JP7288812B2 - Phthalocyanine-based compound, heat-absorbing material containing the same, and method for producing phthalocyanine-based compound - Google Patents

Description

TECHNICAL FIELD The present invention relates to a phthalocyanine-based compound, a heat-absorbing material containing the same, and a method for producing a phthalocyanine-based compound.

BACKGROUND ART For the purpose of shielding heat rays from solar energy, heat-shielding films, heat-shielding resin glasses, heat-reflecting glasses, and the like are used in windows of buildings and vehicles. In general, the spectrum of sunlight is widely distributed in the ultraviolet-visible-infrared region, and in order to sufficiently obtain the above heat ray shielding effect, it is necessary to selectively absorb heat rays with wavelengths in the range of 670 nm or more. is necessary. In addition, in applications such as buildings and vehicles, good visibility is also required, so it is necessary to ensure sufficient transparency (visible light transmittance) while maintaining heat ray shielding performance.

Conventionally, as a heat ray absorbing/shielding glass, a plate glass coated with a metal oxide film having a high reflectance is known. This heat-absorbing/shielding glass is obtained by adding a small amount of metal such as iron, nickel, cobalt, etc. to an ordinary glass raw material to color it, thereby imparting selective transmission of light depending on the wavelength. However, none of the metal oxides used as conventional heat-absorbing/shielding materials can selectively absorb the near-infrared region in the range of 670 to 850 nm. need to increase the amount added. However, in such a case, the transparency of the glass may be lowered, and it is not preferable in terms of cost. In addition, since the technology for uniformly coating the surface of a large-area thin film layer using a metal oxide has not yet been fully developed, conventional metal oxide coating (coating) methods cannot be applied to large-area objects. It was difficult to form a uniform coated surface on the surface of the

On the other hand, various near-infrared absorbing dyes that selectively absorb light in a specific wavelength range have been developed. In particular, phthalocyanine compounds have high visible light transmittance, high near-infrared absorption efficiency, excellent selective absorption in the near-infrared region, excellent solvent solubility, and excellent compatibility with resins. It also has excellent properties such as heat resistance, light resistance, and weather resistance. For example, Patent Document 1 discloses a naphthalocyanine compound obtained by introducing a substituted or unsubstituted phenoxy group into a naphthalocyanine compound having a naphthalene skeleton on one of the four sides of the basic skeleton, and using the naphthalocyanine compound as a heat-absorbing material. is disclosed.

JP 2014-122205 A

However, in order to further improve the functionality of heat-absorbing materials, there is a demand for heat-absorbing materials that are excellent in durability (light resistance) while maintaining good heat-absorbing ability. In addition to these properties, good transparency in the visible light region is also required.

Accordingly, an object of the present invention is to provide a phthalocyanine compound having good heat ray absorption ability and visible light transmittance and excellent light resistance.

In order to solve the above problems, as a result of extensive research, the present inventors have found that a multimer (dimer or trimer or higher multimer) in which the phthalocyanine skeleton is linked in a specific form, , found that a phthalocyanine compound having a maximum absorption wavelength of 700 nm or more not only has good heat ray absorption ability and visible light transmittance, but also has excellent light resistance, and completed the present invention based on the above findings. . Therefore, the heat-absorbing material containing the phthalocyanine-based compound has good heat-absorbing ability and visible light transmittance (transparency), and also has excellent light resistance.

That is, the above object is a phthalocyanine compound in which two or three or more phthalocyanine skeletons are linked via an oxygen atom by a divalent or trivalent organic group, wherein the oxygen atom is the phthalocyanine It is achieved by a phthalocyanine-based compound that is bonded to a carbon atom that constitutes the skeleton and has a maximum absorption wavelength of 700 nm or more.

The phthalocyanine compound according to the present invention has good heat ray absorption ability and visible light transmittance, and is excellent in light resistance.

Embodiments of the present invention will be described below. In addition, although the constituent elements, embodiments, and the like of the present invention will be described in detail below, these are examples of embodiments of the present invention, and the present invention is not limited to these contents. In the present specification, the range "X to Y" includes X and Y and means "X or more and Y or less". In this specification, unless otherwise specified, operations and measurements of physical properties are performed under the conditions of room temperature (20 to 25° C.)/relative humidity of 40 to 50% RH.

One form of the present invention is a phthalocyanine compound in which two or three or more, that is, two or more phthalocyanine skeletons are linked via an oxygen atom by a divalent or trivalent organic group, The oxygen atom relates to a phthalocyanine-based compound having a maximum absorption wavelength of 700 nm or more, wherein the oxygen atom is bonded to a carbon atom constituting the phthalocyanine skeleton. In the present specification, the phthalocyanine-based compound is also simply referred to as "phthalocyanine-based compound" or "phthalocyanine-based compound according to the present invention".

A phthalocyanine compound according to one aspect of the present invention satisfies the following (i) and (ii);
(i) 2 or 3 or more, that is, 2 or more phthalocyanine skeletons are linked via an oxygen atom by a divalent or trivalent organic group, and the oxygen atom is a phthalocyanine skeleton is attached to the carbon atoms that make up the
(ii) having a maximum absorption wavelength of 700 nm or longer;

It has been found that the phthalocyanine compounds satisfying the above (i) and (ii) exhibit excellent light resistance in addition to having good heat ray absorption and visible light transmittance. In addition, the phthalocyanine-based compound according to the present invention has a very high visible light transmittance even when mixed with a resin, as compared with the phthalocyanine-based compound according to the prior art. That is, even when mixed with a resin, it has high transparency. Further, the phthalocyanine compounds satisfying the above (i) and (ii) are excellent in heat resistance, and yellowing after light irradiation is also suppressed.

Although the reason why the phthalocyanine-based compound according to the present invention exhibits high light resistance without deteriorating good heat absorption ability and visible light transmittance as described above is unknown, it is presumed as follows. In addition, the present invention is not limited to the following estimation.

In general, the light resistance of molecular compounds having planarity tends to be improved when the compounds are laminated while maintaining their planarity. Here, as shown in (i) above, the phthalocyanine compound according to the present invention is a phthalocyanine skeleton multimer (e.g., dimer isomers and trimers or higher). Thus, it is presumed that the multimer linked in a specific form has a highly planar molecular structure in which each phthalocyanine skeleton is aligned in one plane (within the same plane) in one molecule. be. Therefore, in the phthalocyanine-based compound according to the present invention, the phthalocyanine skeletons in the multimer (e.g., dimer and trimer or higher) are aligned in one plane (in the same plane), It is presumed that high light resistance can be exhibited because each molecule is easily laminated while maintaining high planarity.

On the other hand, a phthalocyanine compound with high planarity and extended conjugation has a broadened absorption spectrum (absorption band). That is, the width of the absorption spectrum (absorption band) is widened. As a result, the absorption extends to the visible light region, which may reduce the visible light transmittance. However, the phthalocyanine compound according to the present invention has a structure in which two or three or more (that is, two or more) phthalocyanine skeletons are linked via an appropriate linker. Broadening of (absorption band) can be moderately suppressed. Therefore, the phthalocyanine compound according to the present invention is considered to have good visible light transmittance.

In addition, the phthalocyanine compound according to the present invention has a maximum absorption wavelength of 700 nm or longer, as shown in (ii) above. Therefore, the phthalocyanine compound according to the present invention has a high absorption in the wavelength region (670 to 850 nm) that greatly contributes to the heat absorption ability of sunlight, so that good heat absorption ability can be obtained.

[Phthalocyanine compound]
In the phthalocyanine compound according to the present invention, as described in (i) above, two or three or more phthalocyanine skeletons, that is, two or more phthalocyanine skeletons are linked via an oxygen atom by a divalent or trivalent organic group. has a structure At this time, the oxygen atoms are bonded to the carbon atoms forming the phthalocyanine skeleton.

As used herein, the term "phthalocyanine skeleton" refers to a structure having a structure represented by the following formula as a nucleus:

The phthalocyanine skeleton includes, in addition to the metal-free phthalocyanines described above, phthalocyanines having metals, metal oxides, metal halides, and the like as the center.

Further, the term "phthalocyanine-based compound" means, in addition to a phthalocyanine compound, a naphthalocyanine compound in which a part of the phthalocyanine skeleton represented by the above formula is replaced with a naphthalocyanine skeleton, and the following structure (b') adjacent to the phthalocyanine skeleton. Also included are phthalocyanine compounds that are introduced at two sites.

In the phthalocyanine compound, as shown in (i) above, the divalent or trivalent organic group has two or more (for example, two or three or more) phthalocyanine skeletons via oxygen atoms. Link. As used herein, the term "organic group" refers to a group containing carbon atoms. Although the number of carbon atoms contained in the organic group is not particularly limited, it is preferably 1-50, more preferably 3-30. When such an organic group connects the phthalocyanine skeleton via oxygen, the molecules are easily laminated with each other in a state of high planarity, and the light resistance is improved. In addition, it is preferable because the maximum absorption wavelength (λmax) suitable for heat ray absorption can be easily obtained.

Also, in this specification, a divalent or trivalent organic group and an oxygen atom may be collectively referred to as a "linker" or "linking group." The linker has oxygen atoms at both ends (in the case of a divalent organic group) or three ends (in the case of a trivalent organic group), and the oxygen atoms are respectively bonded to the carbon atoms constituting the phthalocyanine skeleton. do. With such a structure, the phthalocyanine compound according to the present invention can easily form a state in which each molecule is laminated while maintaining high planarity, and can exhibit high light resistance.

Further, as shown in (ii) above, the phthalocyanine compound according to the present invention has a maximum absorption wavelength (λmax) of 700 nm or more. In the present specification, the "maximum absorption wavelength" means the maximum absorption wavelength in the visible light region to the near infrared region (360 to 850 nm, particularly 400 to 850 nm wavelength region), described in the examples below. A value measured by the method of That is, the value obtained by the following method is adopted as the maximum absorption wavelength. First, it is mixed with a polyvinyl butyral resin such that the content of the phthalocyanine compound is 1.6% by weight (relative to the total amount of the phthalocyanine compound and the resin). Next, tetrahydrofuran as a solvent is added to the above mixture so that the solid content concentration becomes 20% by weight, and dissolved to obtain a coating solution. The resulting coating solution is then applied to glass using a #60 bar coater and allowed to dry at room temperature. After that, it is further dried at 100° C. for 10 minutes to form a phthalocyanine-based compound-containing butyral coating film. The absorbance of the coating film is measured using a spectrophotometer to determine the maximum absorption wavelength (λmax). As the spectrophotometer, for example, "U-2910" manufactured by Hitachi High-Technologies Corporation can be used.

More specifically, the maximum absorption wavelength (λmax) of the phthalocyanine compound according to the present invention exists in a long wavelength region of 700 nm or more, preferably 720 to 850 nm, more preferably 725 to 840 nm, and even more preferably 735 nm. ~830 nm, particularly preferably in the wavelength range from 740 nm to 800 nm. Therefore, since the maximum absorption wavelength exists in such a range, the phthalocyanine compound according to the present invention has good heat ray absorption ability. Therefore, the heat ray absorbing material containing the phthalocyanine compound according to the present invention preferably absorbs light in the wavelength range of 720 to 850 nm, more preferably 725 to 840 nm, still more preferably 735 to 830 nm, and particularly preferably 740 to 800 nm. It can selectively absorb, for example, heat-absorbing laminated glass (laminated glass heat-shielding interlayer), heat-shielding film, heat-shielding resin glass, such as windows of vehicles (e.g., automobiles, buses, trains, etc.) and buildings. When used in heat-reflecting glass, it can effectively suppress the temperature rise inside a vehicle or room.

