) generated during the 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 and magnesium carbonate. Of these, potassium carbonate, calcium carbonate and calcium hydroxide are preferred. Further, 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 and the like generated during the reaction. It is 0-4.0 mol, Preferably it is 1.0-2.0 mol.

  In addition, the reaction conditions for the phthalonitrile derivative and the precursor are not particularly limited as long as the reaction of both proceeds to obtain a desired phthalonitrile compound. Specifically, the reaction temperature is usually 20 to 150 ° C, preferably 40 to 120 ° C. Moreover, reaction time is 0.5 to 60 hours normally, Preferably it is 1 to 50 hours.

  When tetrafluorophthalonitrile is used as a starting material, the precursor can be made to react randomly with the fluorine atoms at the 3-6 positions of tetrafluorophthalonitrile by appropriately setting the reaction conditions. . Specifically, the reaction temperature is usually 40 to 80 ° C., preferably 60 to 80 ° C. Moreover, reaction time is 6 to 48 hours normally, Preferably it is 10 to 24 hours.

  The phthalonitrile compounds (1) to (4) of the above formulas (I) to (IV) are obtained by the above reaction. After the reaction, crystallization, filtration, washing and drying are performed according to a conventionally known method. Also good. By such an operation, the phthalonitrile compound can be obtained efficiently and with high purity.

  Next, the cyclization reaction is selected from the group consisting of phthalonitrile compounds (1) to (4) of formulas (I) to (IV) and a metal, metal oxide, metal carbonyl, metal halide, and organic acid metal. It is preferable to react one species in a molten state or in an organic solvent. The metal, metal oxide, metal carbonyl, metal halide, and organic acid metal that 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. For example, a metal such as iron, magnesium, nickel, cobalt, copper, palladium, zinc, vanadium, titanium, indium and tin enumerated in the term M in the above formula (1), of the metal, Metal halides such as chloride, bromide and iodide, metal oxides such as vanadium oxide, titanyl oxide and copper oxide, organic acid metals such as acetate, and metal carbonyls such as complex compounds such as acetylacetonate and carbonyl iron Etc. 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, iodine Metal halides such as cobalt iodide, indium iodide, aluminum iodide, copper bromide, zinc bromide, cobalt bromide, aluminum bromide; vanadium monoxide, vanadium trioxide, vanadium tetroxide, vanadium pentoxide, dioxide Titanium, iron monoxide, iron sesquioxide, iron tetroxide, manganese oxide, nickel monoxide, cobalt monoxide, cobalt sesquioxide, cobalt dioxide, cuprous oxide, cupric oxide, copper sesquioxide, palladium oxide and Metal oxides such as zinc oxide; organic acids such as copper acetate, zinc acetate, cobalt acetate, copper benzoate, zinc benzoate Genus; and complex compounds and cobalt carbonyl such as acetyl acetonate, iron carbonyl, and metal carbonyls such as nickel carbonyl. Of these, preferred are metals, metal oxides and metal halides, more preferred are metal halides, and further preferred are aluminum iodide, vanadium chloride, copper chloride and zinc iodide, and more preferred. Vanadium chloride, copper chloride and zinc iodide, particularly preferably vanadium chloride. When vanadium chloride is used, the central metal is vanadyl.

  The cyclization reaction of the phthalonitrile compound is not particularly limited, and conventionally known methods such as Japanese Patent No. 28216249 and Japanese Patent Application Laid-Open No. 2008-231153 can be applied alone or appropriately modified. Although the phthalonitrile compound represented by the above formulas (I) to (IV) and the metal compound can be reacted in a molten state without a solvent (cyclization reaction), they can be reacted in an organic solvent (cyclization reaction). It is preferable to make it. The organic solvent may be any inert solvent that has low reactivity with the phthalonitrile compound as a starting material, and preferably does not exhibit reactivity. For example, benzene, toluene, xylene, nitrobenzene, monochlorobenzene, o -Inert solvents such as chlorotoluene, dichlorobenzene, trichlorobenzene, 1-chloronaphthalene, 1-methylnaphthalene, ethylene glycol, and benzonitrile; methanol, ethanol, 1-propanol, 2-propanol, 1- Alcohols such as 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, dimethyl sulfoxide, aprotic polar solvents such as sulfolane. Of these, 1-chloronaphthalene, 1-methylnaphthalene, 1-octanol, dichlorobenzene and benzonitrile are preferably used, and more preferably 1-octanol, dichlorobenzene and benzonitrile are used. These solvents may be used alone or in combination of two or more.

  The reaction conditions of the phthalonitrile compounds (1) to (4) of the formulas (I) to (IV) and the metal compound in the above embodiment are not particularly limited as long as the reaction proceeds, but for example, The total amount of the phthalonitrile compounds (1) to (4) is 1 to 500 parts by weight, preferably 10 to 350 parts by weight, and the metal compound is 100 parts by weight of the organic solvent. Preferably it is 1.0-2.0 mol with respect to 4 mol, More preferably, it charges in the range of 1.0-1.5 mol. The cyclization is not particularly limited, but the reaction is preferably performed at a reaction temperature of 30 to 250 ° C, more preferably 80 to 200 ° C. Although reaction time is not specifically limited, Preferably it is 3 to 24 hours. Moreover, although the said reaction may be performed in air | atmosphere atmosphere, it is preferable to carry out in inert gas atmosphere (For example, under distribution | circulation of nitrogen gas, helium gas, argon gas, etc.).

  After the cyclization reaction, crystallization, filtration, washing and drying may be performed according to a conventionally known method. By such an operation, the phthalocyanine compound can be obtained efficiently and with high purity.

  The phthalocyanine compound of the present invention has a high transmittance at 550 nm and a low transmittance at 700 nm, and has an excellent balance. Further, the phthalocyanine compound of the present invention is excellent in compatibility with an organic solvent, particularly an ether solvent. For this reason, the phthalocyanine compound of this invention can be used for various uses, such as an infrared cut filter and an infrared cut layer.

  That is, this invention also provides the infrared cut filter containing the phthalocyanine compound of this invention.

  The infrared cut filter of the present invention is not particularly limited as long as it contains the phthalocyanine compound of the present invention, but in addition to the phthalocyanine compound of the present invention (hereinafter also referred to as “phthalocyanine compound (A)”), other phthalocyanine compounds (Hereinafter also referred to as “phthalocyanine compound (B)”). Here, the phthalocyanine compound (B) is not particularly limited, but has a maximum absorption wavelength shorter by 5 to 70 nm and 5 to 50 nm than the maximum absorption wavelength of the phthalocyanine compound (A), and a sub-peak with respect to the absorbance at the maximum absorption wavelength. A low associative phthalocyanine compound having an absorbance ratio of 0.3 or less is preferable. Such a phthalocyanine compound (B) has a spectral characteristic that the maximum absorption wavelength is shorter than that of the phthalocyanine compound (A) and the absorbance of the sub-peak is low, that is, close to a single peak at the maximum absorption wavelength. When combined with the phthalocyanine compound (A), the transmittance at 650 nm is about 50%, and the transmittance at 700 nm is as low as possible. The transmission curve between wavelengths becomes smoother. For this reason, when the transmittance at 650 nm is adjusted to 50%, the transmittance at 700 nm and the maximum absorption wavelength becomes smaller, and it can be used more suitably as a dye for an infrared cut filter.

  The sub-peak refers to a peak at a wavelength with the highest absorbance after the main peak of the maximum absorption wavelength. Moreover, based on the spectroscopic curve at the time of calculating | requiring the maximum absorption wavelength of each compound, the maximum absorption wavelength and the value of the light absorbency with respect to the main peak of the subpeak in a phthalocyanine compound (B) are determined. The spectral curve obtained in the acrylic resin by the method described in the following examples is used.

  The ratio of the absorbance at the subpeak to the absorbance at the maximum absorption wavelength of the phthalocyanine compound (B) is usually 0.01 or more, preferably 0.1 to 0.3, more preferably 0.15 to 0.26. It is.

  The maximum absorption wavelength of the phthalocyanine compound (B) is preferably 680 to 740 nm in consideration of the spectral characteristics of the phthalocyanine compound (A) used. In the infrared cut filter, the phthalocyanine compound (A) may be used alone or in combination of two or more. Further, the phthalocyanine compound (B) may be used alone or in combination of two or more. When mixed and used, the absorption spectrum of the entire phthalocyanine compound (A) (a mixture of a plurality of phthalocyanine compounds (A)) and the absorption spectrum of the entire phthalocyanine compound (B) (a mixture of a plurality of phthalocyanine compounds (B)) The spectroscopic curve is measured according to the blending ratio in the composition, and each maximum absorption wavelength may be obtained.

  Although it does not specifically limit as a phthalocyanine compound (B) as long as the said conditions are satisfy | filled, The phthalocyanine compound shown by the following formula | equation (8) is mentioned.

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

In said formula (9), R < ¹⁰ > is respectively independently the halogen atom, the C1-C20 alkyl group which may have a substituent, and the carbon number 6-6 which may have a substituent. 30 aryl group, cyano group, or —COOR ¹¹ (wherein R ¹¹ is an optionally substituted alkyl group having 1 to 20 carbon atoms), and l is an integer of 0 to 5. is there,
Represents a substituent represented by (a),
_{4 of} Z ₁ ′, Z ₄ ′, Z ₅ ′, Z ₈ ′, Z ₉ ′, Z ₁₂ ′, Z ₁₃ ′ and Z ₁₆ ′ are substituents (a),
M represents a metal, a metal oxide or a metal halide.

  Here, in the formula (9), the halogen atom is a fluorine atom, a chlorine atom, a bromine atom and an iodine atom, preferably a fluorine atom or a chlorine atom, more preferably a chlorine atom.

  Further, the unsubstituted alkyl group having 1 to 20 carbon atoms may be any of a linear, branched or cyclic alkyl group having 1 to 20 carbon atoms, and preferably 1 to 8 carbon atoms. A linear, branched or cyclic alkyl group. Specifically, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert-butyl group, n-pentyl group, isopentyl group, neopentyl group, 1, 2-dimethylpropyl group, n-hexyl group, cyclohexyl group, 1,3-dimethylbutyl group, 1-isopropylpropyl group, 1,2-dimethylbutyl group, n-heptyl group, 1,4-dimethylpentyl group, 2 -Methyl 1-isopropylpropyl group, 1-ethyl-3-methylbutyl group, n-octyl group, 2-ethylhexyl group and the like can be mentioned. Of these, methyl, ethyl, n-propyl, isopropyl and n-butyl groups are preferred.

  Specifically, the unsubstituted aryl group having 6 to 30 carbon atoms includes, for example, a non-condensed hydrocarbon group such as a phenyl group, a biphenyl group, and a terphenyl group; a pentarenyl group, an indenyl group, a naphthyl group, an azulenyl group, Heptalenyl group, biphenylenyl group, fluorenyl group, acenaphthylenyl group, preadenyl group, acenaphthenyl group, phenalenyl group, phenanthryl group, anthryl group, fluoranthenyl group, acephenanthrenyl group, aceanthrylenyl group, triphenylenyl group, pyrenyl group , Condensed polycyclic hydrocarbon groups such as a chrycenyl group and a naphthacenyl group. Of these, a phenyl group, a biphenyl group, and a naphthyl group are preferable.

When R ¹⁰ is a group of the formula: —COOR ¹¹ , R ¹¹ is an alkyl group having 1 to 20 carbon atoms which may have a substituent, and the alkyl group in this case is the same as the alkyl group It is.

  In addition, examples of the substituent (hereinafter referred to as an optional substituent) optionally present in the alkyl group or aryl group include, for example, a halogen atom, an acyl group, an alkyl group, a phenyl group, an alkoxy group, and a halogenated alkyl group. , Halogenated alkoxy group, nitro group, amino group, alkylamino group, alkylcarbonylamino group, arylamino group, arylcarbonylamino group, carbonyl group, alkoxycarbonyl group, alkylaminocarbonyl group, alkoxysulfonyl group, alkylthio group, carbamoyl Groups, aryloxycarbonyl groups, oxyalkyl ether groups, cyano groups and the like can be exemplified, but are not limited thereto. These kinds of substituents may be the same or different when a plurality of substituents are substituted. Some of the above substituents are shown below with more specific examples.

  Among the optional substituents, the halogen atom is a fluorine atom, a chlorine atom, a bromine atom and an iodine atom, preferably a fluorine atom or a chlorine atom, more preferably a chlorine atom.

  Among the optional substituents, the acyl group is preferably an acyl group having 2 to 21 carbon atoms, and includes an acetyl group, an ethylcarbonyl group, a propylcarbonyl group, a butylcarbonyl group, a pentylcarbonyl group, a hexylcarbonyl group, and a benzoyl group. Group, pt-butylbenzoyl group, and the like.

  Of the optional substituents, the alkyl group is the same as the above-described alkyl group.

  Among the optional substituents, the alkoxy group is preferably an alkoxy group having 1 to 20 carbon atoms, and is a linear, branched or cyclic alkoxy group having 1 to 20 carbon atoms, preferably carbon atoms. It is a linear, branched or cyclic alkoxy group of several to eight. Specifically, methoxy group, ethoxy group, n-propoxy group, isopropoxy group, n-butoxy group, isobutoxy group, sec-butoxy group, tert-butoxy group, n-pentyloxy group, isopentyloxy group, neo Examples include pentyloxy group, 1,2-dimethyl-propoxy group, n-hexyloxy group, cyclohexyloxy group, 1,3-dimethylbutoxy group, 1-isopropylpropoxy group and the like. Of these, methoxy and ethoxy groups are preferred.

  Among the optional substituents, the halogenated alkyl group is a group in which a part of a linear, branched or cyclic alkyl group having 1 to 20 carbon atoms is halogenated, preferably having 1 to 1 carbon atoms. A part of eight linear, branched or cyclic alkyl groups is halogenated. Specific examples include chloromethyl group, bromomethyl group, trifluoromethyl group, chloroethyl group, 2,2,2-trichloroethyl group, bromoethyl group, chloropropyl group, bromopropyl group and the like.

  Among the arbitrary substituents, the halogenated alkoxy group is a group in which a part of a linear, branched or cyclic alkoxy group having 1 to 20 carbon atoms is halogenated, preferably having 1 to 1 carbon atoms. A part of eight linear, branched or cyclic alkoxy groups are halogenated. Specific examples include chloromethoxy group, bromomethoxy group, trifluoromethoxy group, chloroethoxy group, 2,2,2-trichloroethoxy group, bromoethoxy group, chloropropoxy group, bromopropoxy group and the like.

  Among the optional substituents, the alkylamino group is an alkylamino group having an alkyl moiety having 1 to 20 carbon atoms, preferably an alkylamino group having an alkyl moiety having 1 to 8 carbon atoms. Specifically, methylamino group, ethylamino group, n-propylamino group, n-butylamino group, sec-butylamino group, n-pentylamino group, n-hexylamino group, n-heptylamino group, n -An octylamino group, 2-ethylhexylamino group, etc. are mentioned. Of these, a methylamino group, an ethylamino group, an n-propylamino group, and an n-butylamino group are preferable.

  Among the optional substituents, the alkylcarbonylamino group is an alkylcarbonylamino group having an alkyl moiety having 1 to 20 carbon atoms, preferably an alkylcarbonylamino group having an alkyl moiety having 1 to 8 carbon atoms. . Specifically, acetylamino group, ethylcarbonylamino group, n-propylcarbonylamino group, iso-propylcarbonylamino group, n-butylcarbonylamino group, iso-butylcarbonylamino group, sec-butylcarbonylamino group, t -Butylcarbonylamino group, n-pentylcarbonylamino group, n-hexylcarbonylamino group, cyclohexylcarbonylamino group, n-heptylcarbonylamino group, 3-heptylcarbonylamino group, n-octylcarbonylamino group and the like can be mentioned.

  Among the optional substituents, the arylamino group includes a phenylamino group, a p-methylphenylamino group, a pt-butylphenylamino group, a diphenylamino group, a di-p-methylphenylamino group, and a di-pt. -A butylphenylamino group etc. are mentioned.

  Among the optional substituents, the arylcarbonylamino group includes benzoylamino group, p-chlorobenzoylamino group, p-methoxybenzoylamino group, p-t-butylbenzoylamino group, p-trifluoromethylbenzoylamino group, m -A trifluoromethyl benzoylamino group etc. are mentioned.

  Among the optional substituents, the alkoxycarbonyl group refers to an alkoxycarbonyl which may contain a hetero atom in the alkyl group part of the alkoxy group, or an alkoxycarbonyl which may contain a hetero atom. The alkoxy group is the same as the above-described alkoxy group. Specific examples include methoxycarbonyl group, ethoxycarbonyl group, n-propoxycarbonyl group, isopropoxycarbonyl group, n-butoxycarbonyl group, isobutoxycarbonyl group, sec-butoxycarbonyl group, tert-butoxycarbonyl group and the like. . Of these, a methoxycarbonyl group and an ethoxycarbonyl group are preferred.

  Among the optional substituents, the alkylaminocarbonyl group is an alkylaminocarbonyl group having an alkyl moiety having 1 to 20 carbon atoms, preferably an alkylaminocarbonyl group having an alkyl moiety having 1 to 8 carbon atoms. Specifically, methylaminocarbonyl group, ethylaminocarbonyl group, n-propylaminocarbonyl group, n-butylaminocarbonyl group, sec-butylaminocarbonyl group, n-pentylaminocarbonyl group, n-hexylaminocarbonyl group, n-heptylaminocarbonyl group, n-octylaminocarbonyl group, 2-ethylhexylaminocarbonyl group, dimethylaminocarbonyl group, diethylaminocarbonyl group, di-n-propylaminocarbonyl group, di-n-butylaminocarbonyl group, di- Examples include sec-butylaminocarbonyl group, di-n-pentylaminocarbonyl group, di-n-hexylaminocarbonyl group, di-n-heptylaminocarbonyl group, di-n-octylaminocarbonyl group and the like.

  Among the optional substituents, the alkoxysulfonyl group is a sulfonyl group having a linear, branched or cyclic alkoxy group having 1 to 20 carbon atoms. Specific examples include a methylsulfonyl group, an ethylsulfonyl group, a propylsulfonyl group, an isopropylsulfonyl group, and a butylsulfonyl group.

  Among the optional substituents, the alkylthio group is an alkylthio group having an alkyl moiety having 1 to 20 carbon atoms, preferably an alkylthio group having an alkyl moiety having 1 to 8 carbon atoms. Specific examples include a methylthio group, an ethylthio group, a t-butylthio group, a di-tert-butylthio group, a 2-methyl-1-ethylthio group, and a 2-butyl-1-methylthio group.

  Among the optional substituents, the aryloxycarbonyl group is an aryloxycarbonyl group having an aryl moiety having 6 to 18 carbon atoms, and specific examples include phenoxycarbonyl and naphthoxycarbonyl groups.

  Among the optional substituents, the oxyalkyl ether group includes ethylene glycol heptyl ether, oxyethylene oleyl ether, oxypropylene butyl ether, oxypropylene 2-ethylhexyl ether, and the like.

  In addition, the said arbitrary substituent does not substitute the same kind of substituent. For example, any substituent that substitutes an alkyl group does not include an alkyl group.

  Further, the description and preferred examples of the metal, metal oxide or metal halide in the central metal M in the above formula (9) are the same as those described in the section of the formula (1).

  In formula (9), l is an integer of 0 to 5, preferably 1 or 2.

  Moreover, as a phthalocyanine compound (B), the phthalocyanine compound shown by the following formula | equation (10) is mentioned. The phthalocyanine compound represented by the formula (10) is disclosed in JP 2010-077408.

In formula (10), Z ₁ ″ to Z ₁₆ ″ each independently represents a hydrogen atom, the following chemical formula (11):

Or a group represented by the following chemical formula (13):

It is group shown by these.

In formula (11), X is an oxygen atom or a sulfur atom, preferably an oxygen atom, A ₁ is a phenyl group, a phenyl group having 1 to 5 substituents R ¹² , or a 1 to 7 substituent R ^12. And is preferably a phenyl group or a phenyl group having 1 to 5 substituents R ¹² . Each of the substituents R ¹² is independently substituted with a nitro group, COOR ¹³ , OR ¹⁴ (R ¹⁴ is an alkyl group having 1 to 8 carbon atoms), a halogen atom, an aryl group, a cyano group, or a halogen atom. R ¹³ is an alkyl group having 1 to 8 carbon atoms (in this case, the alkyl group is an alkyloxy group having 1 to 8 carbon atoms, a halogen atom or an aryl group). Group optionally substituted with a group), or a group represented by the following chemical formula (12);

In the formula, R ¹⁵ is an alkylene group having 1 to 3 carbon atoms, R ¹⁶ is an alkyl group having 1 to 8 carbon atoms, and b is an integer of 1 to 4.

In Formula (13), R ¹⁷ is an alkylene group having 1 to 3 carbon atoms, R ¹⁸ is an alkyl group having 1 to 8 carbon atoms, and a is an integer of 0 to 4.

In formula (10), _{1 to 3} of Z ₁ ″, Z ₄ ″, Z ₅ ″, Z ₈ ″, Z ₉ ″, Z ₁₂ ″, Z ₁₃ ″ and Z ₁₆ ″ are represented by chemical formula (11) or A group represented by the chemical formula (13), wherein _{3 to 1 of} Z ₂ ″, Z ₃ ″, Z ₆ ″, Z ₇ ″, Z ₁₀ ″, Z ₁₁ ″, Z ₁₄ ″ and Z ₁₅ ″ are It is a group represented by the chemical formula (11) or the chemical formula (13), and a total of four of Z ₁ ″ to Z ₁₆ ″ are groups represented by the chemical formula (11) or the chemical formula (13), and Z ₁ ″ to At least one of Z ₁₆ ″ is a group represented by the chemical formula (11), and M represents a metal-free, metal, metal oxide, or metal halide.