In addition, the phthalocyanine-based compound according to the present invention has a high transmittance in the visible light range from 400 to 650 nm, particularly around 510 nm. As described above, the phthalocyanine compound according to the present invention is particularly excellent in transmittance of green light around 510 nm, which is highly visible to the human eye. is obtained. As a more specific example, the phthalocyanine compound according to the present invention particularly easily transmits light with a wavelength of around 510 nm (blue light to green light), so the visibility of an LED lamp that emits blue light to green light is improved. can be improved. Therefore, for example, since the visibility of headlights and outdoor lights using LEDs is improved, the phthalocyanine compound according to the present invention can be suitably used as an intermediate film for vehicle windshields (heat-absorbing laminated glass).

From the viewpoint of having good heat ray absorption ability and visible light transmittance and excellent light resistance, the phthalocyanine compound according to the present invention is represented by the following formula (1) or the following formula (2) or the following formula (3) It is preferred that the compound is:

In the above formulas (1), (2) and (3),
A ₁ to A ₁₆ each independently bind to any of the binding sites represented by *, and the remainder each independently represent a hydrogen atom,
Each R ₁ is independently a halogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, an ester group having 2 to 21 carbon atoms (-C(=O) OR ₂ R ₂ represents an alkyl group having 1 to 20 carbon atoms), or —R ₃ —C(=O)OR ₄ (R ₃ is an alkylene group having 1 to 20 carbon atoms, R ₄ is represents an alkyl group having 1 to 20 carbon atoms),
p is each independently an integer of 0 to 5,
m is each independently an integer of 1 to 15,
m' is each independently an integer of 1 to 14,
each X independently represents a halogen atom,
n is each independently an integer of 0 to 4,
k is each independently an integer of 0 to 3,
each q is independently an integer of 0 to 3;
each o is independently an integer of 0 to 6;
a1 is 1 to 6;
each M is independently a metal, metal oxide or metal halide;
Y is an organic group which may have a divalent or trivalent oxygen atom,
The following formula (b) or (b'):

The binding sites represented by * in structure (b) or (b') represented by are A ₁ to A ₄ , A ₅ to A 8 , A ₉ to A 12 , A ₉ to A ₁₂ , Bond as two adjacent substituents of A ₁₃ to A ₁₆ .

That is, preferred forms of the phthalocyanine compound according to the present invention include the dimer represented by the above formula (1), the trimer represented by the above formula (2), and the above formula (3). It is multimeric.

In the present specification, the substituents of A ₁ , A ₄ , A ₅ , A ₈ , A ₉ , A ₁₂ , A ₁₃ and A ₁₆ in the above formulas (1) to (3) are simply “α-position A ₁ , A ₄ , A ₅ , A ₈ , A ₉ , A ₁₂ , A ₁₃ and A ₁₆ are also collectively referred to as the “α-position”. Similarly, in the above formulas (1) to (3), the substituents of A ₂ , A ₃ , A ₆ , A ₇ , A ₁₀ , A ₁₁ , A ₁₄ and A ₁₅ are simply replaced by “β-position substitution A ₂ , A ₃ , A ₆ , A ₇ , A ₁₀ , A ₁₁ , A ₁₄ and A ₁₅ are also collectively referred to as the “β-position”.

In the above formulas (1) to (3), A ₁ to A ₁₆ are each independently any of the binding sites represented by "*" on each substituent, each structure, each halogen atom or linker. or represents a hydrogen atom. That is, A ₁ to A ₁₆ each independently bind to any of the binding sites represented by "*" on each substituent, each structure, each halogen atom or linker, and the remaining A ₁ to A ₁₆ represents a hydrogen atom. wherein each substituent, each structure, each halogen atom and a linker (Y(O) ₂ —((Y(—O—) ₂ or —O—Y—O—) or Y(O) ₃ —(Y( The binding site (ie, A ₁ to A ₁₆ ) on the phthalocyanine skeleton to which —O—) ₃ ))) binds and the position of the hydrogen atom may be the same or different in each phthalocyanine skeleton. For example, in formula (2), when one end of the linker is bound to _A1 of one phthalocyanine skeleton, the other end of the linker may be bound to _A1 of the other phthalocyanine skeleton, or other It may bind to the binding site (ie, any one of A ₂ to A ₁₆ ).

Further, in a plurality of phthalocyanine skeletons contained in one molecule, the substituted substituents, structures, types of halogen atoms and the number of these may be the same or different. For example, in the dimer represented by formula (1), substituents (a) represented by the following formula (a) are added to A ₁ , A ₅ , A ₉ and A ₁₃ on one phthalocyanine skeleton. While each is substituted, the substituent (a) substituted on the other phthalocyanine skeleton may be substituted with A ₂ , A ₆ , A ₁₀ and A ₁₄ . Furthermore, R ₁ and p substituted on these substituents (a) may be the same or different. However, considering the ease of synthesis, suppressing broadening of the absorption spectrum (absorption band), and obtaining good visible light transmittance, substituents substituted on multiple phthalocyanine skeletons, each structure, each halogen The types of atoms and their numbers are preferably identical to each other.

Any one of A ₁ to A ₁₆ on one phthalocyanine skeleton is attached to a linker (Y(--O--) ₂ or Y(--O--) ₃ ). Binds to any of the binding sites. The remaining A ₁ to A ₁₆ are, respectively, a substituent (a) represented by the following formula (a), a binding site of the structure (b) represented by the following formula (b), and the following formula (b′). The binding site of structure (b′) where is bound to any one of the halogen atom and hydrogen atom represented by “X”:

In the above formula (a),
Each R ₁ is independently a halogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, an ester group having 2 to 21 carbon atoms (-C(=O) OR ₂ R ₂ represents an alkyl group having 1 to 20 carbon atoms), or —R ₃ —C(=O)OR ₄ (R ₃ is an alkylene group having 1 to 20 carbon atoms, R ₄ is represents an alkyl group having 1 to 20 carbon atoms),
p is an integer from 0 to 5;

In the above _formulas ( _{b ) and} ( _{b '} ), * _{represents the} It represents a site that binds as two adjacent substituents. In this specification, the substituent having structure (b) represented by formula (b) above is also referred to as "substituent (b)." Similarly, the substituent having the structure (b') represented by the formula (b') is also referred to as "substituent (b')".

Hereinafter, the substituent (a), the structure (b), the structure (b'), the halogen atom represented by "X", the linker and the central metal represented by "M" to be substituted on the phthalocyanine skeleton will be described respectively. .

(substituent (a))
The substituent (a) in the above formulas (1) to (3) is a substituted or unsubstituted phenoxy group represented by the above formula (a).

In the above formula (a), each R ₁ is independently a halogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, an ester group having 2 to 21 carbon atoms (- C(=O)OR ₂ ; R ₂ represents an alkyl group having 1 to 20 carbon atoms), or —R ₃ —C(=O)OR ₄ (R ₃ is a alkylene group, R ₄ represents an alkyl group having 1 to 20 carbon atoms). When a plurality of R ₁ are present in the same phenoxy group (p is an integer of 2 to 5), each R ₁ may be the same or different.

When a halogen atom, an alkyl group having 1 to 20 carbon atoms, or an aryl group having 6 to 30 carbon atoms is introduced into the phenoxy group as R ₁ , due to the extension of the conjugated system and the electron-donating property due to the introduction, The maximum absorption wavelength (λmax) of the phthalocyanine compound shifts to the long wavelength side. As a result, visible light transmittance is improved while maintaining good heat ray absorption ability. Furthermore, the extension of the conjugated system as described above increases the electronic stability within the molecule. As a result, when a medium such as a resin is used as the heat-absorbing material, the interaction between the medium and the phthalocyanine compound caused by the irradiation of ultraviolet rays can be suppressed, and as a result, the decomposition of the phthalocyanine compound can be effectively suppressed/prevented. . Therefore, a heat ray absorbing material using such a phthalocyanine compound has further improved light resistance.

R ₁ may be a halogen atom, an ester group having 2 to 21 carbon atoms or —R ₃ —C(=O)OR ₄ (R ₃ is an alkylene group having 1 to 20 carbon atoms, R ₄ is a carbon (representing an alkyl group having 1 to 20 atoms) is introduced into the phenoxy group, the absorption spectrum (absorption band) becomes sharper due to increased electro-attraction and steric hindrance, and the visible light transmittance improves. do. In addition, compatibility with solvents and resins is improved.

Among the above substituents, considering heat ray absorption ability, transparency (improved visible light transmittance), light resistance and solvent solubility, R ₁ is each independently a halogen atom, a It is preferably selected from the group consisting of 20 alkyl groups and 6 to 30 carbon atom aryl groups.

Furthermore, from the viewpoint of further improving the light resistance in addition to improving the heat ray absorption ability and the visible light transmittance in a well-balanced manner, R ₁ is each independently a halogen atom or an alkyl having 1 to 8 carbon atoms. and aryl groups having 6 to 10 carbon atoms, more preferably selected from the group consisting of halogen atoms, alkyl groups having 1 to 5 carbon atoms, and aryl groups having 6 to 10 carbon atoms. It is particularly preferred to be selected from

In formula (a) above, each p is independently an integer of 0 to 5, and the number of R ₁ introduced into the phenoxy group is not particularly limited. From the viewpoint of further improving the visible light transmittance, each p is preferably an integer of 0 to 3, more preferably an integer of 0 to 2. That is, in a preferred embodiment of the present invention, in the above formulas (1) to (3), each R ₁ is independently a halogen atom, an alkyl group having 1 to 20 carbon atoms, or an alkyl group having 6 to 30 carbon atoms. represents an aryl group; p is an integer of 0-3. In a more preferred embodiment of the present invention, in the above formulas (1) to (3), each R ₁ is independently a halogen atom, an alkyl group having 1 to 8 carbon atoms, or an aryl group having 6 to 10 carbon atoms. represents a group; p is an integer of 0-2. Furthermore, p is particularly preferably an integer of 1 or 2 from the viewpoint of improving light resistance. That is, in a particularly preferred embodiment of the present invention, in the above formulas (1) to (3), each R ₁ is independently a halogen atom, an alkyl group having 1 to 5 carbon atoms, or an alkyl group having 6 to 10 carbon atoms. p is 1 or 2. Also, the bonding position of the substituent _R1 to the phenoxy group is not particularly limited. For example, when p is 1, the substituent is placed at the ortho-position (2-position), meta-position (3-position) or para-position (4-position) relative to the oxygen atom of the phenoxy group. can be Among these, the 2nd and 4th positions are preferred, and the 2nd position is more preferred, in consideration of selective absorption in a specific wavelength region, solvent solubility, and the like. When p is 2, the substituents are 2,3-positions, 2,4-positions, 2,5-positions, 2,6-positions, 3,4-positions, and 3,5-positions relative to the oxygen atoms of the phenoxy group. can be placed in any position. Among these, 2,4-position, 2,5-position, and 2,6-position are preferable, and 2,5-position and 2,6-position are more preferable, considering visible light transmittance and the like.