Among the phthalocyanine compounds represented by the chemical formula (10), Z _{1 to} Z ₁₆ preferably each independently represent a hydrogen atom or a group represented by the chemical formula (11).

In addition, at least one, preferably all, of the groups represented by the chemical formula (11) is preferably -X-A ₁ in which the substituent R ¹² is a nitro group, COOR ¹³ , a halogen atom, or a cyano group. . In addition, at least one, preferably all of the groups represented by the chemical formula (11) are represented by the following chemical formula (14):

In the chemical formula (14), X is the same definition as in the chemical formula (11), R ¹² corresponds to the substituent R ¹² and c is an integer of 1 to 5: (15):

In the chemical formula (15), X is the same definition as in the chemical formula (11), R ¹² corresponds to the substituent R ¹² , and c ′ is an integer of 1 to 7. It is preferable.

  Here, the description and preferred examples of the metal, metal oxide or metal halide in the central metal M in the formula (10) are the same as those described in the section of the formula (1). The aryl group is the same as that described in the column of formula (9).

As the phthalocyanine compound (B), in the above formula _{(10), Z 1 ",} Z 4", Z 5 ", Z 8", Z 9 ", Z 12", Z 13 " and _{Z 16"} is Each independently a halogen atom or the following formula:

Represents a 2,6-substituted phenoxy group represented by (also simply referred to as “2,6-substituted phenoxy group” in the present specification),
At this time, _{four of} Z ₁ ″, Z ₄ ″, Z ₅ ″, Z ₈ ″, Z ₉ ″, Z ₁₂ ″, Z ₁₃ ″ and Z ₁₆ ″ represent halogen atoms, and R ¹³ and R ¹⁴ Each independently represents a methyl group, an ethyl group or a halogen atom; Z ₂ ″, Z ₃ ″, Z ₆ ″, Z ₇ ″, Z ₁₀ ″, Z ₁₁ ″, Z ₁₄ ″ and Z ₁₅ ″ are Independently, the following formula:

In (herein, simply referred to as "substituted phenoxy group") substituted phenoxy group represented represent, this time, R ¹⁵ represents a halogen atom, when R ¹⁵ is plurally present, each R ¹⁵ May be the same or different and d is an integer from 1 to 5; M represents a metal-free, metal, metal oxide or metal halide;
The phthalocyanine compound shown by these is mentioned. A phthalocyanine compound represented by the following formula is disclosed in Japanese Patent Application Laid-Open No. 2008-050599.

In the above formula (10), Z ₁ ″, Z ₄ ″, Z ₅ ″, Z ₈ ″, Z ₉ ″, Z ₁₂ ″, Z ₁₃ ″ and Z ₁₆ ″, which are α-position substituents of the phthalocyanine nucleus, are Represents a halogen atom or a 2,6-substituted phenoxy group. In this case, Z ₁ ″, Z ₄ ″, Z ₅ ″, Z ₈ ″, Z ₉ ″, Z ₁₂ ″, Z ₁₃ ″ and Z ₁₆ ″ may be the same or different. Further, four of the α-position substituents of the phthalocyanine nucleus are halogen atoms, that is, the β-position of the phthalocyanine nucleus is occupied by four halogen atoms and four 2,6-substituted phenoxy groups. In this case, the position where the four halogen atoms and the four 2,6-substituted phenoxy groups occupy the α-position of the phthalocyanine nucleus is arbitrary and not particularly limited, but the two remaining positions of the benzene ring (for example, Z ₁ ″ and Z ₄ ″) are each bonded with a halogen atom and a 2,6-substituted phenoxy group; two residual groups of the benzene ring (for example, Z ₁ ″ and Z ₄ ″) have 2,6- In the case where two substituted phenoxy groups are bonded; in the case where two halogen atoms are bonded to the two remaining positions of the benzene ring (for example, Z ₁ ″ and Z ₄ ″), any may be used, but preferably each benzene ring Are bonded to one of the remaining residues (for example, Z ₁ ″ and Z ₄ ″) one by one, a halogen atom and a 2,6-substituted phenoxy group. In any of the above cases, the α-position of the phthalocyanine nucleus is occupied by a total of four halogen atoms and a total of four 2,6-substituted phenoxy groups.

In the above formula (10), the α-position halogen atom of the phthalocyanine nucleus is not particularly limited, and any of a fluorine atom, a chlorine atom, a bromine atom and an iodine atom can be selected. Z ₁ ″, Z ₄ ″, Z ₅ ″, Z ₈ ″, Z ₉ ″, Z ₁₂ ″, Z ₁₃ ″ and Z ₁₆ ″ are preferably a fluorine atom or a chlorine atom, and particularly preferably a fluorine atom. is there.

In the above formula showing a 2,6-substituted phenoxy group, R ¹³ and R ¹⁴ represent a methyl group, an ethyl group or a halogen atom. At this time, R ¹³ and R ¹⁴ may be the same or different. The halogen atom represented by R ³ and R ⁴ is not particularly limited and may be any of a fluorine atom, a chlorine atom, a bromine atom and an iodine atom, preferably a fluorine atom and a chlorine atom, particularly preferably Is a chlorine atom. Of the above, R ¹³ and R ¹⁴ are preferably a methyl group or an ethyl group, and most preferably R ¹³ and R ¹⁴ are both methyl groups.

Further, in the above formula (10), Z ₂ ″, Z ₃ ″, Z ₆ ″, Z ₇ ″, Z ₁₀ ″, Z ₁₁ ″, Z ₁₄ ″ and Z ₁₅ which are β-position substituents of the phthalocyanine nucleus. "Represents a substituted phenoxy group. At this time, Z ₂ ″, Z ₃ ″, Z ₆ ″, Z ₇ ″, Z ₁₀ ″, Z ₁₁ ″, Z ₁₄ ″ and Z ₁₅ ″ may be the same or different.

In the above formula showing a substituted phenoxy group, R ¹⁵ represents a halogen atom. At this time, when there are a plurality of R ¹⁵ (d is 2 or more), R ¹⁵ may be the same or different. R ¹⁵ in the above formula means that d hydrogen atoms at any position of the benzene ring remaining position (position where no oxygen atom is present) are substituted with d R ¹⁵ . The halogen atom as R ¹⁵ is not particularly limited, and any of a fluorine atom, a chlorine atom, a bromine atom and an iodine atom can be selected, and preferably a fluorine atom, a chlorine atom or a bromine atom. And particularly preferably a chlorine atom. D represents the number of the substituent R ¹⁵ bonded to the remaining position of the phenoxy group, and is an integer of 1 to 5, preferably an integer of 2 to 3, and most preferably 2. Position a substituent R ¹⁵ is bound to the remaining position of the phenoxy group is not particularly limited, it is suitably selected depending on the type of bond number (d) and substituents R ¹⁵ substituents R ^15. For example, when d is 2, preferred are 2,6, 2,3, 2,5, etc., and 2,6 is most preferred. Further, when d is 3, preferred are 2,4,6, 2,3,6, etc., and 2,4,6 is most preferred.

  Further, the explanation and preferred examples of the metal, metal oxide or metal halide in the central metal M in the formula (10) are the same as those explained in the section of the formula (1).

  Preferable examples of the phthalocyanine compound (B) according to the above form include the following compounds. The following formula representing the phthalocyanine compound (a) indicates that four fluorine atoms and four substituted phenoxy groups are bonded to the eight α-positions of the phthalocyanine nucleus. The position is arbitrary. The same applies to other examples of phthalocyanine compounds.

  When the infrared cut filter of the present invention contains the phthalocyanine compounds (A) and (B), the mixing ratio (weight ratio in the composition) of the phthalocyanine compound (A) and the phthalocyanine (B) is particularly limited. Although it is not, it is preferable that it is phthalocyanine (A): phthalocyanine (B) = 1: 0.05-2.5 by content weight ratio, and it is more preferable that it is 1: 0.1-1.

  The phthalocyanine compound (A) of the present invention and the phthalocyanine composition containing the phthalocyanine compound (A) and the phthalocyanine compound (B) (hereinafter also simply referred to as “phthalocyanine composition”) are suitably used for an infrared cut filter. Hereinafter, the phthalocyanine compound (A) or phthalocyanine composition according to the present invention is simply referred to as “phthalocyanines”.

  The infrared cut filter is not particularly limited, but includes a resin layer containing phthalocyanines and an optical multilayer film in order to realize a thin film while reducing the angle dependency of the reflection type filter. It is preferable that it is a type | mold infrared cut filter. At this time, as described below, the resin layer may also serve as the base material.

  As a form using phthalocyanines for the infrared cut filter, (i) a form in which an optical multilayer film (reflective film) is laminated on at least one of the base material composed of a resin layer containing a phthalocyanine and a resin support film (Ii) a form in which an optical multilayer film (reflection film) is laminated on at least one of the resin base material containing phthalocyanines, (iii) an optical multilayer film is formed on at least one of the resin base material, Examples include a resin layer containing a resin layer containing a phthalocyanine or a resin layer containing a phthalocyanine and a resin support film on the optical multilayer film.

  In the case of the form (i), even if phthalocyanines are difficult to disperse in the base resin, the effect of the present invention can be imparted by coating the surface with a resin layer. Since the absorption characteristics can be controlled by changing the phthalocyanine concentration in the resin layer and the coating thickness of the resin layer, the film thickness of the support film is hardly changed by, for example, coating the resin layer very thinly. The effect of the invention can be imparted, the thickness of the support film can be adjusted, or the resin layer can be used for surface modification such as reduction of surface scratches on the support film.

  Moreover, it is also preferable to set it as the resin sheet which pinched | interposed the resin layer with the support body film.

  As the support film in the form (i) or (iii), it is preferable to use a resin having excellent transparency. Specifically, for example, (meth) acrylic resin, epoxy resin, polycarbonate resin, polyester resin, fluorinated aromatic polymer, poly (amide) imide resin, polyamide resin, aramid resin, polycycloolefin resin, etc. may be used. it can. Among these, fluorinated aromatic polymer, poly (amide) imide resin, polyamide resin, aramid resin, polycycloolefin resin, epoxy resin, and acrylic resin are excellent in heat resistance when the optical multilayer film is formed by vapor deposition. preferable.

  The resin substrate in the form (iii) can be the same as the support film described above, and the preferred form is the same as in the case of the support film.

  In the form (ii), the resin layer containing the pigment also serves as the support film. In the form (ii), the method for producing the resin sheet is not particularly limited, but a method for producing the resin sheet by forming a resin layer on the surface of an arbitrary base material (resin film or glass plate) by a solvent casting method and peeling it. Is preferred.

  In the form in which the phthalocyanines are uniformly dispersed in the resin layer, the method for forming the resin layer in which the pigment is dispersed is not particularly limited, and for example, a kneading method or a solvent casting method can be employed. Among these, it is preferable to employ a solvent casting method. Thereby, since a pigment | dye can be disperse | distributed more uniformly, the light absorption film excellent in light selective absorption can be formed. In addition, since the pigment can be dispersed at a high concentration, it is possible to reduce the thickness of the pigment and meet demands for reducing the height of members such as an imaging lens element. Furthermore, since the resin layer can be formed at a relatively low temperature, a dye having a relatively low heat resistance can also be used.

  The solvent (organic solvent) used in the solvent casting method is not particularly limited as long as it can dissolve the resin-forming component for forming the resin layer, and can be appropriately selected depending on the type of resin. (2-butanone), ketones such as methyl isobutyl ketone (4-methyl-2-pentanone), cyclohexanone; PGMEA (2-acetoxy-1-methoxypropane), ethylene glycol mono-n-butyl ether, ethylene glycol monoethyl ether Glycol derivatives such as ethylene glycol ethyl ether acetate (ether compounds, ester compounds, ether ester compounds, etc.); amides such as N, N-dimethylacetamide; esters such as ethyl acetate, propyl acetate, butyl acetate; N-methyl -Pyrrolidone (Y Specifically, pyrrolidones such as 1-methyl-2-pyrrolidone); aromatic hydrocarbons such as toluene and xylene; aliphatic hydrocarbons such as cyclohexane and heptane; ethers such as diethyl ether and dipyl ether Etc. are suitable. More preferred are methyl ethyl ketone, ethyl acetate, and N, N-dimethylacetamide.

  The amount of the solvent used is preferably 150% by weight or more, and more preferably 1900% by weight or less with respect to 100% by weight of the total amount of the binder resin for forming the resin layer. More preferably, it is 200% by weight or more and 1400% by weight or less.

  In the solvent casting method, a dispersion in which a pigment is uniformly dispersed in a solution obtained by dissolving a resin forming component (binder resin) for forming a resin layer in a solvent is applied onto a substrate and dried (cured). ) To form a resin layer (film formation). When a liquid resin raw material is used as the resin forming component, the dye may be directly dispersed in the resin raw material, or the dye may be dispersed after the resin raw material is diluted with a solvent.

  The binder resin contained in the resin layer is not particularly limited as long as it has high solubility in the phthalocyanines according to the present invention. For example, fluorinated aromatic polymer, poly (amide) imide resin, polyamide resin, aramid Examples include resins, polycycloolefin resins, epoxy resins (compounds), acrylic resins (compounds), vinyl monomers ((meth) acrylic compounds, styrene compounds, etc.), poly (amide) imide precursors, and the like. The fluorinated aromatic polymer includes an aromatic ring having at least one fluorine group and at least one bond selected from the group consisting of an ether bond, a ketone bond, a sulfone bond, an amide bond, an imide bond and an ester bond. Examples include polymers composed of repeating units including, for example, fluorine-containing polyimide, polyether, polyetherimide, polyether ketone, polyether sulfone, polyamide ether, polyamide, polyether nitrile. And polyester. The poly (amide) imide precursor is a raw material for forming a poly (amide) imide resin, that is, a compound that is subjected to an imidization reaction. For example, a polyamic acid is preferable. Specifically, for example, HPC-7000-30 manufactured by Hitachi Chemical Co., Ltd. is preferably used.

  From the viewpoint of visible light permeability, it is preferable to use a poly (amide) imide resin, a fluorinated aromatic polymer such as FPEK, and / or a poly (amide) imide precursor as the binder resin.

  The resin layer may contain other light-absorbing dyes other than phthalocyanines. Other light absorbing dyes include other phthalocyanine dyes, cyanine dyes, porphyrin dyes, pyromethene dyes, azo dyes, quinone dyes, squarylium dyes, triarylmethane dyes, indigo dyes, Copper ion dyes and diimonium dyes are preferred. Other phthalocyanine dyes, cyanine dyes, porphyrin dyes, and copper ion dyes are preferred because of their high transmittance in the visible light region.

  The concentration (content) of the phthalocyanines in the resin layer is preferably 0.0001 wt% or more and less than 15 wt% with respect to 100 wt% of the total amount of the resin layer. More preferably, it is 0.001% by weight or more and less than 10% by weight. More preferably, it is 0.1 wt% or more and less than 10 wt%, particularly preferably 0.5 wt% or more and less than 10 wt%, with respect to 100 wt% of the total amount of the resin layer.

  The thickness of the resin layer is preferably 1 mm or less. As a result, the infrared cut filter can be sufficiently thinned to meet the demand for lowering the height of optical members and the like. More preferably, it is 200 micrometers or less as thickness of a resin layer, More preferably, it is 100 micrometers or less. Moreover, in the form which consists of the resin layer containing a pigment | dye and a support body film, it is preferable that the thickness of the said resin layer is 10 micrometers or less, and the thickness of a support body film is 100 micrometers or less.

  As the optical multilayer film, an inorganic multilayer film or the like that can control the refractive index of each wavelength is suitable in that it has excellent heat resistance. As the inorganic multilayer film, a refractive index control multilayer film in which a low refractive index material and a high refractive index material are alternately laminated on a base material or other functional material layers by a vacuum deposition method, a sputtering method or the like is preferable. . The optical multilayer film is also preferably a transparent conductive film. As the transparent conductive film, a transparent conductive film as a film that reflects infrared rays, such as indium-tin oxide (ITO), is preferable. Among these, an inorganic multilayer film is preferable.

  As the inorganic multilayer film, a dielectric multilayer film in which dielectric layers A and dielectric layers B having a refractive index higher than that of the dielectric layer A are alternately stacked is preferable. As a material constituting the dielectric layer A, a material having a refractive index of 1.6 or less can be normally used, and a material having a refractive index range of 1.2 to 1.6 is preferably selected. As the material, for example, silica, alumina, lanthanum fluoride, magnesium fluoride, sodium hexafluoride sodium, and the like are suitable. As a material constituting the dielectric layer B, a material having a refractive index of 1.7 or more can be used, and a material having a refractive index range of 1.7 to 2.5 is preferably selected. Examples of the material include titanium oxide, zirconium oxide, tantalum pentoxide, niobium pentoxide, lanthanum oxide, yttrium oxide, zinc oxide, zinc sulfide, indium oxide as a main component, and small amounts of titanium oxide, tin oxide, cerium oxide, and the like. What was contained is suitable.

  In general, the thickness of each of the dielectric layer A and the dielectric layer B is preferably 0.1λ to 0.5λ when the wavelength of light to be blocked is λ (nm). When the thickness is out of the above range, the product (n × d) of the refractive index (n) and the film thickness (d) is significantly different from the optical film thickness calculated by λ / 4, and the optical characteristics of reflection and refraction are different. May be lost, and control for blocking / transmitting a specific wavelength may not be possible.

  The method for laminating the dielectric layer A and the dielectric layer B is not particularly limited as long as a dielectric multilayer film in which these material layers are laminated is formed. For example, CVD, sputtering, vacuum deposition Thus, a dielectric multilayer film can be formed by alternately laminating the dielectric layers A and B.

  The optical multilayer film such as the inorganic multilayer film can be suitably formed by the above method or the like, but in order to reduce the possibility that the infrared cut filter is deformed and curled or cracked by vapor deposition, the following This method can be used. Specifically, a multilayer film is formed by forming a vapor deposition layer on a temporary substrate such as glass that has been subjected to a release treatment, and transferring the vapor deposition layer to a resin sheet that is a substrate of an infrared cut filter to form a multilayer film. A transfer method is preferred. In this case, it is preferable to form an adhesive layer on the resin sheet. When the resin sheet is formed of an organic material, specifically, a resin composition, the dielectric layer and the like are vapor-deposited on an uncured and semi-cured resin sheet (resin composition). A method of curing the sheet is preferred. When such a method is used, the substrate becomes fluid and becomes in a liquid state during cooling after multi-layer deposition, so the difference in thermal expansion coefficient between the resin composition and the dielectric layer does not matter. The deformation (curl) of the infrared cut filter can be suppressed.

  As described above, the vapor deposition method is preferably used for forming the optical multilayer film (preferably the inorganic multilayer film) on the resin sheet, but the vapor deposition temperature is preferably 100 ° C. or higher. More preferably, it is 120 degreeC or more, More preferably, it is 150 degreeC or more. When vapor deposition is performed at such a high temperature, the inorganic film (inorganic film constituting the inorganic multilayer film) becomes dense and hard, and there are advantages such as improving various resistances and improving the yield.

  The optical multilayer film is formed on at least one surface of the resin sheet. The optical multilayer film may be formed on only one surface of the resin sheet or may be formed on both surfaces of the resin sheet, but is preferably formed on both surfaces. Thereby, the curvature of the infrared cut filter which concerns on this invention, and the crack of an optical multilayer film can be reduced. Moreover, in the form in which the resin sheet is composed of the resin layer containing the dye and the support film, the optical multilayer film is preferably formed on the surface of the resin layer.

  When the optical multilayer film has the optical multilayer film only on one surface of the resin sheet, the number of optical multilayer films is preferably in the range of 10 to 80 layers, and more preferably in the range of 25 to 50 layers. On the other hand, when it has the said optical multilayer film on both surfaces of a resin sheet, the range of 10-80 layers is preferable as a total of the lamination | stacking number of the said optical multilayer film on both surfaces of a resin sheet, More preferably, it is 25-50. The range of layers. The optical multilayer film preferably has a thickness of 0.5 to 10 μm. More preferably, it is 2-8 micrometers. In the form in which the optical multilayer film is formed on both surfaces of the resin sheet, the total thickness of the optical multilayer films on both surfaces is preferably within the above range.

  The infrared cut filter preferably has a thickness of 1 mm or less. Here, the thickness of the infrared cut filter refers to the maximum thickness of the infrared cut filter. The thickness of the infrared cut filter is more preferably 200 μm or less, more preferably 150 μm or less, particularly preferably 120 μm or less, and most preferably 60 μm or less in that it can meet the demand for thinning. In addition, the thickness of the infrared cut filter is preferably 1 μm or more, more preferably 10 μm or more, and further preferably 30 μm or more in terms of excellent reflow resistance, particularly heat resistance at a temperature of 260 ° C. The thickness range of the infrared cut filter is preferably 1 to 150 μm, more preferably 10 to 120 μm, still more preferably 30 to 120 μm, and particularly preferably 30 to 60 μm.

  By setting the thickness of the infrared cut filter to 1 mm or less, the infrared cut filter can be reduced in size and weight, and can be suitably used for various applications. In particular, it can be suitably used in optical applications such as optical members. In optical applications, as with other optical members, infrared cut filters are strongly required to be small and light. The infrared cut filter of the present invention can achieve a reduction in thickness by setting the thickness to 1 mm or less, and in particular, when used in a lens unit such as an imaging lens, the lens unit can be reduced in height. In other words, when a thin infrared cut filter of 1 mm or less is used as the optical member, the optical path can be shortened and the optical member can be made small.

  By using a reflection-absorption filter composed of a dye-containing absorption layer and an optical multilayer film such as an inorganic vapor deposition film as an infrared cut filter, the incident angle dependence of the light blocking characteristic can be sufficiently reduced. it can.