Here, the halogen atom represented by R ₁ includes a fluorine atom, a chlorine atom, a bromine atom and an iodine atom. Among these, a fluorine atom or a chlorine atom is preferred, and a fluorine atom is more preferred, from the viewpoint of improving visible light transmittance and light resistance.

The alkyl group having 1 to 20 carbon atoms represented by R ₁ is not particularly limited, but examples include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec- butyl group, tert-butyl group, n-pentyl group, isopentyl, neopentyl, n-hexyl group, cyclohexyl group, n-heptyl group, n-octyl group, 2-ethylhexyl group, n-nonyl group, n-decyl group, n-undecyl group, n-dodecyl group, n-tridecyl group, n-tetradecyl group, 2-tetraoctyl group, n-pentadecyl group, n-hexadecyl group, 2-hexyldecyl group, n-heptadecyl group, 1-octyl linear or branched alkyl groups such as nonyl group, n-octadecyl group, n-nonadecyl group and n-icosyl group; and cyclic alkyl groups such as cyclohexyl group and cyclooctyl group. Among these, linear or branched alkyl groups having 1 to 8 carbon atoms are preferred, methyl group, ethyl group, n-propyl group and isopropyl group are particularly preferred, and methyl group is most preferred. By having the alkyl group, the maximum absorption wavelength tends to exist in a specific wavelength region, and good heat ray absorption ability can be exhibited.

The aryl group having 6 to 30 carbon atoms represented by R ₁ is not particularly limited, and examples thereof include non-condensed hydrocarbon groups such as phenyl group and biphenyl group; pentalenyl group, indenyl group, naphthyl group and azulenyl group. , a heptalenyl group, a biphenylenyl group, a fluorenyl group, and an acenaphthylenyl group. Among these, a phenyl group and a naphthyl group are preferred, and a phenyl group is particularly preferred. By having the above aryl group, the maximum absorption wavelength tends to exist in a specific wavelength region, and good heat ray absorption ability can be exhibited. Moreover, since the electrons are delocalized, the light resistance is also improved.

An ester group having 2 to 21 carbon atoms represented by R ₁ is represented by the formula: -C(=O)OR ₂ . At this time, R ₂ represents an alkyl group having 1 to 20 carbon atoms. Here, the alkyl group having 1 to 20 carbon atoms is not particularly limited, and includes the same alkyl groups as those described above, so description thereof is omitted here. Among these, from the viewpoint of improving visible light transmittance, light resistance, durability, solvent solubility, and compatibility with resins, R ₂ is a linear or branched alkyl group having 1 to 8 carbon atoms. is preferred, a methyl group and an ethyl group are more preferred, and a methyl group is particularly preferred.

In the substituent —R ₃ —C(=O)OR ₄ represented by R ₁ , R ₃ represents an alkylene group having 1 to 20 carbon atoms, and R ₄ represents an alkyl group having 1 to 20 carbon atoms. . Here, the alkylene group having 1 to 20 carbon atoms as R ₃ is not particularly limited, but examples include methylene group, ethylene group, propylene group, trimethylene group, tetramethylene group, pentamethylene group and hexamethylene group. straight-chain or branched-chain alkylene groups such as Among these, from the viewpoint of improving visible light transmittance, light resistance, durability, solvent solubility, and compatibility with resins, R ₃ is a linear or branched alkylene group having 1 to 8 carbon atoms. is preferred, a methylene group and an ethylene group are more preferred, and a methylene group is particularly preferred. In addition, the alkyl group having 1 to 20 carbon atoms as R ₄ is not particularly limited, and the same alkyl groups as those described above can be mentioned, so the description is omitted here. Among these, from the viewpoint of improving visible light transmittance, light resistance, durability, solvent solubility, and compatibility with resins, R ₄ is a linear or branched alkyl group having 1 to 8 carbon atoms. is preferred, a methyl group and an ethyl group are more preferred, and a methyl group is particularly preferred.

In the phthalocyanine compounds of formulas (1) to (3) according to the present invention, 1 to 15 substituents (a) are introduced on each phthalocyanine skeleton at both terminals. That is, m in the above formulas (1) to (3) is each independently an integer of 1 to 15. From the viewpoint of further improving light resistance in addition to good heat absorption ability and visible light transmittance, when the substituent (b′) is not present (o is 0), m is independently , preferably an integer of 5 to 15, more preferably an integer of 8 to 15, and particularly preferably an integer of 10 to 15. Further, when the substituent (b') is present (o is 1 or more), the above formula (1 ) to (3) each independently preferably represents an integer of 5 to 7.

In the phthalocyanine compound of formula (3) according to the present invention, 1 to 14 substituents (a) in the phthalocyanine skeleton in the central portion are introduced onto each phthalocyanine skeleton. That is, each m' in the above formula (3) is independently an integer of 1 to 14. From the viewpoint of further improving light resistance in addition to good heat absorption ability and visible light transmittance, when the substituent (b') is not present (o is 0), m' is independently is preferably an integer of 5-7. Further, when the substituent (b') is present (o is 1 or more), in addition to good heat ray absorption ability and visible light transmittance, from the viewpoint of further improving light resistance, m' is Each independently preferably is an integer of 3 to 5.

Among these, at least one or more substituents (a) are a phenoxy group (that is, a substituent with p = 0 in the above formula (a)), a 4-fluorophenoxy group (that is, the above formula (a) in which R ₁ is a fluorine atom and a substituent where p = 1), a 2,5-dimethylphenoxy group (that is, in formula (a) above, R ₁ is a methyl group and a substituent where p = 2), 2 ,6-dimethylphenoxy group (that is, in formula (a) above, R ₁ is a methyl group and a substituent with p=2), or a 2-phenylphenoxy group (that is, in formula (a) above, R ₁ is a phenyl group, a substituent where p = 1), a 2,5-dimethylphenoxy group (that is, a substituent where R ₁ is a methyl group and p = 2 in the above formula (a)), 2, 6-dimethylphenoxy group (that is, in formula (a) above, R ₁ is a methyl group, a substituent with p = 2), or 2-phenylphenoxy group (that is, in formula (a) above, R ₁ is phenyl group, a substituent where p=1). One kind of these substituents may be introduced onto one phthalocyanine skeleton, or two or more kinds thereof may be introduced. Further, when the substituent (b') does not exist (o is 0), it is preferable that 8 or more of these substituents are introduced on one phthalocyanine skeleton, and 10 or more. more preferred. A phthalocyanine-based compound having such a structure has improved heat absorption ability and visible light transmittance, and further improved light resistance. Further, when substituents (b') are present (o is 1 or more), the number of these substituents is preferably 5 to 7 on one phthalocyanine skeleton.

(structure (b) (substituent (b))
Structure (b) (substituent (b)) in the above formulas (1) to (3) is represented by the above formula (b). The binding sites represented by "*" in the above formula (b) are adjacent among A ₁ to A ₄ , A ₅ to A ₈ , A ₉ to A ₁₂ and A ₁₃ to A ₁₆ on the phthalocyanine skeleton; A naphthalocyanine skeleton is formed by bonding as two substituents.

By introducing the structure (b), it is possible to form molecules having higher planarity, so that each molecule is easily stacked with each other in a state of high planarity. As a result, a phthalocyanine compound capable of exhibiting high light resistance is obtained.

Further, the extension of the conjugated system by the introduction of the above structure (b) increases the electronic stability in the molecule. As a result, when a medium such as a resin is used as the heat-absorbing material, the attack of the phthalocyanine compound by active oxygen, radicals, etc. caused by ultraviolet irradiation can be suppressed, and as a result, the decomposition of the phthalocyanine compound can be effectively suppressed.・Can be prevented. Therefore, a heat absorbing material using such a phthalocyanine compound has excellent light resistance.

Furthermore, the extension of the conjugated system as described above shifts the maximum absorption wavelength (λmax) of the phthalocyanine compound to the longer wavelength side. As a result, visible light transmittance is improved while maintaining good heat ray absorption ability.

In the present specification, the term "two adjacent substituents" refers to a substituent on one benzene ring and another substituent present at the ortho position (2-position) relative to the substituent. And point to. For example, “two adjacent substituents” are A ₁ and A ₂ , A ₂ and A ₃ , A ₃ and A ₄ and the like. Therefore, "the binding sites represented by * in the structure (b) are A ₁ to A ₄ , A ₅ to A ₈ , A ₉ to A ₁₂ , A ₁₃ to A ₁₆ in the formulas (1) to (3). “bond as two adjacent substituents of A 1 to A 16 ” means that one of the adjacent substituents on one benzene ring among A ₁ to A ₁₆ is one of the structure (b) represented by the above formula (b) and the other of the adjacent substituents is bound to the other binding site of the structure (b) represented by the above formula (b).

In the phthalocyanine compound according to the present invention, 0 to 3 structures (b) are introduced onto each phthalocyanine skeleton. That is, k in the above formulas (1) to (3) is each independently an integer of 0 to 3. From the viewpoint of suppressing broadening of the absorption spectrum (absorption band) and obtaining good visible light transmittance, each k is preferably an integer of 0 to 2, and is 0 or 1. and more preferred. Furthermore, k is particularly preferably 1 from the viewpoint of further improving the durability.

The introduction position of structure (b) is not particularly limited. For example, among A ₁ to A ₄ , a form in which one binding site of structure (b) is bound to A ₁ and the other binding site of structure (b) is bound to A ₂ (α-position to β-position) or a form in which one binding site of structure (b) is bound to _A2 and the other binding site of structure (b) is bound to _A3 (between β positions). In particular, the structure (b) is preferably formed so as to bridge the adjacent β-positions in order to maintain good heat absorption and visible light transmittance and at the same time obtain higher light resistance. That is, two adjacent substituents substituted by the structure (b) represented by the formula (b) are A ₂ to A ₃ , A ₆ to A ₇ , A ₁₀ to A ₁₁ , A ₁₄ to A ₁₅ is preferably selected from a combination of

(structure (b') (substituent (b'))
Structure (b') (substituent (b')) in the above formulas (1) to (3) is represented by the above formula (b'). The binding sites represented by "*" in the above formula (b') are adjacent among A ₁ to A ₄ , A ₅ to A ₈ , A ₉ to A ₁₂ and A ₁₃ to A ₁₆ on the phthalocyanine skeleton; bond as two substituents.

By introducing the structure (b'), molecules having higher planarity can be formed, so that the molecules are easily stacked on each other in a state of high planarity. As a result, a phthalocyanine compound capable of exhibiting high light resistance is obtained.

Further, the extension of the conjugated system by introducing the structure (b') increases the electronic stability in the molecule. As a result, when a medium such as a resin is used as the heat-absorbing material, the attack of the phthalocyanine compound by active oxygen, radicals, etc. caused by ultraviolet irradiation can be suppressed, and as a result, the decomposition of the phthalocyanine compound can be effectively suppressed.・Can be prevented. Therefore, a heat absorbing material using such a phthalocyanine compound has excellent light resistance.

Furthermore, the extension of the conjugated system as described above shifts the maximum absorption wavelength (λmax) of the phthalocyanine compound to the longer wavelength side. As a result, visible light transmittance is improved while maintaining good heat ray absorption ability.