The infrared cut filter of the present invention can sufficiently reduce the incident angle dependency of the light blocking characteristic and can be sufficiently thinned, so that it is a heat ray cut filter to be mounted on a glass of an automobile or a building. Not only is it useful as an IR cut filter for optical device applications, display device applications, mechanical components, electrical / electronic components, etc., but it also blocks optical noise in camera module (also called solid-state image sensor) applications and corrects visibility. This is useful as a filter. Specifically, it can be suitably used for various applications, and is particularly useful as an IR cut filter for a camera module.
In particular, it is useful as a filter for camera modules such as digital still cameras and mobile phone cameras that are becoming thinner and lighter.

  FIG. 1 schematically shows an example of a camera module. The camera module shown in FIG. 1 includes a lens (imaging lens) 1, a barrel 2 that holds the lens 1, an infrared cut filter 3, a holder 4 that holds members, a cover glass 5, and a sensor 6 such as a CCD or CMOS. . The infrared cut filter has a role of cutting light of a desired wavelength (in the camera module, for example, light having a wavelength of 700 nm or more) to prevent malfunction of the CMOS sensor.

  That is, the present invention also provides a solid-state imaging device having at least the infrared cut filter, lens unit portion, and sensor portion of the present invention. Normally, in a solid-state imaging device using a reflection type infrared cut filter, a lens unit section using a large number of lenses in order to suppress the influence caused by the incident angle dependency (occurrence of color unevenness due to the incident angle). However, in the solid-state imaging device of the present invention, the influence due to the incident angle dependency is sufficiently eliminated by using the above-described infrared cut filter, so that the number of lenses constituting the lens unit portion is reduced. Thus, a reduction in thickness and weight can be realized. In addition, about a lens unit part, the form as described in WO2008 / 081892 can be employ | adopted preferably.

  As another embodiment of the present invention, there is a solid-state imaging device having an infrared cut layer containing the phthalocyanine compound according to the present invention. That is, this invention also provides the solid-state image sensor which has an infrared cut layer containing a phthalocyanine compound, a lens unit part, and a sensor part at least.

  The infrared cut layer contains a binder resin in addition to the phthalocyanine compound. The form of cutting unnecessary infrared rays without forming a filter is high in productivity, and can solve the problem that the yield decreases due to warping of the filter when the infrared cut filter is installed on the sensor.

  As an arrangement of the infrared cut layer in the solid-state imaging device, as disclosed in International Publication No. 2004/006336, a configuration that covers the entire sensor of the solid-state imaging device, JP 2012-118294 A, JP 2012-118295 A, or the like. The form etc. which are made to contain in a soldering resist are mentioned as disclosed by gazette. The infrared cut layer may refer to a member having an infrared cut ability by containing a phthalocyanine compound in a member having another function.

  Since the present invention is characterized in that it contains a phthalocyanine compound, the method for producing an infrared cut layer can be applied by appropriately referring to known knowledge or combining them. For example, the method disclosed in International Publication No. 2004/006336 is preferable for producing the infrared cut layer of the present invention, but is not limited thereto.

  For example, a photosensitive resin composition containing the phthalocyanines of the present invention is applied onto a semiconductor substrate on which a photoelectric conversion element, a light shielding layer, and the like are formed by spin coating or the like, and dried. Next, after that, exposure is performed through a photomask as necessary. Then, if necessary, alkali development is performed to obtain an infrared cut layer. A color resist is formed thereon, and a color filter is formed by photolithography using an exposure apparatus. Furthermore, a microlens can be formed to form a solid-state imaging device.

  Hereinafter, a method for producing a photosensitive resin composition using the phthalocyanine compound of the present invention will be described more specifically.

  The photosensitive resin composition contains the phthalocyanine compound of the present invention, but preferably further contains a solvent, a photosensitive resin composition, a dispersant, or the like.

  Examples of the solvent include toluene, xylene, benzene, ethylbenzene, tetralin, styrene, cyclohexane, dichloromethane, chloroform, ethyl chloride, 1,1,1-trichloroethane, 1-chlorobutane, cyclohexyl chloride, trans-dichloroethylene, cyclohexanol, methyl. Cellosolve, n-propanol, n-butanol, 2-ethylbutanol, n-heptanol, 2-ethylhexanol, butoxyethanol, diacetone alcohol, benzaldehyde, γ-butyrolactone, acetone, methyl ethyl ketone, dibutyl ketone, methyl-i-butyl ketone, Methyl-i-amyl ketone, cyclohexane, acetophenone, methylal, furan, β-β-dichloroethyl ether, dioxane, Trahydrofuran, ethyl acetate, n-butyl acetate, amyl acetate, n-butyl acetate, cyclohexylamine, ethanolamine, dimethylformamide, acetonitrile, nitromethane, nitroethane, 2-nitropropane, nitrobenzene, dimethylsulfoxide, diethylene glycol dimethyl ether, diethylene glycol Examples include monomethyl ether, propylene glycol monomethyl ether acetate (PGMEA), ethylene glycol monomethyl ether acetate, cyclohexanone, and N-methylpyrrolidone. Among them, diethylene glycol dimethyl ether, propylene glycol monomethyl ether acetate, cyclohexanone, and the like are preferable from the viewpoint of boiling point and viscosity.

  The phthalocyanine compound is preferably 1 to 20% by weight, more preferably 2 to 10% by weight, based on the solvent.

  Next, the photosensitive resin composition that can be used in the present invention undergoes a chemical reaction by the action of light, resulting in a change in solubility or affinity for the solvent or a change from liquid to solid. For example, an acrylic or maleimide resin is used as a binder resin (base polymer), and photosensitive monomers (photopolymerizable monomers) and photopolymerization initiators made of various acrylic esters or methacrylic esters are added thereto. Photopolymerization type photosensitive resin composition, or photodimerization type photosensitive resin composition using an acrylic resin liquid to be photodimerized, and the like. preferable. The term “acrylic resin liquid” as used herein means a solution obtained by dissolving an acrylic resin in a solvent to be used so as to have an appropriate viscosity, and includes a solvent-free liquid acrylic resin liquid. There may be. That is, in the composition of the present invention, a solvent is not necessarily required, and even if it is a solventless composition, the photosensitive resin composition is in a liquid state and can uniformly dissolve the above-described dye, In addition, a solvent may not be used as long as it has an appropriate viscosity as a resist preparation solution. In this case, a usable dye can be selected by measuring the solubility of the dye in advance using toluene or toluene and diethylene glycol dimethyl ether.

  As the acrylic or maleimide resin, at least 10% by weight of monomers and oligomers constituting the acrylic resin or maleimide resin are selected from compounds having acrylic acid, methacrylic acid, acrylic acid ester, methacrylic acid ester and maleimide group. Preferably, the compound having an acrylic acid, methacrylic acid or maleimide group is preferably 1 to 50% by weight, more preferably 5 to 35% by weight, and the compound having an acrylic acid, methacrylic acid or maleimide group is preferably 10 to 90% by weight. Part, more preferably 30 to 80 parts by weight.

  As monomers and oligomers constituting the acrylic resin, (meth) acrylic acid, methyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, octyl (meth) acrylate, Benzyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, (meth) acrylamide, N-hydroxymethylacrylamide, acrylonitrile, styrene, vinyl acetate, maleic acid, fumaric acid, polyethylene glycol Di (meth) acrylate, trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, dipentaerythritol hexa (meth) acrylate, dipenta Examples include hexa (meth) acrylate, melamine (meth) acrylate, and epoxy (meth) acrylate prepolymers of caprolactone adducts of thrisitol hexa (meth) acrylate. Examples of acrylic resins include (meth) acrylic acid, hydroxyalkyl ( Polymerized with (meth) acrylate, acrylic resin obtained by polymerizing various alkyl (meth) acrylates, (meth) acrylic acid, hydroxyalkyl (meth) acrylate, various alkyl (meth) acrylates, benzyl (meth) acrylate, and styrene. An acrylic resin obtained by polymerizing an acrylic resin, (meth) acrylic acid, and various alkyl (meth) acrylates is preferable.

  Examples of monomers constituting the maleimide resin include fragrances such as N-phenylmaleimide, N-benzylmaleimide, N-hydroxyphenylmaleimide, N-methylphenylmaleimide, N-methoxyphenylmaleimide, N-chlorophenylmaleimide, and N-naphthylmaleimide. In addition to group-substituted maleimides, alkyl-substituted maleimides such as N-methylmaleimide, N-ethylmaleimide, N-propylmaleimide, and N-cyclohexylmaleimide can be exemplified.

  Examples of the photosensitive monomer that can be a component of the photosensitive resin composition include monomers constituting the acrylic resin, preferably trimethylolpropane trimethacrylate, dipentaerythritol hexaacrylate, pentaerythritol triacrylate, Polyfunctional (meth) acrylates such as pentaerythritol tetraacrylate are exemplified.

  The amount of the photosensitive monomer used is preferably 40 to 90 parts by weight, more preferably 60 to 70 parts by weight with respect to 100 parts by weight of the acrylic resin.

  Examples of the photopolymerization initiator that can be a composition component of the photopolymerizable photosensitive resin composition include, for example, benzoin alkyl ether compounds, acetophenone compounds, benzophenone compounds, phenyl ketone compounds, thioxanthone compounds, triazine compounds, Examples include imidazole compounds and anthraquinone compounds. More specifically, 4-phenoxydichloroacetophenone, 4-t-butyl-dichloroacetophenone, diethoxyacetophenone, 1- (4-isopropylphenyl) -2-hydroxy-2-methylpropan-1-one, 1-hydroxy Acetophenone compounds such as cyclohexyl phenyl ketone, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butan-1-one, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzyldimethyl ketal, etc. Benzoin alkyl ether compounds, benzophenone, benzoylbenzoic acid, methyl benzoylbenzoate, 4-phenylbenzophenone, hydroxybenzophenone, acrylated benzophenone, 4-benzoyl- Benzophenone compounds such as' -methyldiphenyl sulfide, thioxanthone compounds such as thioxanthone, 2-chlorothioxanthone, 2-methylthioxanthone, isopropylthioxanthone 2,4-diisopropylthioxanthone, 2,4,6- Trichloro-s-triazine, 2-phenyl-4,6-bis (trichloromethyl) -s-triazine, 2- (p-methoxyphenyl) -4,6-bis (trichloromethyl) -s-triazine, 2- ( p-tolyl) -4,6-bis (trichloromethyl) -s-triazine, 2-pienyl-4,6-bis (trichloromethyl) -s-triazine, 2,4-bis (trichloromethyl) -6-styryl -S-triazine, 2- (naphth-1-yl) -4,6-bis (trichloromethyl)- -Triazine, 2- (4-methoxy-naphth-1-yl) -4,6-bis (trichloromethyl) -s-triazine, 2,4-trichloromethyl- (piperonyl) -6-triazine, 2,4- Triazine compounds such as trichloromethyl (4′-methoxystyryl) -6-triazine, 2- (2,3-dichlorophenyl) -4,5-diphenylimidazole dimer, 2- (2,3-dichlorophenyl) -4 , 5-bis (3-methoxyphenyl) -imidazole dimer, 2- (2,3-dichlorophenyl) -4,5-bis (4-methoxyphenyl) -imidazole dimer, 2- (2,3- Dichlorophenyl) -4,5-bis (4-chlorophenyl) -imidazole dimer, 2- (2,3-dichlorophenyl) -4,5-di (2-furyl) -imida Zole, imidazole compounds such as 2,2′-bis (2-chlorophenyl) -4,5,4 ′, 5′-tetraphenyl-1,2′-biimidazole, Irgacure 369, Irgacure 907 (both are Ciba Geigyca And acetophenone compounds such as trade names).

  The addition amount of the photopolymerization initiator is not particularly limited, but for acetophenone compounds (Irgacure 369, etc.), a photosensitive monomer (photopolymerizable monomer; for example, dipentaerythritol hexaacrylate, etc.) is 100. When it is set to be parts by weight, it is preferably added in a proportion of 1 to 30 parts by weight, more preferably 5 to 15 parts by weight.

  In addition, arbitrary components, such as a thermal polymerization inhibitor, can be added to the photosensitive resin composition as needed. The thermal polymerization inhibitor is added for the purpose of improving storage stability. For example, hydroquinone, p-methoxyphenol, di-t-butyl-p-cresol, pyrogallol, t-butylcatechol, benzoquinone, 4 , 4′-thiobis (3-methyl-6-tert-butylphenol), 2,2′-methylene (4-methyl-6-tert-butylphenol), 2- (mercaptobenzimidazole) and the like. Moreover, you may add a photodegradation prevention agent as needed.

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 the names of the following compounds, Pc represents a phthalocyanine nucleus. In the names of the following compounds, “α- (substituent A) _a , β- (substituent A) _x-a Pc (0 <a <x)” is described as follows. Mean that an average of a substituents at the α-position and an average of x-a substituents at the β-position are introduced, that is, a total of x substituents A are introduced at the α-position and the β-position. Means that.

(Example 1) [VOPc- {α- (2,5-Cl ₂ C ₆ H ₃ O)} _x , {β- (2,5-Cl ₂ C ₆ H ₃ O)} _6-x Cl ₁₀ ] Synthesis of (0 ≦ x <6) In a 200 ml four-necked separable flask, 7.98 g (0.030 mol) of tetrachlorophthalonitrile, 7.43 g (0.045 mol) of 2,5-dichlorophenol, carbonic acid 6.86 g (0.050 mol) of potassium and 25.58 g of benzonitrile were charged and reacted at 80 ° C. for 10 hours to obtain a reaction solution containing a desired phthalonitrile compound. After cooling, the solution obtained by suction filtration was concentrated to adjust the phthalonitrile compound concentration to 30 wt%.

  To a 100 ml four-necked separable flask, 1.53 g (0.010 mol) of vanadium chloride and 1.27 g (0.010 mol) of octanol were added, and nitrogen gas was supplied to the liquid phase part at 170 ° C. And stirred for 20 hours. After cooling, the reaction solution was dropped into methanol (283.4 g) corresponding to 20 times the sum of the weight of the obtained phthalocyanine compound, and stirred for 30 minutes to precipitate crystals. After the obtained crystals were suction filtered, washing and purification were performed by adding methanol (141.7 g) of 1/2 times the amount at the time of crystallization and stirring for 30 minutes. After suction filtration, the taken out crystals were vacuum-dried at about 90 ° C. overnight to obtain 12.45 g of the desired phthalocyanine compound (yield based on tetrachlorophthalonitrile: 87.9 mol%).

Example 2 [VOPc- {α- (2,5-Cl ₂ C ₆ H ₃ O)} _x , {β- (2,5-Cl ₂ C ₆ H ₃ O)} _8-x Cl ₈ ] Synthesis of (0 ≦ x <8) In a 200 ml four-necked separable flask, 7.98 g (0.030 mol) of tetrachlorophthalonitrile, 9.98 g (0.060 mol) of 2,5-dichlorophenol, carbonic acid 9.25 g (0.066 mol) of potassium and 25.38 g of benzonitrile were charged and reacted at 80 ° C. for 10 hours to obtain a reaction solution containing a desired phthalonitrile compound. After cooling, the solution obtained by suction filtration was concentrated to adjust the phthalonitrile compound concentration to 30 wt%.

  To a 100 ml four-necked separable flask, 1.53 g (0.010 mol) of vanadium chloride and 1.27 g (0.010 mol) of octanol were added, and nitrogen gas was supplied to the liquid phase part at 170 ° C. And stirred for 20 hours. After cooling, the completely same operation as Example 1 was performed, and 14.19 g (yield with respect to tetrafluoro phthalonitrile: 88.3 mol%) of target objects was obtained.

(Example 3) [VOPc- {α- (2,5-Cl ₂ C ₆ H ₃ O)} _x , {β- (2,5-Cl ₂ C ₆ H ₃ O)} _10-x Cl ₆ ] Synthesis of (0 ≦ x <10) In a four-necked separable flask in 200 ml, tetrachlorophthalonitrile 7.98 g (0.030 mol) and 2,5-dichlorophenol 12.35 g (0.075 mol), carbonic acid 11.40 g (0.083 mol) of potassium and 25.84 g of benzonitrile were charged and reacted at 80 ° C. for 10 hours to obtain a reaction solution containing a desired phthalonitrile compound. After cooling, the solution obtained by suction filtration was concentrated to prepare a phthalonitrile compound concentration of 30 wt%.

  To a 100 ml four-necked separable flask, 1.53 g (0.010 mol) of vanadium chloride and 1.27 g (0.010 mol) of octanol were added, and nitrogen gas was supplied to the liquid phase part at 170 ° C. And stirred for 20 hours. After cooling, the completely same operation as Example 1 was performed, and the target object 14.03g (yield 78.1 mol% with respect to tetrachlorophthalonitrile) was obtained.

(Example _{4) [VOPc- {α- (2,5} -Cl 2 C 6 H 3 O)} x, {β- (2,5-Cl 2 C 6 H 3 O)} 12-x Cl 4] Synthesis of (0 ≦ x <12) In a four-necked separable flask in 200 ml, tetrachlorophthalonitrile 7.98 g (0.030 mol), 2,5-dichlorophenol 14.85 g (0.090 mol), carbonic acid 13.68 g (0.099 mol) of potassium and 25.84 g of benzonitrile were charged and reacted at 80 ° C. for 10 hours to obtain a reaction solution containing a desired phthalonitrile compound. After cooling, the solution obtained by suction filtration was concentrated to prepare a phthalonitrile compound concentration of 30 wt%.

  To a 100 ml four-necked separable flask, 1.53 g (0.010 mol) of vanadium chloride and 1.27 g (0.010 mol) of octanol were added, and nitrogen gas was supplied to the liquid phase part at 170 ° C. And stirred for 20 hours. After cooling, the completely same operation as Example 1 was performed, and the target object 14.77g (yield 74.4 mol% with respect to tetrachlorophthalonitrile) was obtained.

(Example 5) [VOPc- {α- (2,5-Cl ₂ C ₆ H ₃ O) _x (2,6- (CH ₃ ) ₂ C ₆ H ₃ O) _y }, {β- (2, 5-Cl ₂ C ₆ H ₃ O) _4-x (2,6- (CH ₃ ) ₂ C ₆ H ₃ O) _4-y } Cl ₈ ] (0 ≦ x <4, 0 ≦ y <4) Synthesis In a 200 ml four-necked separable flask, tetrachlorophthalonitrile 8.30 g (0.031 mol), 2,5-dichlorophenol 5.09 g (0.031 mol), 2,6-dimethylphenol 3.81 g (0.031 mol), 9.50 g (0.068 mol) of potassium carbonate, and 21.90 g of benzonitrile were allowed to react at 80 ° C. for 10 hours to obtain a reaction solution containing a desired phthalonitrile compound. After cooling, the solution obtained by suction filtration was concentrated to prepare a phthalonitrile compound concentration of 30 wt%.
Add 1003 ml of the obtained reaction solution, 1.53 g (0.010 mol) of vanadium chloride and 1.27 g (0.010 mol) of octanol to a four-necked separable flask. And stirred for 20 hours. After cooling, the completely same operation as Example 1 was performed, and the target object 12.90g (yield 83.5 mol% with respect to tetrachlorophthalonitrile) was obtained.

(Example 6) [VOPc- {α- (2,5-Cl ₂ C ₆ H ₃ O)} _x , {β- (2,5-Cl ₂ C ₆ H ₃ O)} _10-x F ₆ ] Synthesis of (0 ≦ x <10) In a four-necked separable flask in 200 ml, tetrafluorophthalonitrile 6.00 g (0.030 mol) and 2,5-dichlorophenol 12.35 g (0.075 mol), carbonic acid 10.74 g (0.083 mol) of potassium and 25.84 g of benzonitrile were charged and reacted at 80 ° C. for 10 hours to obtain a reaction solution containing a desired phthalonitrile compound. After cooling, the solution obtained by suction filtration was concentrated to prepare a phthalonitrile compound concentration of 30 wt%.

  To a 100 ml four-necked separable flask, 1.53 g (0.010 mol) of vanadium chloride and 1.27 g (0.010 mol) of octanol were added, and nitrogen gas was supplied to the liquid phase part at 170 ° C. And stirred for 20 hours. After cooling, the completely same operation as Example 1 was performed, and 13.85 g (yield 80.4 mol% with respect to tetrafluoro phthalonitrile) of target objects was obtained.

(Example 7) [ZnPc- {α- (2,5-Cl ₂ C ₆ H ₃ O)} _x , {β- (2,5-Cl ₂ C ₆ H ₃ O)} _10-x F ₆ ] Synthesis of (0 ≦ x <10) In a 200 ml four-necked separable flask, 6.00 g (0.030 mol) of tetrafluorophthalonitrile, 12.40 g (0.075 mol) of 2,5-dichlorophenol, carbonic acid 12.5 g (0.09 mol) of potassium and 25.76 g of benzonitrile were charged and reacted at 80 ° C. for 10 hours to obtain a reaction solution containing a desired phthalonitrile compound. After cooling, the solution obtained by suction filtration was concentrated to adjust the phthalonitrile compound concentration to 30 wt%.

  The obtained reaction solution, 2.40 g (0.0075 g) of zinc iodide, was added to a 100 ml four-necked separable flask, and reacted at 160 ° C. for 20 hours under nitrogen flow (10 ml / min). After cooling, the completely same operation as Example 1 was performed, and 12.24 g (yield with respect to tetrafluoro phthalonitrile: 76.6 mol%) of target objects was obtained.

(Example 8) [ZnPc- {α- (2,5-Cl ₂ C ₆ H ₃ O)} _x , {β- (2,6-Cl ₂ C ₆ H ₃ O)} _12-x F ₄ ] Synthesis of (0 ≦ x <12) In a four-necked separable flask in 200 ml, tetrafluorophthalonitrile 4.00 g (0.020 mol) and 2,5-dichlorophenol 9.87 g (0.060 mol), carbonic acid 9.16 g (0.066 mol) of potassium and 15.00 g of benzonitrile were charged and reacted at 80 ° C. for 10 hours to obtain a reaction solution containing a desired phthalonitrile compound. After cooling, the solution obtained by suction filtration was concentrated to prepare a phthalonitrile compound concentration of 30 wt%.