In the present specification, the term "two adjacent substituents" refers to a substituent on one benzene ring and another substituent present at the ortho position (2-position) relative to the substituent. And point to. For example, “two adjacent substituents” are A ₁ and A ₂ , A ₂ and A ₃ , A ₃ and A ₄ and the like. Therefore, "the binding sites represented by * in structure (b') are A ₁ to A ₄ , A ₅ to A ₈ , A ₉ to A ₁₂ , A ₁₃ to A ₁₆ are bound as two adjacent substituents” means that one of the adjacent substituents on one benzene ring among A ₁ to A ₁₆ has the structure (b′ ), and the other of the adjacent substituents is bound to the other binding site of the structure (b') represented by the above formula (b') Say.

In the structure (b′) of the following formula (b′), q is the number of carbon atoms in the alkylene group (—C _q H _2q —) connecting two phenoxy groups (—O—Ph; Ph=phenyl group). represents Each q is independently an integer of 0-3. From the viewpoint of suppressing broadening of the absorption spectrum (absorption band) and obtaining good visible light transmittance, q is preferably 0 or 1, particularly preferably 0.

Moreover, in the above structure (b'), the position where the two phenoxy groups are linked is not particularly limited. Specifically, the 2-position of one phenoxy group and the 2-position of the other phenoxy group are preferably linked to the 3-position of one phenoxy group and the 3-position of the other phenoxy group. More preferably, the 2-position and the 2-position of the other phenoxy group are linked. That is, the substituent (b') preferably has the following structure.

In the phthalocyanine compound according to the present invention, 0 to 6 structures (b') are introduced onto each phthalocyanine skeleton. That is, o in the above formulas (1) to (3) is each independently an integer of 0 to 6. From the viewpoint of suppressing broadening of the absorption spectrum (absorption band) and obtaining good visible light transmittance, o is each independently preferably an integer of 0 to 5, and 0 (structure (b ')) or 3 to 4 are more preferable. When structures (b) and (b') coexist, the total number of structures (b) and (b') introduced into the phthalocyanine skeleton (total of o and k) is not particularly limited, but absorption From the viewpoint of suppressing broadening of the spectrum (absorption band) and obtaining good visible light transmittance, it is preferably an integer of 3 to 5, and more preferably 4.

The introduction position of structure (b') is not particularly limited. For example, among A ₁ to A ₄ , a form in which one binding site of structure (b) is bound to A ₁ and the other binding site of structure (b) is bound to A ₂ (α-position to β-position) or a form in which one binding site of structure (b) is bound to _A2 and the other binding site of structure (b') is bound to _A3 (between β positions) . In particular, the structure (b') is preferably formed so as to bridge the adjacent β-positions in order to maintain good heat absorption and visible light transmittance and at the same time obtain higher light resistance. That is, the two adjacent substituents substituted by the structure (b') represented by the formula (b') are A ₂ to A ₃ , A ₆ to A ₇ , A ₁₀ to A ₁₁ , A ₁₄ to A ₁₅ combinations are preferred.

(halogen atom)
“X” in the above formulas (1) to (3) represents a halogen atom. Halogen atoms represented by X include fluorine, chlorine, bromine and iodine atoms. Among these, a fluorine atom or a chlorine atom is preferred, and a chlorine atom is more preferred, from the viewpoint of improving visible light transmittance and light resistance.

In the phthalocyanine compound according to the present invention, 0 to 4 halogen atoms are introduced onto each phthalocyanine skeleton. That is, n in the above formulas (1) to (3) is each independently an integer of 0 to 4. From the viewpoint of lengthening the maximum absorption wavelength (λmax) and obtaining better heat ray absorption ability, each n is preferably an integer of 0 to 2, more preferably 0 or 1, 0 is particularly preferred.

(a1)
The phthalocyanine-based compound of the above formula (3) has three or more [(a1+2)] phthalocyanine skeletons into which a specific number of substituents (a), (b) and (b′) and halogen atoms (X) are introduced, and a linker It has a structure linked via (-O-Y-O-). Here, the total number of linkages of such a phthalocyanine skeleton is 3 to 8, preferably 3 to 6. That is, a1 in the above formula (3) is 1 to 6, preferably 1 to 4, more preferably 1. With such a number of connections, the light resistance can be further improved while maintaining the solubility, good heat absorption ability and visible light transmittance.

As will be described in detail below, raw materials (phthalonitrile compound, phthalonitrile compound derivative) are mixed in a desired ratio when producing the phthalocyanine compound according to the present invention. At this time, the produced phthalocyanine compound may be in the form of a mixture having various structures. Therefore, a1 in the above formula (3) may be a decimal point. Similarly, for a single phthalocyanine-based compound, the substituent (a), structure (b), structure (b') substituted on the phthalocyanine skeleton, and the halogen atom represented by "X" are integers. On the other hand, when the produced phthalocyanine-based compound is a mixture, the entire mixture is analyzed, or theoretically, the substituents (a), structure (b), and structure (b') substituted on the phthalocyanine skeleton , the number of introduction (substitution) of halogen atoms represented by "X" is represented by a decimal point.

(Preferred forms of substituents, etc.)
In the phthalocyanine compound according to the present invention, each phthalocyanine skeleton has 9 to 11 substituents (a) from the viewpoint of obtaining excellent light resistance in addition to good heat absorption ability and visible light transmittance. and at least one structure (b); or 4 to 7 substituents (a), 0 or 1 structure (b), and 3 or 4 structures (b′) It is preferable to have In addition, the maximum absorption wavelength (λmax) of the phthalocyanine compound can be present in the range of 740 to 850 nm by arranging the substituents in this way. Therefore, the phthalocyanine-based compound according to the present embodiment can selectively absorb light in the specific wavelength range, and can exhibit an excellent heat ray shielding effect. Further, a phthalocyanine compound having such a substituent is particularly excellent in visible light transmittance when mixed with a resin. Furthermore, since the phthalocyanine compound according to the present embodiment has excellent light resistance and weather resistance, it exhibits excellent durability even when used as a heat ray absorbing material for buildings, automobiles, and the like.

Further, from the same point of view, the phthalocyanine compound according to the present invention has, in the above formulas (1) to (3), 11 out of A ₁ to A _{16 of A 1 to A 16} being the substituent (a), and 1 have structure (b), and the remainder of A ₁ to A ₁₆ are hydrogen atoms; five substituents (a), one structure (b), and structure (b′) or 7 of said substituents (a), 0 of said structure (b) and 4 of said structure (b'). That is, in the above formulas (1) to (3), one set of two adjacent substituents of A ₁ to A ₄ , A ₅ to A ₈ , A ₉ to A ₁₂ , and A ₁₃ to A ₁₆ is the above Structure (b) represented by formula (b) (k=1), 11 of the remaining A ₁ to A ₁₆ are substituents (a) (m=11), and n is 0 of two adjacent substituents of A ₁ to A ₄ , A ₅ to A ₈ , A ₉ to A ₁₂ and A ₁₃ to A ₁₆ ; Yes (k = 1), 3 sets are the structure (b') represented by the above formula (b') (o = 3), and among the remaining A ₁ to A ₁₆ , 5 are substituents (a) (m=5) and n is 0; or four sets of two adjacent substituents of A ₁ -A ₄ , A ₅ -A ₈ , A ₉ -A ₁₂ , A ₁₃ -A ₁₆ is the structure (b′) represented by the above formula (b′) (o=4), and among the remaining A ₁ to A ₁₆ , 7 are substituents (a) (m=7), n is preferably 0.

The position of the substituent (a), the position of the structure (b), and the position of the structure (b') are not particularly limited. The introduction positions and types of the substituent (a) and the structures (b) and (b′) to A ₁ to A ₁₆ may be uniform or non-uniform, but the substituent (a) and the structure (b) and (b') are preferably introduced substantially uniformly (at one or two introduction positions or types), and more preferably uniformly introduced throughout. Specifically, if the structural units including A ₁ to A ₄ , A ₅ to A ₈ , A ₉ to A ₁₂ and A ₁₃ to A ₁₆ are structural units A, B, C and D, respectively, Units A to D preferably each have the same substituent (a). By adopting such a form, the absorption spectrum (absorption band) can be made sharper, the visible light transmittance can be improved, and the light resistance can be further improved.

(linker)
“Y(O) ₂ —” or “Y(O) ₃ —” representing a linker in formulas (1) to (3) connects each phthalocyanine skeleton. At this time, the terminal oxygen atom contained in the linker is bonded to the carbon atom constituting each phthalocyanine skeleton. Y contained in the linker is a divalent or trivalent organic group which may have an oxygen atom. Here, the organic group is not particularly limited as long as it contains a carbon atom and, if necessary, an oxygen atom. A phthalocyanine compound having good heat ray absorption ability and visible light transmittance and excellent light resistance can be obtained. From this point of view, it is preferable to have the following structure. That is, in the above formulas (1) to (3), Y is
A linear or branched alkylene group having 1 to 20 carbon atoms, a cyclic alkylene group having 3 to 20 carbon atoms, the following formula (3-1):

[In the above formula (3-1),
Each R ₁₁ is independently a halogen atom, an alkyl group having 1 to 20 carbon atoms, or an ester group having 2 to 21 carbon atoms (—C(=O)OR ₁₂ ; R ₁₂ is a carbon atom number representing an alkyl group of 1 to 20),
q is an integer of 0 to 3], and the following formula (3-2):

[In the above formula (3-2),
R ₁₃ is —C(R ₁₄ )(R ₁₅ )—(R ₁₄ and R ₁₅ are each independently a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, or an aryl group having 6 to 30 carbon atoms group), or —SO ₂ —,
R ₁₆ and R ₁₇ are each independently a halogen atom, an alkyl group having 1 to 20 carbon atoms, or an ester group having 2 to 21 carbon atoms (—C(=O)OR ₁₈ ; R ₁₈ is an alkyl group having 1 to 20 carbon atoms); r and s are each independently an integer of 0 to 2]. an organic group of; or
A linear or branched trivalent aliphatic hydrocarbon group having 1 to 20 carbon atoms, a cyclic trivalent aliphatic hydrocarbon group having 3 to 20 carbon atoms, the following formula (4-1):

[In the above formula (4-1),
Each R ₂₁ is independently a halogen atom, an alkyl group having 1 to 20 carbon atoms, or an ester group having 2 to 21 carbon atoms (—C(=O)OR ₂₂ , where R ₂₂ is represents an alkyl group having 1 to 20 carbon atoms; t is an integer of 0 to 2], the following formula (4-2):

[In the above formula (4-2),
R ₂₃ represents a hydrogen atom or an alkyl group having 1 to 20 carbon atoms);
R ₂₅ to R ₂₇ are each independently a halogen atom, an alkyl group having 1 to 20 carbon atoms, or an ester group having 2 to 21 carbon atoms (—C(=O)OR ₂₈ ; R ₂₈ is u, v and w are each independently an integer of 0 to 2], and the following formula (4- 3):

[In the above formula (4-3),
R ₂₈ , R ₂₉ and R ₃₀ are each independently a halogen atom, an alkyl group having 1 to 20 carbon atoms, or an ester group having 2 to 21 carbon atoms (—C(=O)OR ₃₂ ; R ₃₂ represents an alkyl group having 1 to 20 carbon atoms);
x1' and x4' are each independently an integer from 1 to 4;
x2' and x5' are each independently 1 or 2;
x3' is an integer from 0 to 3;
y1′ and y2′ are each independently an integer of 0 to 2] and are trivalent organic groups selected from the group consisting of aromatic ring-linking groups represented by

Hereinafter, the structure of Y will be described in detail separately for a divalent organic group and a trivalent organic group.

<<Y (divalent organic group)>>
When Y is a divalent organic group, Y preferably has the following structure. That is, the divalent organic group Y is a linear or branched alkylene group having 1 to 20 carbon atoms, a cyclic alkylene group having 3 to 20 carbon atoms, represented by the following formula (3-1) An arylene group or an aromatic ring-containing group represented by the following formula (3-2) is preferable:

In the above formula (3-1),
Each R ₁₁ is independently a halogen atom, an alkyl group having 1 to 20 carbon atoms, or an ester group having 2 to 21 carbon atoms (—C(=O)OR ₁₂ ; R ₁₂ is a carbon atom number representing an alkyl group of 1 to 20),
q is an integer from 0 to 3;

In the above formula (3-2),
R ₁₃ is —C(R ₁₄ )(R ₁₅ )—(R ₁₄ and R ₁₅ are each independently a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, or an aryl group having 6 to 30 carbon atoms group), or —SO ₂ —,
R ₁₆ and R ₁₇ are each independently a halogen atom, an alkyl group having 1 to 20 carbon atoms, or an ester group having 2 to 21 carbon atoms (—C(=O)OR ₁₈ ; R ₁₈ is an alkyl group having 1 to 20 carbon atoms); r and s are each independently an integer of 0 to 2;

- A linear or branched alkylene group having 1 to 20 carbon atoms In the above formulas (1) to (3), a linear or branched alkylene group having 1 to 20 carbon atoms as the divalent organic group Y The alkylene group is not particularly limited, and examples thereof include linear or branched alkylene groups such as a methylene group, ethylene group, propylene group, trimethylene group, tetramethylene group, pentamethylene group and hexamethylene group. Among these, from the viewpoint of reducing the steric hindrance between the phthalocyanine skeletons to form molecules with high planarity and improving the light resistance, a straight-chain divalent organic group Y having 1 to 20 carbon atoms Alternatively, the branched alkylene group is preferably a straight or branched alkylene group having 2 to 8 carbon atoms, more preferably a trimethylene group, a tetramethylene group or a pentamethylene group, and particularly preferably a trimethylene group.

- A cyclic alkylene group having 3 to 20 carbon atoms In the above formulas (1) to (3), the cyclic alkylene group having 3 to 20 carbon atoms as the divalent organic group Y is not particularly limited. , for example, cyclic alkylene groups such as a cyclopentylene group, a cyclohexylene group, and an adamantylene group. Among these, a cyclic alkylene having 3 to 20 carbon atoms as the divalent organic group Y is used from the viewpoint of reducing steric hindrance between phthalocyanine skeletons to form molecules with high planarity and enhancing light resistance. The group is preferably a cyclic alkylene group having 4 to 10 carbon atoms, more preferably a cyclohexylene group, even more preferably an o-cyclohexylene group or a p-cyclohexylene group, and particularly preferably a p-cyclohexylene group.

An arylene group represented by formula (3-1) In the above formula (3-1), each R ₁₁ is independently a halogen atom, an alkyl group having 1 to 20 carbon atoms, or 2 carbon atoms. ∼21 ester groups (-C(=O)OR ₁₂ ; R ₁₂ represents an alkyl group having 1 to 20 carbon atoms). When a plurality of R ₁₁ are present in the same phenylene group (q is an integer of 2 to 3), each R ₁₁ may be the same or different.

When an alkyl group having 1 to 20 carbon atoms is introduced into the phenylene group as R ₁₁ , the maximum absorption wavelength (λmax) of the phthalocyanine compound becomes longer due to the extension of the conjugated system due to the introduction and the electron-donating property. shift to the side. As a result, visible light transmittance is improved while maintaining good heat ray absorption ability. Furthermore, the extension of the conjugated system as described above increases the electronic stability within the molecule. As a result, when a medium such as a resin is used as the heat-absorbing material, the attack of the phthalocyanine compound by active oxygen, radicals, etc. caused by ultraviolet irradiation can be suppressed, and as a result, the decomposition of the phthalocyanine compound can be effectively suppressed.・Can be prevented. Therefore, a heat ray absorbing material using such a phthalocyanine compound has further improved light resistance.

In addition, when a halogen atom or an ester group having 2 to 21 carbon atoms is introduced into the phenylene group as R ₁₁ , the absorption spectrum (absorption band) becomes sharp due to increased electron-withdrawing properties and steric hindrance. and the visible light transmittance is improved. In addition, compatibility with solvents and resins is improved.

Among the above substituents, considering heat ray absorption ability, transparency (improved visible light transmittance), light resistance, solvent solubility, etc., when q is 1 or more, R ₁₁ is each independently preferably selected from the group consisting of an alkyl group having 1 to 20 carbon atoms and an ester group having 2 to 21 carbon atoms, and an alkyl group having 1 to 8 carbon atoms and an ester group having 2 to 10 carbon atoms; is particularly preferably selected from the group consisting of

Specific examples of the halogen atom, the alkyl group having 1 to 20 carbon atoms and the ester group having 2 to 21 carbon atoms as R ₁₁ are not particularly limited, and are the same as the specific examples relating to R ₁ above. Therefore, the description is omitted here. Among these, from the viewpoint of improving visible light transmittance, light resistance, durability, solvent solubility, and compatibility with resins, when q is 1 or more, R ₁₁ has 1 to 8 carbon atoms. It is preferably selected from the group consisting of linear or branched alkyl groups and ester groups having 2 to 10 carbon atoms, more preferably methyl, ethyl or --COOCH ₃ , particularly preferably methyl.

In the above formula (3-1), q is an integer of 0-3. From the viewpoint of maintaining good visible light transmittance and improving light resistance, each q is preferably an integer of 0 or 1, more preferably 0. Also, when q is 1 or more, the bonding position of the substituent R ₁₁ to the phenylene group is not particularly limited. In addition, the bonding position of the oxygen atom constituting the linker to the phenylene group is not particularly limited, but from the viewpoint of reducing the steric hindrance between the phthalocyanine skeletons to form a highly planar molecule and increasing the light resistance, the linker is used. The two constituent oxygens are preferably substituted at the 1,2-position (ortho-position) or 1,4-position (para-position), and particularly preferably substituted at the 1,4-position (para-position).

- Aromatic ring-containing group represented by formula (3-2) In the above formula (3-2), R ₁₃ is a substituent represented by the formula: -C(R ₁₄ )(R ₁₅ )-, or - SO ₂ -.

At this time, R ₁₄ and R ₁₅ each independently represent a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, or an aryl group having 6 to 30 carbon atoms. R ₁₄ and R ₁₅ may be the same or different.

When an alkyl group having 1 to 20 carbon atoms or an aryl group having 6 to 30 carbon atoms is introduced as R ₁₄ or R ₁₅ , phthalocyanine compounds are produced due to expansion of the conjugated system and electron donating properties due to the introduction. The maximum absorption wavelength (λmax) of is shifted to the long wavelength side. As a result, visible light transmittance is improved while maintaining good heat ray absorption ability. Furthermore, the extension of the conjugated system as described above increases the electronic stability within the molecule. As a result, when a medium such as a resin is used as the heat-absorbing material, the attack of the phthalocyanine compound by active oxygen, radicals, etc. caused by ultraviolet irradiation can be suppressed, and as a result, the decomposition of the phthalocyanine compound can be effectively suppressed.・Can be prevented. Therefore, a heat ray absorbing material using such a phthalocyanine compound has further improved light resistance.

Among the above substituents, considering heat ray absorption ability, transparency (improved visible light transmittance), light resistance and solvent solubility, R ₁₄ and R ₁₅ each independently have 1 to 1 carbon atoms. It is preferably selected from 20 alkyl groups, particularly preferably from alkyl groups having 1 to 8 carbon atoms.

Specific examples of the alkyl group having 1 to 20 carbon atoms and the aryl group having 6 to 30 carbon atoms as R ₁₄ and R ₁₅ are not particularly limited, and are the same as the specific examples relating to R ₁ above. Therefore, the description is omitted here. Among these, from the viewpoint of improving visible light transmittance, light resistance, durability, solvent solubility, and compatibility with resins, R ₁₄ and R ₁₅ each independently have 1 to 8 carbon atoms. A straight or branched chain alkyl group is preferable, a methyl group and an ethyl group are more preferable, and a methyl group is particularly preferable.

As described above, R ₁₃ is a substituent represented by the formula: —C(R ₁₄ )(R ₁₅ )— (R ₁₄ and R ₁₅ are each independently a linear or branched group having 1 to 8 carbon atoms). chain alkyl group), or —SO ₂ —, preferably a substituent represented by the formula: —C(R ₁₄ )(R ₁₅ )— (R ₁₄ and R ₁₅ are methyl groups), or —SO _2- is more preferred.

In the above formula (3-2), R ₁₆ and R ₁₇ each independently represent a halogen atom, an alkyl group having 1 to 20 carbon atoms, or an ester group having 2 to 21 carbon atoms (-C(= O) OR ₁₈ ; R ₁₈ represents an alkyl group having 1 to 20 carbon atoms); When a plurality of R ₁₆ and R ₁₇ are present in the same phenylene group (r and/or s is 2), R ₁₆ and R ₁₇ may be the same or different. may be

Specific examples of a halogen atom, an alkyl group having 1 to 20 carbon atoms and an ester group having 2 to 21 carbon atoms as R ₁₆ and R ₁₇ are not particularly limited, and are the same as the specific examples relating to R ₁ above. are omitted here. Among these, from the viewpoint of improving visible light transmittance, light resistance, durability, solvent solubility, and compatibility with resins, when r and/or s is 1 or more, R ₁₆ and R ₁₇ are Each independently, a linear or branched alkyl group having 1 to 8 carbon atoms is preferable, a methyl group and an ethyl group are more preferable, and a methyl group is particularly preferable.

In the above formula (3-2), r and s are each independently an integer of 0-2. From the viewpoint of maintaining good visible light transmittance and improving light resistance, r and s are each independently preferably an integer of 0 or 1, and more preferably 0. Also, when r and/or s is 1 or more, the bonding positions of the substituents _R16 and _R17 to the phenylene group are not particularly limited. In addition, the bonding position of the oxygen atom constituting the linker to the phenylene group is not particularly limited, but from the viewpoint of reducing the steric hindrance between the phthalocyanine skeletons to form a highly planar molecule and increasing the light resistance, the linker is used. The two constituent oxygens are preferably substituted at the 4-position (para-position) relative to _R13 .