  The obtained reaction solution, 1.79 g (0.0056 mol) of zinc iodide, was added to a 100 ml four-necked separable flask, and reacted at 160 ° C. for 20 hours under nitrogen flow (10 ml / min). After cooling, the completely same operation as Example 1 was performed, and the target object 7.68g (yield 64.2 mol% with respect to tetrafluoro phthalonitrile) was obtained.

Example 9 [VOPc- {α- (4-COOCH ₃ C ₆ H ₄ O) _x (2,6- (CH ₃ ) ₂ C ₆ H ₃ O) _y }, {β- (4-COOCH _{3 C 6 H 3 O) 4-} x (2,6- (CH 3) 2 C 6 H 3 O) 4-y} F 8] ( four in 0 ≦ x <4,0 ≦ y synthesis 200ml of <4) In a one-necked separable flask, 6.00 g (0.031 mol) of tetrafluorophthalonitrile, 4.56 g (0.030 mol) of methyl 4-hydroxybenzoate, 3.81 g (0.030 mol) of 2,6-dimethylphenol. Mol), 9.12 g (0.066 mol) of potassium carbonate, and 21.50 g of benzonitrile were allowed to react at 80 ° C. for 10 hours to obtain a reaction solution containing the desired phthalonitrile compound. After cooling, the solution obtained by suction filtration was concentrated to prepare a phthalonitrile compound concentration of 30 wt%.

  To a 100 ml four-necked separable flask, 1.53 g (0.010 mol) of vanadium chloride and 1.27 g (0.010 mol) of octanol were added, and nitrogen gas was supplied to the liquid phase part at 170 ° C. And stirred for 20 hours. After cooling, the completely same operation as Example 1 was performed, and 10.23 g (yield 75.6 mol% with respect to tetrafluoro phthalonitrile) of target objects was obtained.

Example 10 [VOPc- {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)} _{10- x Cl 6] (0 ≦ x} <10) in a four-neck separable flask synthesis 200ml of tetrachloro phthalonitrile 5.43 g (0.020 mol) and 4-hydroxybenzoic acid methoxyethyl 9.91 g (0. 050 mol), 7.6 g (0.055 mol) of potassium carbonate, and 15.81 g of benzonitrile were reacted at 80 ° C. for 10 hours to obtain a reaction solution containing a desired phthalonitrile compound. After cooling, the solution obtained by suction filtration was concentrated to prepare a phthalonitrile compound concentration of 30 wt%.

  To a 100 ml four-necked separable flask, 0.79 g (0.0050 mol) of vanadium chloride and 0.64 g (0.050 mol) of octanol were added, and nitrogen gas was supplied to the liquid phase part at 170 ° C. And stirred for 20 hours. After cooling, the completely same operation as Example 1 was performed, and the target object 3.4g (yield 23.6 mol% with respect to tetrachlorophthalonitrile) was obtained.

(Example 11) [CuPc- {α- (2-COOCH ₃ C ₆ H ₄ O)} _x , {β- (2-COOCH ₃ C ₆ H ₄ O) _10-x F ₆ ] (0 ≦ x < 10) Synthesis In a 100 ml four-necked separable flask, tetrafluoronitrile 4.00 g (0.020 mol), methyl salicylate 7.68 g (0.050 mol), potassium carbonate 8.29 g (0.060 mol) Then, 16.01 g of acetonitrile was charged and reacted at 80 ° C. for 10 hours to obtain a reaction solution containing a desired phthalonitrile compound. After cooling, the solution obtained by suction filtration was distilled off the aceto solvent under reduced pressure, and 21.70 g of diethylene glycol monomethyl ether was added.

  To a 100 ml four-necked separable flask, 0.55 g (0.0055 g) of the obtained reaction solution and copper (II) chloride was added, and the mixture was reacted at 180 ° C. for 5 hours under nitrogen flow (10 ml / min). After cooling, the completely same operation as Example 1 was performed, and 5.56g (yield with respect to tetrafluoro phthalonitrile: 57.8 mol%) of target objects was obtained.

(Example 12) [ZnPc- {α- (4-NO ₂ C ₆ H ₄ O)} _x , {β- (4-NO ₂ C ₆ H ₄ O)} _10-x Cl ₆ ] (0 ≦ x <10) Synthesis In a 200 ml four-necked separable flask, tetrachloronitrile 7.96 g (0.030 mol), 4-nitrophenol 10.54 g (0.075 mol), potassium carbonate 12.5 g (0. 09 mol) and 20.05 g of benzonitrile were charged and reacted at 80 ° C. for 10 hours to obtain a reaction solution containing the desired phthalonitrile compound. After cooling, the solution obtained by suction filtration was concentrated to prepare a phthalonitrile compound concentration of 30 wt%.

  The obtained reaction solution, 2.49 g (0.0078 mol) of zinc iodide, was added to a 100 ml four-necked separable flask, and reacted at 160 ° C. for 20 hours under nitrogen flow (10 ml / min). After cooling, the completely same operation as Example 1 was performed, and 13.51 g (yield 84.4 mol% with respect to tetrachloro phthalonitrile) of target objects was obtained.

(Example _{13) [VOPc- {α- (2} -C 10 H 7 O)} x, {β- (2-C 10 H 7 O)} 8-x Cl 8] of (0 ≦ x <8) Synthesis In a 200 ml four-necked separable flask, tetrachlorophthalonitrile 10.08 g (0.038 mol) and 2-naphthol 10.85 g (0.075 mol), potassium carbonate 11.43 g (0.083 mol), 40.00 g of benzonitrile was charged and reacted at 80 ° C. for 10 hours to obtain a reaction solution containing a desired phthalonitrile compound. After cooling, the solution obtained by suction filtration was concentrated to prepare a phthalonitrile compound concentration of 30 wt%.

  To the 100 ml four-necked separable flask, 2.22 g (0.014 mol) of vanadium chloride and 1.84 g (0.014 mol) of octanol were added, and nitrogen gas was supplied at 170 ° C. And stirred for 20 hours. After cooling, the completely same operation as Example 1 was performed, and 15.63 g (yield 90.6 mol% with respect to tetrachlorophthalonitrile) of a target object was obtained.

(Example 14) [VOPc- {α- (4-CNC ₆ H ₄ O) _x (2-CH ₃ OC ₆ H ₄ O) _y }, {β- (4-CNC ₆ H ₄ O) _4-x to _{(2-CH 3 OC 6 H} 4 O) 8-y} Cl 4] (0 ≦ x <4,0 ≦ y <8) four-necked separable flask synthesis 200ml of tetrachloro phthalonitrile 7.98g (0.031 mol), 3.72 g (0.030 mol) of 4-cyanophenol, 7.74 g (0.060 mol) of 2-methoxyphenol, 13.68 g (0.099 mol) of potassium carbonate, benzonitrile 21 .50 g was charged and reacted at 80 ° C. for 10 hours to obtain a reaction solution containing a desired phthalonitrile compound. After cooling, the solution obtained by suction filtration was concentrated to prepare a phthalonitrile compound concentration of 30 wt%.

  To a 100 ml four-necked separable flask, 1.53 g (0.010 mol) of vanadium chloride and 1.27 g (0.010 mol) of octanol were added, and nitrogen gas was supplied to the liquid phase part at 170 ° C. And stirred for 20 hours. After cooling, the completely same operation as Example 1 was performed, and the target object 12.90g (yield 91.3 mol% with respect to tetrachlorophthalonitrile) was obtained.

(Example 15) [ZnPc- {α- (2-PhC ₆ H ₄ O)} _x , {β- (2-PhC ₆ H ₄ O)} _10-x F ₆ ] (0 ≦ x <10) Synthesis In a four-necked separable flask in 200 ml, tetrafluoronitrile 6.00 g (0.030 mol), 2-phenylphenol 12.89 g (0.075 mol), potassium carbonate 10.34 g (0.083 mol), 25.76 g of benzonitrile was charged and reacted at 80 ° C. for 10 hours to obtain a reaction solution containing a desired phthalonitrile compound. After cooling, the solution obtained by suction filtration was concentrated to prepare a phthalonitrile compound concentration of 30 wt%.

  The obtained reaction solution, 2.40 g (0.0075 mol) of zinc iodide, was added to a 100 ml four-necked separable flask and reacted at 160 ° C. for 20 hours under nitrogen flow (10 ml / min). After cooling, the completely same operation as Example 1 was performed, and 13.24 g (yield 82.9 mol% with respect to tetrafluoro phthalonitrile) of target objects was obtained.

(Example _{16) [ZnPc- {α- (4} -CONHC 2 H 4 OCH 3 C 6 H 4 O)} x, {β- (4-CONHC 2 H 4 OCH 3 C 6 H 4 O)} 10- _x F _6] in a four-neck separable flask synthesis 200ml of (0 ≦ x <10), tetrachloro nitrile 7.98 g (0.030 mol) and 4-hydroxy-N-(2-methoxyethyl benzamide) 14 .79 g (0.075 mol), potassium carbonate 10.74 g (0.083 mol), and benzonitrile 25.76 g were charged and reacted at 80 ° C. for 10 hours to obtain a reaction solution containing a desired phthalonitrile compound. After cooling, the solution obtained by suction filtration was concentrated to prepare a phthalonitrile compound concentration of 30 wt%.

  The obtained reaction solution, 2.40 g (0.0075 mol) of zinc iodide, was added to a 100 ml four-necked separable flask and reacted at 160 ° C. for 20 hours under nitrogen flow (10 ml / min). After cooling, the completely same operation as Example 1 was performed, and the target object 13.84g (yield of 86.6 mol% with respect to tetrafluoro phthalonitrile) was obtained.

(Example _{17) [VOPc- {α- (4} -SO 2 NH 2 C 6 H 4 O) x, {β- (4-SO 2 NH 2 C 6 H 4 O) 10-x} Cl 6] ( Synthesis of 0 ≦ x <10) In a four-necked separable flask in 200 ml, tetrachlorophthalonitrile 7.98 g (0.030 mol), 4-hydroxybenzenesulfonamide 10.50 g (0.060 mol), potassium carbonate 9.12 g (0.066 mol) and benzonitrile 25.38 g were charged and reacted at 80 ° C. for 10 hours to obtain a reaction solution containing a desired phthalonitrile compound. After cooling, the solution obtained by suction filtration was concentrated to prepare a phthalonitrile compound concentration of 30 wt%.

  To a 100 ml four-necked separable flask, 1.53 g (0.010 mol) of vanadium chloride and 1.27 g (0.010 mol) of octanol were added, and nitrogen gas was supplied to the liquid phase part at 170 ° C. And stirred for 20 hours. After cooling, the completely same operation as Example 1 was performed, and 15.35 g (yield 92.0 mol% with respect to tetrachlorophthalonitrile) of a target object was obtained.