<<Y (trivalent organic group)>>
When Y is a trivalent organic group, Y preferably has the following structure. That is, the trivalent organic group Y is a linear or branched trivalent aliphatic hydrocarbon group having 1 to 20 carbon atoms, a cyclic trivalent aliphatic hydrocarbon group having 3 to 20 carbon atoms, A trivalent aromatic hydrocarbon group represented by the following formula (4-1), an aromatic ring-containing group represented by the following formula (4-2), or an aromatic ring represented by the following formula (4-3) Preferably the linking group is:

In the above formula (4-1),
Each R ₂₁ is independently a halogen atom, an alkyl group having 1 to 20 carbon atoms, or an ester group having 2 to 21 carbon atoms (—C(=O)OR ₂₂ , where R ₂₂ is t is an integer of 0-2.

In the above formula (4-2),
R ₂₃ represents a hydrogen atom or an alkyl group having 1 to 20 carbon atoms;
R ₂₅ to R ₂₇ are each independently a halogen atom, an alkyl group having 1 to 20 carbon atoms, or an ester group having 2 to 21 carbon atoms (—C(=O)OR ₂₈ ; R ₂₈ is u, v and w are each independently an integer of 0-2.

In the above formula (4-3),
R ₂₈ , R ₂₉ and R ₃₀ are each independently a halogen atom, an alkyl group having 1 to 20 carbon atoms, or an ester group having 2 to 21 carbon atoms (—C(=O)OR ₃₂ ; R ₃₂ represents an alkyl group having 1 to 20 carbon atoms);
x1' and x4' are each independently an integer from 1 to 4;
x2' and x5' are each independently 1 or 2;
x3' is an integer from 0 to 3;
y1' and y2' are each independently an integer of 0-2.

・A linear or branched trivalent aliphatic hydrocarbon group having 1 to 20 carbon atoms In the above formulas (1) to (3), a straight chain having 1 to 20 carbon atoms as the trivalent organic group Y Alternatively, the branched trivalent aliphatic hydrocarbon group is not particularly limited. For example, residues (alkyl triyl group). Among these, from the viewpoint of forming a molecule with high planarity by reducing steric hindrance between phthalocyanine skeletons and improving light resistance, the trivalent organic group Y having 1 to 20 carbon atoms is linear or The branched trivalent aliphatic hydrocarbon group is preferably a straight or branched trivalent aliphatic hydrocarbon group having 2 to 8 carbon atoms.

- A cyclic trivalent aliphatic hydrocarbon group having 3 to 20 carbon atoms In the above formulas (1) to (3), a cyclic trivalent aliphatic hydrocarbon group having 3 to 20 carbon atoms as the trivalent organic group Y. There are no particular restrictions on the group hydrocarbon group. Examples thereof include residues (cycloalkyltriyl groups) obtained by removing three hydrogen atoms from cyclic aliphatic hydrocarbons such as cyclopentane, cyclohexane, cyclooctane and adamantane. Among these, from the viewpoint of reducing the steric hindrance between the phthalocyanine skeletons to form molecules with high planarity and improving light resistance, a cyclic trivalent organic group Y having 3 to 20 carbon atoms is used. The valent aliphatic hydrocarbon group is preferably a cyclic trivalent aliphatic hydrocarbon group having 5 to 10 carbon atoms.

- A trivalent aromatic hydrocarbon group represented by the formula (4-1) In the above formula (4-1), each R ₂₁ is independently a halogen atom, an alkyl group having 1 to 20 carbon atoms, Alternatively, it is an ester group having 2 to 21 carbon atoms (-C(=O)OR ₂₂ ; R ₂₂ represents an alkyl group having 1 to 20 carbon atoms). When a plurality of R ₂₁ are present on the same benzene ring (t is an integer of 2), each R ₂₁ may be the same or different.

Among the above substituents, considering heat ray absorption ability, transparency (improved visible light transmittance), light resistance, solvent solubility, etc., when t is 1 or more, R ₂₁ is each independently preferably selected from the group consisting of an alkyl group having 1 to 20 carbon atoms and an ester group having 2 to 21 carbon atoms, and an alkyl group having 1 to 8 carbon atoms and an ester group having 2 to 10 carbon atoms; is particularly preferably selected from the group consisting of

Specific examples of a halogen atom, an alkyl group having 1 to 20 carbon atoms and an ester group having 2 to 21 carbon atoms as R ₂₁ are not particularly limited, and are the same as the specific examples for R ₁ above. Therefore, the description is omitted here. Among these, from the viewpoint of improving visible light transmittance, light resistance, durability, solvent solubility, and compatibility with resins, when t is 1 or more, R ₂₁ has 1 to 8 carbon atoms. A straight or branched chain alkyl group is preferable, a methyl group and an ethyl group are more preferable, and a methyl group is particularly preferable.

In the above formula (4-1), t is an integer of 0-2. From the viewpoint of maintaining good visible light transmittance and improving light resistance, each t is preferably an integer of 0 or 1, more preferably 0. Further, when t is 1 or more, the bonding position of the substituent R ₂₁ on the benzene ring is not particularly limited. In addition, the bonding position of the oxygen atom that constitutes the linker to the benzene ring is not particularly limited. It is preferable that the three constituent oxygens are substituted with each other at the 1-, 3-, and 5-positions, respectively.

Aromatic Ring-Containing Group Represented by Formula (4-2) In formula (4-2) above, R ₂₃ is a hydrogen atom or an alkyl group having 1 to 20 carbon atoms.

When an alkyl group having 1 to 20 carbon atoms is introduced as R ₂₃ , the maximum absorption wavelength (λmax) of the phthalocyanine compound shifts to the long wavelength side due to the expansion of the conjugated system and the electron donating property due to the introduction. do. As a result, visible light transmittance is improved while maintaining good heat ray absorption ability. Furthermore, the extension of the conjugated system as described above increases the electronic stability within the molecule. As a result, when a medium such as a resin is used as the heat-absorbing material, the attack of the phthalocyanine compound by active oxygen, radicals, etc. caused by ultraviolet irradiation can be suppressed, and as a result, the decomposition of the phthalocyanine compound can be effectively suppressed.・Can be prevented. Therefore, a heat ray absorbing material using such a phthalocyanine compound has further improved light resistance.

Considering R ₂₃ , heat absorption ability, transparency (improved visible light transmittance), light resistance and solvent solubility, R ₂₃ is selected from alkyl groups having 1 to 20 carbon atoms. Preferably, it is particularly preferably selected from alkyl groups having 1 to 8 carbon atoms.

Specific examples of the alkyl group having 1 to 20 carbon atoms as R ₂₃ are not particularly limited, and the same specific examples as those for R ₁ above can be mentioned, and thus description thereof is omitted here. Among these, from the viewpoint of improving visible light transmittance, light resistance, durability, solvent solubility, and compatibility with resins, R ₂₃ is each independently a linear chain having 1 to 8 carbon atoms or A branched alkyl group is preferable, a methyl group and an ethyl group are more preferable, and a methyl group is particularly preferable.

In the above formula (4-2), R ₂₅ to R ₂₇ are each independently a halogen atom, an alkyl group having 1 to 20 carbon atoms, or an ester group having 2 to 21 carbon atoms (-C(= O) OR ₂₈ ; R ₂₈ represents an alkyl group having 1 to 20 carbon atoms). When a plurality of R ₂₅ to R ₂₇ are present on the same benzene ring (any of u, v and w is 2), each of R ₂₅ to R ₂₇ may be the same. Alternatively, they may be different.

Specific examples of a halogen atom, an alkyl group having 1 to 20 carbon atoms, and an ester group having 2 to 21 carbon atoms as R ₂₅ to R ₂₇ are not particularly limited, and are the same as the specific examples relating to R ₁ above. are omitted here. Among these, from the viewpoint of improving visible light transmittance, light resistance, durability, solvent solubility, and compatibility with resins, R ₂₅ to R ₂₇ each independently have 1 to 8 carbon atoms. A straight or branched chain alkyl group is preferable, a methyl group and an ethyl group are more preferable, and a methyl group is particularly preferable.

In the above formula (4-2), u, v and w are each independently an integer of 0-2. From the viewpoint of maintaining good visible light transmittance and improving light resistance, u, v and w are each independently preferably an integer of 0 or 1, more preferably 0. Also, the bonding positions of the substituents R ₂₅ to R ₂₇ on the benzene ring are not particularly limited. In addition, the bonding position of the oxygen atom that constitutes the linker to the benzene ring is not particularly limited. The two constituent oxygens are preferably substituted at the 4-position (para-position) with respect to the central carbon substituted with R ₂₃ .

- Aromatic ring connecting group represented by formula (4-3) In formula (4-3) above, R ₂₈ , R ₂₉ and R ₃₀ (R ₂₈ to R ₃₀ ) are each independently a halogen atom and a carbon atom. It is an alkyl group having 1 to 20 atoms or an ester group having 2 to 21 carbon atoms (-C(=O)OR ₃₂ ; R ₃₂ represents an alkyl group having 1 to 20 carbon atoms). When a plurality of R ₂₈ to R ₃₀ are present on the same benzene ring (any of x1′, x3′ and x4′ is 2 or more), R ₂₈ to R ₃₀ are each the same or may be different.

Specific examples of a halogen atom, an alkyl group having 1 to 20 carbon atoms and an ester group having 2 to 21 carbon atoms as R ₂₈ to R ₃₀ are not particularly limited, and are the same as the specific examples relating to R ₁ above. are omitted here. Among these, from the viewpoint of improving visible light transmittance, light resistance, durability, solvent solubility, and compatibility with resins, R ₂₈ to R ₃₀ each independently have 1 to 8 carbon atoms. A straight or branched chain alkyl group is preferable, a methyl group and an ethyl group are more preferable, and a methyl group is particularly preferable.

In the above formula (4-3), x1' and x4' are each independently an integer of 1-4. From the viewpoint of maintaining good visible light transmittance and improving light resistance, x1′ and x4′ are each independently preferably an integer of 0 or 1, more preferably 1. Also, the bonding positions of the substituents R ₂₈ to R ₃₀ on the benzene ring are not particularly limited. For example, when x1′ and x4′ are 1, the substituent is ortho-position (2-position), meta-position (3-position) or para-position (4-position) with respect to the oxygen atom bonded to the phthalocyanine skeleton. It can be placed in any position. Among these, the substituent is placed at the 4-position with respect to the oxygen atom bonded to the phthalocyanine skeleton from the viewpoint of reducing the steric hindrance between the phthalocyanine skeletons to form a highly planar molecule and increasing the light resistance. preferably.

In addition, the following formula (4-3-1) structure (also referred to as "structure (4-3-1)") and the following formula (4-3-2) structure (also referred to as "structure (4-3-2)" ), the oxygen atom (the left bond in the structure below) and the alkylene group (-(CH ₂ ) _y1′- in the structure (4-3-1) below and the structure (4- The arrangement (linkage relationship) with —(CH ₂ ) _y2′ —) in 3-2) is not particularly limited. For example, an alkylene group (-(CH ₂ ) _y1' - in the structure below) is ortho-position (2-position) and meta-position ( 3-position) or para-position (4-position). Among these, the alkylene group is preferably located at the 2-position with respect to the oxygen atom bonded to the phthalocyanine skeleton. Similarly, the alkylene group (-(CH ₂ ) _y2' -) is ortho-position (2-position), meta-position (3-position ) or in the para position (4-position). Among these, the alkylene group is preferably located at the 2-position with respect to the oxygen atom bonded to the phthalocyanine skeleton.

In the above formula (4-3), x2' and x5' are each independently 1 or 2, preferably 1.

Also, y1' and y2' are each independently an integer of 0 to 2, more preferably 1.

In the above formula (4-3), x3' is an integer of 0-3. From the viewpoint of maintaining good visible light transmittance and improving light resistance, x3′ is preferably an integer of 0 or 1, more preferably 1. Also, the bonding position of the substituent R ₂₉ on the benzene ring is not particularly limited. For example, when x3′ is 1, the substituent is either ortho-position (2-position), meta-position (3-position) or para-position (4-position) with respect to the oxygen atom bonded to the phthalocyanine skeleton. position. Among these, the substituent is placed at the 4-position with respect to the oxygen atom bonded to the phthalocyanine skeleton from the viewpoint of reducing the steric hindrance between the phthalocyanine skeletons to form a highly planar molecule and increasing the light resistance. preferably.

In the structure below, the oxygen atom that binds to the phthalocyanine skeleton (the upper right bond in the structure below) and the bond that binds to structure (4-3-1) (the left bond in the structure below) and the structure The arrangement (connection relationship) with the bond that binds to (4-3-2) (the bond on the right side in the structure below) is not particularly limited. From the viewpoint of reducing the steric hindrance between the phthalocyanine skeletons to form a molecule with high planarity and improving the light resistance, the bond and the structure (4-3-2) that bind to the structure (4-3-1) are preferably located at positions 2 and 6, respectively, with respect to the oxygen atom that binds to the phthalocyanine skeleton (the upper right bond in the structure below).

Therefore, preferred examples of the aromatic ring-linking group represented by formula (4-3) include those having the following structures.

· Preferred form of linker (bivalent or trivalent organic group) Among the above, from the viewpoint of improving light resistance, Y is an arylene group represented by the above formula (3-1), and the above formula (3-). 2), a trivalent aromatic hydrocarbon group represented by the above formula (4-1), an aromatic ring-containing group represented by the above formula (4-2) and the above (4 It is preferably selected from aromatic ring-connecting groups represented by -3). With these linkers, the extension of the conjugated system facilitates the delocalization of electrons and increases the electronic stability, thereby further improving the light resistance. From the same point of view, the arylene group represented by the above formula (3-1) is more preferable. Furthermore, from the same point of view, among the arylene groups represented by the above formula (3-1), the oxygen atoms (of the phthalocyanine skeleton) at the 1,2-position (ortho-position) or 1,4-position (para-position) constituting the linker It is preferable that the 1,4-position (para-position) is bonded to the oxygen atoms that constitute the linker.

(Central metal (M))
M representing the central metal in the above formulas (1) to (3) is a metal, metal oxide or metal halide. Here, examples of metals include iron, magnesium, nickel, cobalt, copper, palladium, zinc, vanadium, titanium, indium, and tin. Examples of metal oxides include titanyl and vanadyl (VO). Examples of metal halides include aluminum chloride, indium chloride, germanium chloride, tin(II) chloride, tin(IV) chloride, and silicon chloride. Preferably, the central metal M is selected from copper, zinc, vanadium and metal oxides and halides thereof. Among them, the central metal M is preferably selected from copper, zinc and vanadyl from the viewpoint of obtaining good visible light transmittance. By selecting M from these, it is possible to sharpen the absorption spectrum (absorption band) and further improve the visible light transmittance. Moreover, from the viewpoint of further improving the light resistance, the central metal M is preferably copper or vanadyl, more preferably copper. In particular, copper can exist as a divalent ion in the phthalocyanine skeleton without other atoms (for example, vanadyl has an oxygen atom in addition to V, which lowers the planarity), resulting in high planarity. It is possible to obtain a phthalocyanine compound having As a result, a plurality of copper molecules are easily laminated, and the dye molecules are easily stabilized. From this point of view as well, it is considered that this contributes to the improvement of the light resistance. On the other hand, the central metal M is preferably zinc or vanadyl, more preferably zinc, from the viewpoint of improving the visible light transmittance and improving the solubility in solvents and the like.

《Preferred form》
The phthalocyanine-based compound according to the present invention contains a naphthalene skeleton and is bivalent or trivalent via an oxygen atom, from the viewpoint that molecules are easily laminated while maintaining high planarity and high light resistance is obtained. It is preferred that they are linked by an organic group. Furthermore, from the same point of view, the phthalocyanine compound according to the present invention is more preferably in the form in which k is 1 in the above formulas (1) and (2). Further, the phthalocyanine-based compound according to the present invention more preferably has at least two (especially three) phthalocyanine skeletons in which k is 1 in the above formula (3).

As another preferred form, in the above formulas (1) and (2), the sum of k, m and n (k+m+n) is preferably 10-15, more preferably 12-15. Further, in the above formulas (1) to (3), the sum of k, m, n and o (k+m+n+o) is preferably 9-11. With such a form, high light resistance can be obtained while maintaining good heat ray absorption and visible light transmittance. Furthermore, in the above formulas (1) and (2), it is more preferable that k is 1 and m is 11 to 13, and that k is 1 and m is 11 is particularly preferable. In the above formulas (1) to (3), k is 1, m is 4 to 6, o is 2 to 4; k is 0, m is 6 to 8, o is 3 to 5; more preferably k is 1, m is 5 and o is 3; k is 0, m is 7 and o is 4. Further, in the above formula (3), k is 1, m' is 3 to 5, o is 2 to 4; k is 0, m' is 5 to 7, o is 3 more preferably k is 1, m' is 4 and o is 3; k is 0, m is 6 and o is 4. With such a form, high light resistance can be obtained while maintaining good heat ray absorption and visible light transmittance.

Still another preferred form of the phthalocyanine compound according to the present invention is that two phthalocyanine skeletons are linked via an oxygen atom by a divalent organic group. Furthermore, the phthalocyanine compound according to the present invention is more preferably represented by the above formula (1). Alternatively, the phthalocyanine-based compound according to the present invention is more preferably represented by (2) above, in which Y is an aromatic ring-connecting group represented by formula (4-3) above. With such a form, the planarity of the molecules is increased, and the molecules are easily overlapped, so that the light resistance is improved.

Preferred specific examples of the phthalocyanine compound according to the present invention include compounds represented by the following formulas (I) to (V). In the following formulas (I) to (V), A1, A2, C1 and C2 are each bound to the β-position of the phthalocyanine skeleton, and B1, B2, D1 and D2 are each bound to the α-position of the phthalocyanine skeleton. represents a substituent. Further, the substituents as A1, A2, B1, B2, C1, C2, D1 and D2 each independently represent any one of R-1 to R12 shown below. These substituents may be the same or different. Further, that A1, A2, C1 or C2 is a substituent R-12 means that the structure (b′) (substituent (b′)) in which q is 0 bridges the β-positions adjacent to each other. means. That is, each structural unit including A ₁ to A ₄ , A ₅ to A ₈ , A ₉ to A ₁₂ , and A ₁₃ to A ₁₆ has the structure shown below. In the structure below, there is no substituent at the α-position, but a substituent shown in Table 1 below is introduced.

In addition, X represents a linker and represents any one of X-1 to X-13 shown below. However, the linker X in the following formulas (I) and (II) is selected from X1 to X10 having a divalent organic group, and the linker X in the following (III) and (IV) has a trivalent organic group Selected from X11 to X13. a, b, c and d represent the number of A1 or C1, A2 or C2, B1 or D1, B2 or D2, respectively. Preferred combinations of these substituents, their numbers and linkers are shown in Table 1 below.

Further preferred examples of the phthalocyanine compound according to the present invention include the following compounds. In the following abbreviations of phthalocyanine compounds, abbreviations are given in the order of β-position substituent, α-position substituent, (naphthalene skeleton if included) linker, and central metal. In the abbreviations, Ph is a phenyl group, a phenylene group or a trivalent benzene ring, Me is a methyl group, Pr is a trimethylene group, Cyh is a cyclohexylene group, Pc is a phthalocyanine nucleus, and Np is a naphthalene skeleton. Represent. In (2,2'-PhOPhO), each structural unit including A ₁ to A ₄ , A ₅ to A ₈ , A ₉ to A ₁₂ , and A ₁₃ to A ₁₆ has the structure shown below. have In the structures below, there is no substituent at the α-position, but a substituent defined for each is introduced.

Furthermore, (4-CH ₃ PhO)CH ₂ (4-CH ₃ PhO)CH ₂ (4-CH ₃ PhO) represents the trivalent linker of X-13 above. The description just before Pc indicates the central metal. Furthermore, the description immediately preceding (metal center-Pc) indicates a linker. Note that the naphthalene skeleton occupies a part of the phthalocyanine nucleus, and strictly speaking, it is not a separate bond of the naphthalene skeleton to the phthalocyanine nucleus. Describe.

Regarding the phthalocyanine compound (i), among the compounds indicated by abbreviations, representative compounds are illustrated as structural formulas, but the compounds indicated by the following abbreviations have several isomers with different substitution positions. . That is, as long as the number of each substituent in the phthalocyanine compound is the same, the substitution position is not limited to positions other than the α and β positions. In addition, the following compound numbers are also common to the compounds in the Examples section.

phthalocyanine compound (ii)
[(2,5-Me ₂ PhO) ₁₆ (2,6-Me ₂ PhO) ₈ (2,5-Me ₂ PhO) ₆ (1,4-OPhO)(CuPc) ₂ ] (abbreviation)
phthalocyanine compound (iii)
[(2,5-Me ₂ PhO) ₁₂ (2,6-Me ₂ PhO) ₆ (2,5-Me ₂ PhO) ₄ (Np) ₂ (1,4-OPhO) (CuPc) ₂ ] (abbreviation)
Phthalocyanine compound (iv)
[(2-PhPhO) ₁₂ (PhO) ₆ (2-PhPhO) ₄ (Np) ₂ (1,2-OPhO)(CuPc) ₂ ] (abbreviation)
Phthalocyanine compound (v)
[(4-FPhO) ₆ (2-PhPhO) ₆ (2-PhPhO) ₁₀ (Np) ₂ (1,4-OPhO)(CuPc) ₂ ] (abbreviation)
Phthalocyanine compound (vi)
[(2,5-Me ₂ PhO) ₁₈ (2,6-Me ₂ PhO) ₉ (2,5-Me ₂ PhO) ₆ (Np) ₃ (Ph(O) ₃ )(CuPc) ₃ ] (abbreviation)
phthalocyanine compound (vii)
[(2,5-Me ₂ PhO) ₁₂ (2,6-Me ₂ PhO) ₆ (2,5-Me ₂ PhO) ₄ (Np) ₂ (1,4-OCyhO)(CuPc) ₂ ] (abbreviation)
phthalocyanine compound (viii)
[(2,5-Me ₂ PhO) ₁₂ (2,6-Me ₂ PhO) ₆ (2,5-Me ₂ PhO) ₄ (Np) ₂ (1,3-OPrO)(CuPc) ₃ ] (abbreviation)
phthalocyanine compound (ix)
[(2,5-Me ₂ PhO) ₂₄ (2,6-Me ₂ PhO) ₁₂ (2,5-Me ₂ PhO) ₉ (C(Me)(Ph) ₃ (O) ₃ )(CuPc) ₂ ] (abbreviation)
phthalocyanine compound (xvi)
[(2,2′-PhOPhO) ₇ (2-PhPhO) ₇ (PhO) ₅ (1,4-OPhO)Np(CuPc) ₂ ] (abbreviation)
phthalocyanine compounds (xvii)
[(2,2′-PhOPhO) ₁₆₂₁ (2,6-(CH ₃ ) ₂ PhO) ₁₆₂₁ (PhO) ₁₁ (1,4-OPhO) ₅ (Np) ₃ (CuPc) ₆ ] (abbreviation)
phthalocyanine compounds (xviii)
[(2,2′-PhOPhO) ₁₁ (2-PhPhO) ₁₁ (PhO) ₈ {(4-CH ₃ PhO)CH ₂ (4-CH ₃ PhO)CH ₂ (4-CH ₃ PhO)}Np(CuPc ) ₃ ] (abbreviation).