(Comparative Example _{1) [VOPc- {α- (2,5} -Cl 2 C 6 H 3 O)} x, {β- (2,5-Cl 2 C 6 H 3 O)} 4-x Cl 4] Synthesis of (0 ≦ x <4) In a four-necked separable flask in 200 ml, tetrachlorophthalonitrile 7.98 g (0.030 mol), 2,5-dichlorophenol 7.41 g (0.045 mol), carbonic acid 6.84 g (0.050 mol) of potassium and 25.58 g of benzonitrile were charged and reacted at 80 ° C. for 10 hours to obtain a reaction solution containing a desired phthalonitrile compound. After cooling, the solution obtained by suction filtration was concentrated to prepare a phthalonitrile compound concentration of 30 wt%.

  To a 100 ml four-necked separable flask, 1.53 g (0.010 mol) of vanadium chloride and 1.27 g (0.010 mol) of octanol were added, and nitrogen gas was supplied to the liquid phase part at 170 ° C. And stirred for 20 hours. After cooling, the completely same operation as Example 1 was performed, and the target object 12.45g (yield 87.9 mol% with respect to tetrachlorophthalonitrile) was obtained.

[Evaluation]
(Spectral characteristic measurement in acrylic resin)
The spectral characteristics of the phthalocyanine compounds obtained in Examples 1 to 17 and the comparative examples were evaluated according to the following methods.

  0.100 g of each phthalocyanine compound, 1.48 g of acrylic binder polymer and 2.58 g of propylene glycol monomethyl ether acetate (hereinafter abbreviated as PGMEA), 0.350 g of dipentaerythritol hexaacrylate, IRGACURE 369 (Ciba Specialty Chemicals Co., Ltd.) (Made by company) 0.024g is added, and it melt | dissolves and mixes and prepares a resin coating liquid. The obtained resin coating liquid was applied to a glass plate with a spin coater so that the film thickness after drying was 3 μm, and dried at 100 ° C. for 20 minutes. The absorption spectrum of the coating glass plate thus obtained was measured with a spectrophotometer (manufactured by Shimadzu Corporation: UV-1800), and this was used as the spectrum before heating. Next, the coated glass plate whose spectrum before heating was measured was heat-treated at 230 ° C. for 20 minutes. The absorption spectrum of the obtained coating (film thickness after drying: 3 μm) glass plate was measured with a spectrophotometer, and this was used as the spectrum after heating.

The absorbance from 380 nm to 900 nm in each spectrum before and after heating measured in this way was integrated, and the difference between the absorbance before and after heating was measured. Further, ΔE was calculated by the following equation, where E _{1 was} the spectrum before heating, E _{2 was} the spectrum after heating, and ΔE was the difference in measured absorbance.

  In addition, each transmittance at 550 nm, 700 nm, and λmax when each spectrum after heating was normalized so that the transmittance at 650 nm was 50% was calculated. The results are shown in Tables 1 and 2 below.

  From the results of Tables 1 and 2, the phthalocyanine compound of the example has a significantly lower transmittance of near-infrared light at 700 nm and the maximum absorption wavelength (λmax) than the phthalocyanine compound of Comparative Example 1 (in terms of blocking properties). Excellent). Moreover, it turns out that the phthalocyanine compound of an Example has a high visible light transmittance | permeability.

[Phthalocyanine compound (B)]
[Synthesis Example 1] Synthesis of 3- (2,6-dichlorophenoxy) phthalonitrile In a 500 ml four-necked separable flask, 15.0 g (0.087 mol) of 3-nitrophthalonitrile, 2,6-dimethylphenol 11 .2 g (0.091 mol), potassium carbonate 23.9 g (0.17 mol), and acetonitrile 60.0 g were charged and stirred at 60 ° C. overnight. The reaction solution was filtered, acetone was distilled off from the filtrate with a rotary evaporator, and methanol was added for recrystallization. The obtained crystals were filtered and dried under vacuum to obtain 17.5 g of 3- (2,6-diphenoxymethyl) phthalonitrile (yield 69.9% based on 3-nitrophthalonitrile).

Synthesis Example 2 Synthesis of 3- (2-chlorophenoxy) phthalonitrile Into a 500 ml four-necked separable flask, 17.3 g (0.10 mol) of 3-nitrophthalonitrile and 13.6 g of 2-chlorophenol (0 .105 mol), 16.6 g (0.12 mol) of potassium carbonate, and 69.3 g of acetonitrile were charged and stirred at 60 ° C. overnight. The reaction solution was filtered, acetone was distilled off from the filtrate with a rotary evaporator, and methanol was added for recrystallization. The obtained crystals were filtered and vacuum-dried to obtain 27.8 / g of 3- (2-chlorophenoxy) phthalonitrile (yield 91.7% based on 3-nitrophthalonitrile).

Reference Example 1 Synthesis of [CuPc- {α- (2,6-Cl ₂ PhO) ₄ H ₄ } {β-H ₈ }] 3 obtained in Synthesis Example 1 above in a 200 ml four-necked flask -(2,6-dichlorophenoxy) phthalonitrile 4.00 g (0.0144 mol), copper (I) chloride 0.38 g (0.0038 mol), diethylene glycol monomethyl ether 9.33 g, charged with stirring at 180 ° C 10 Reacted for hours. After completion of the reaction, the completely same operation as Example 1 was performed, and 3.22 g of target products were obtained (yield 76.3% based on 3- (2,6-dichlorophenoxy) phthalonitrile).

Reference Example 2 Synthesis of [ZnPc- {α- (2,6-Cl ₂ PhO) ₄ H ₄ } {β-H ₈ }] 3 obtained in Synthesis Example 1 above in a 200 ml four-necked flask -(2,6-dichlorophenoxy) phthalonitrile 2.3 g (0.0080 mol), zinc iodide (II) 0.70 g (0.0022 mol), and benzonitrile 13.1 g were charged and stirred at 160 ° C. for 24 hours. Reacted for hours. After completion of the reaction, the completely same operation as in Example 1 was performed to obtain 0.80 g of the desired product (yield 32.8% based on 3- (2,6-dichlorophenoxy) phthalonitrile).

[Reference Example 3] Synthesis of [ZnPc- {α- (2-ClPhO) ₄ H ₄ } {β-H ₈ }] 3- (2-chloro) obtained in Synthesis Example 2 in a 200 ml four-necked flask Phenoxy) phthalonitrile (10.19 g, 0.040 mol), zinc iodide (II), 3.51 g (0.011 mol), and benzonitrile (23.8 g) were charged and reacted at 160 ° C. with stirring for 24 hours. After completion of the reaction, the completely same operation as Example 1 was performed, and 2.74g of target objects were obtained (yield 25.3% with respect to 3- (2-chlorophenoxy) phthalonitrile).

[Evaluation]
About the phthalocyanine compound (B) obtained by the said reference examples 1-3, it carried out similarly to the evaluation method of phthalocyanine (A), measured the spectral characteristic in an acrylic resin, and the result is shown in following Table 3.

Examples 18-21
(Spectral characteristic measurement in acrylic resin by mixing two kinds of pigments)
Dye A (phthalocyanine compound (A)) and Dye B (phthalocyanine compound (B)) listed in Table 4 below are weighed out so that the total amount is 0.100 g in a weight ratio described in Table 4, and an acrylic binder 1.48 g of polymer (manufactured by Nippon Shokubai Co., Ltd.) and 2.58 g of propylene glycol monomethyl ether acetate (hereinafter abbreviated as PGMEA), 0.350 g of dipentaerythritol hexaacrylate, manufactured by Ciba Specialty Chemicals Co., Ltd. ( IRGACURE369) 0.024g was added, and it melt | dissolved and mixed and prepared the resin coating liquid. The obtained resin coating liquid was applied to a glass plate with a spin coater, dried at 100 ° C. for 20 minutes, and further heat-treated at 230 ° C. for 20 minutes. The absorption spectrum of the resulting coated glass plate was measured with a spectrophotometer (manufactured by Shimadzu Corporation: UV-1800), and the results are shown in Table 4 below.

  From the above results, it is understood that the transmittance at 700 nm is low by combining the phthalocyanine compound (A) and the phthalocyanine compound (B).

1 lens,
2 barrels,
3 Infrared cut filter,
4 holders,
5 Cover glass,
6 Sensor.

Claims (2)

Following formula (1):
In the above formula (1), Z _{1 to} Z ₁₆ are each independently a fluorine atom, a chlorine atom, a bromine atom, the following formula (2):
In the above formula (2), R ¹ is an alkylene group having 1 to 3 carbon atoms, R ² is an alkyl group having 1 to 8 carbon atoms, and R ⁴ is an alkoxy group having 1 to 8 carbon atoms or A halogen atom, m is an integer of 1 to 4, p is an integer of 0 to 4, and n is an integer of 1 to 3.
A substituent represented by (a-1),
In the above formula (2), R ¹ is an alkylene group having 1 to 3 carbon atoms, R ² is an alkyl group having 1 to 8 carbon atoms, and R ⁴ is an alkoxy group having 1 to 8 carbon atoms or A halogen atom, m is an integer of 1 to 4, p is an integer of 0 to 4, and n is 0.
A substituent (a-2) represented by the following formula (3):
In the formula (3), ^{R 4} and p are the same as defined in the above formula (2), ^{R 3} is a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, or the formula :-( ^R 1 O,) _m R ² , wherein R ¹ , R ² and m have the same definition as in the above formula (2).
Substituent (b) represented by the following formula (4):
In the above formula (5), R ⁴ and p have the same definition as in the above formula (2), and R ³ has the same definition as in the above formula (3).
Substituent (c) represented by the following formula (5):
In the above formula (5), X is an oxygen atom or a sulfur atom, Ar is a phenyl group or a naphthyl group which may be substituted with R ⁵ , and in this case, R ⁵ is each independently cyano. A group, a nitro group, COOY, OY, a halogen atom, an aryl group, or an alkyl group having 1 to 8 carbon atoms which may be substituted with a halogen atom, wherein Y is an alkyl group having 1 to 12 carbon atoms Is,
A substituent (d) represented by the following formula (6):
In the above formula (6), X is an oxygen atom or a sulfur atom, R ⁷ is an alkylene group having 1 to 5 carbon atoms, and R ⁶ is substituted with a halogen atom or an alkoxy group having 1 to 8 carbon atoms. Is an optionally substituted alkyl group having 1 to 8 carbon atoms,
A substituent (e) represented by the following formula (7):
In the above formula (7), X is an oxygen atom or a sulfur atom, ^{R 7} is an alkylene group having 1 to 5 carbon atoms, ^{R 8} are each independently an alkoxy group having 1 to 8 carbon atoms Or an alkyl group having 1 to 8 carbon atoms,
A group represented by (f), a group derived from 7-hydroxycoumarin (g), or a group derived from 2,3-dihydroxyquinoxane (h),
At this time, among Z _{1 to} Z ₁₆ , 6 to 12 are any of the substituents (a-1) and (b) to (h), or more than 8 and 12 or less are substituents (a -2) and the balance is a chlorine atom or a bromine atom,
M represents metal-free, metal, metal oxide or metal halide,
A phthalocyanine compound represented by   An infrared cut filter comprising the phthalocyanine compound according to claim 1.