Among the above phthalocyanine compounds, the phthalocyanine compounds (iii) to (viii) and (xvi) to (xviii) are preferred from the viewpoint of having particularly high light resistance.

[Method for producing phthalocyanine compound]
The method for producing the phthalocyanine-based compound according to the present invention is not particularly limited. The method of can be applied with appropriate modifications. Specifically, the method for producing a phthalocyanine compound according to the present invention comprises, in a molten state or in an organic solvent, a phthalonitrile compound and a dimer or trimer of the phthalonitrile compound (phthalonitrile compound derivative), and if necessary A method of carrying out a cyclization reaction using an optionally used dicyanonaphthalene derivative (naphthalonitrile compound) and a metal compound can be preferably used.

Preferred methods for producing the phthalocyanine compound according to the present invention are described below. However, the invention is not limited to the preferred embodiments described below.

The phthalocyanine compound according to the present invention has the following formulas (A) to (C):

In formulas (A) to (C) above, Z ₁ to Z ₁₂ each independently represent a hydrogen atom, a halogen atom, or the following formula (a):

[In the above formula (a), each R ₁ is independently a halogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, an ester group having 2 to 21 carbon atoms ( —C(═O)OR ₂ ; R ₂ represents an alkyl group having 1 to 20 carbon atoms), or —R ₃ —C(═O)OR ₄ (R ₃ has 1 to 20 carbon atoms and R ₄ represents an alkyl group having 1 to 20 carbon atoms),
p is an integer of 0 to 5] or the following formula (b):

[In the above formula (b), * is a site that binds as two adjacent substituents of Z ₁ to Z ₄ , Z ₅ to Z ₈ , and Z ₉ to Z ₁₂ in the above formulas (A) to (C). The structure (b) represented by], or the following formula (b′):

[In formula (b′) above, * is bonded as two adjacent substituents of Z ₁ to Z ₄ , Z ₅ to Z ₈ , and Z ₉ to Z ₁₂ in formulas (A) to (C). represents a site, q is an integer of 0 to 3],
At this time, at least one of Z ₁ to Z ₁₂ is the substituent (a);
Phthalonitrile compounds (A) to (C) represented by
Formula (D) below:

In the above formula (D), Z ₁₃ to Z ₁₈ are each independently a hydrogen atom, a halogen atom, the substituent (a), the structure (b), or the structure (b′), and the formula In (b) and (b′), * represents a site that binds as two adjacent substituents of Z ₁₃ to Z ₁₅ and Z ₁₆ to Z ₁₈ in formula (D) above, and Y is a divalent is an organic group of;

In the above formula (D'), Z ₁₉ to Z ₂₇ are each independently a hydrogen atom, a halogen atom, the substituent (a), the structure (b), or the structure (b'); In formulas (b) and (b'), * is a site that binds as two adjacent substituents of Z ₁₉ to Z ₂₁ , Z ₂₂ to Z ₂₄ , and Z ₂₅ to Z ₂₇ in formula (D'). and Y is a trivalent organic group; and a phthalonitrile compound derivative (D') represented by
Manufactured by a manufacturing method comprising reacting a metal, a metal oxide, a metal alkoxide, a metal carbonyl, a metal halide or an organic acid metal (also collectively referred to herein as a “metal compound”) and preferred.

Therefore, as another aspect of the present invention, the above phthalonitrile compounds (A) to (C) are reacted with metals, metal oxides, metal alkoxides, metal carbonyls, metal halides or organic acid metals (cyclization reaction). A mixture of phthalocyanine-based compounds can also be provided, obtained by

Z ₁ to Z ₁₂ in the above formulas (A) to (C), Z ₁₃ to Z ₁₈ in the above formula (D), and Z ₁₉ to Z ₂₇ in the above formula (D′) are the desired Defined by the structure of the phthalocyanine compound. The phthalonitrile compounds (A) to (C) represented by the above formulas (A) to (C) may be the same or different.

In the above formulas (A) to (C), Z ₁ to Z ₁₂ are each independently a hydrogen atom, a halogen atom, a substituent (a) represented by the above formula (a), and a substituent represented by the above formula (b). The structure (b) represented by the formula (b') or the structure (b') represented by the above formula (b') is represented. At this time, at least one of Z ₁ to Z ₁₂ is the substituent (a). Here, the halogen, the substituent (a), the structure (b) and the structure (b') are the same as those described for A ₁ to A ₁₆ in the section [Phthalocyanine compound] above, so here Description is omitted.

In the above formulas (D) and (D'), Z ₁₉ to Z ₂₇ are each independently a hydrogen atom, a halogen atom, a substituent (a) represented by the above formula (a), the above formula (b) represents the structure (b) represented by or the structure (b') represented by the above formula (b'). In formula (D) above, Y is a divalent organic group, and in formula (D') above, Y is a trivalent organic group. Here, the halogen, substituent (a), structure (b) and structure (b′) are the same as those described for A ₁ to A ₁₆ in the section [Phthalocyanine compound] above, and are divalent or Since Y as a trivalent organic group is also the same as Y in the section [Phthalocyanine compound] above, the description is omitted here. When the phthalonitrile compound derivative (D) or (D') has the structure (b) or (b'), the binding site indicated by "*" in the above formulas (b) and (b') is Two adjacent substitutions of Z ₁₃ to Z ₁₅ , Z ₁₆ to Z ₁₈ in the above formula (D) and Z ₁₉ to Z ₂₁ , Z ₂₂ to Z ₂₄ and Z ₂₅ to Z ₂₇ in the above formula (D') represents the site to be bonded as a group.

When producing a phthalocyanine compound in the form represented by the above formula (1) or (3), the phthalonitrile compounds (A) to (C) represented by the above formulas (A) to (C) and the above formulas A cyclization reaction is performed using a dimer of the phthalonitrile compound represented by (D) (phthalonitrile compound derivative) and a metal compound.

When producing a phthalocyanine compound in the form represented by the above formula (2), the phthalonitrile compounds (A) to (C) represented by the above formulas (A) to (C) and the above formula (D') A trimer (phthalonitrile compound derivative) of a phthalonitrile compound represented by and a metal compound are used to perform a cyclization reaction.

When the desired phthalocyanine compound has structure (b), dicyanonaphthalene derivatives (naphthalonitrile compounds) (eg, 2,3-dicyanonaphthalene) are used as phthalonitrile compounds (A) to (C). may Further, when the desired phthalocyanine compound has structure (b'), dihydroxybiphenyl compounds (eg, 2,2'-dihydroxybiphenyl) may be used as phthalonitrile compounds (A) to (C).

Phthalonitrile compounds (A) to (C) represented by the above formulas (A) to (C), which are starting materials, are disclosed in JP-A-64-45474, JP-A-2009-242791, and JP-A-2011-12167. It can be synthesized by a conventionally known method disclosed in JP-A-2002-302477 and the like, and a commercially available product can also be used. Further, the phthalonitrile compound having a substituent (a) is preferably a halogenated phthalonitrile compound and the formula (a'):

It is obtained by appropriately reacting the compound represented by. Note that R ₁ and p in the above formula (a′) are the same as the definitions related to the substituent (a) explained in the section [Phthalocyanine-based compound] above, so the explanation is omitted here.

Examples of the halogenated phthalonitrile compound include, but are not limited to, tetrafluorophthalonitrile, tetrachlorophthalonitrile, and the like. Among them, tetrafluorophthalonitrile is preferable in consideration of the position selectivity of the substituent.

When a naphthalonitrile compound (2,3-dicyanonaphthalene or its derivative) or a dihydroxybiphenyl compound (2,2'-dihydroxybiphenyl or its derivative) is used as the phthalonitrile compound, a conventionally known method can be used. It may be synthesized or a commercially available product may be used.

Phthalonitrile compound derivatives (D) and (D') represented by the above formulas (D) and (D'), which are starting materials, are disclosed in JP-A-64-45474, JP-A-2009-242791, and JP-A-2009-242791. 2011-12167, JP-A-2002-302477, etc., and can be synthesized by appropriately modifying and applying the known methods.

Specifically, a halogenated phthalonitrile compound, a compound represented by the above formula (a′), and a dihydroxy compound represented by the following formula (d), or represented by the following formula (d′) By coupling a trivalent hydroxy compound in the presence of a basic compound such as potassium carbonate, sodium carbonate, calcium carbonate, potassium hydroxide, sodium hydroxide, calcium hydroxide, potassium fluoride, sodium fluoride, etc. Synthesis is preferred.

The metal compound used in the cyclization reaction for obtaining the phthalocyanine compound is not particularly limited, but the metals exemplified in the section of (central metal (M)) in the above formulas (1) to (3); alkoxides of these metals; metal carbonyls of these metals; metal halides such as chlorides, bromides and iodides of these metals; organic acid metals of these metals;

Specifically, metals such as iron, magnesium, nickel, cobalt, copper, palladium, zinc, vanadium, titanium, indium, tin; vanadium monoxide, vanadium trioxide, vanadium tetroxide, vanadium pentoxide, titanium dioxide, iron oxide, iron sesquioxide, iron tetraoxide, manganese oxide, nickel monoxide, cobalt monoxide, cobalt sesquioxide, cobalt dioxide, cuprous oxide, cupric oxide, copper sesquioxide, palladium oxide, zinc oxide, metal oxides such as germanium monoxide and germanium dioxide; metal alkoxides such as methoxyindium; metal carbonyls such as cobalt carbonyl, iron carbonyl, and nickel carbonyl; vanadium chloride, titanium chloride, copper chloride, zinc chloride, cobalt chloride, nickel chloride , iron chloride, indium chloride, aluminum chloride, tin chloride, gallium chloride, germanium chloride, magnesium chloride, copper iodide, zinc iodide, cobalt iodide, indium iodide, aluminum iodide, gallium iodide, copper bromide, metal halides such as zinc bromide, cobalt bromide, aluminum bromide and gallium bromide; organic acid metals such as copper acetate, zinc acetate, cobalt acetate, copper benzoate and zinc benzoate; acetylacetonate complexes of the above metals and complex compounds such as

Among these, metals, metal oxides and metal halides are preferred, metal halides are more preferred, and vanadium chloride, vanadium iodide, copper chloride, copper iodide, zinc chloride and iodide are more preferred. Zinc, more preferably vanadium chloride, copper chloride and zinc iodide.

Moreover, although the cyclization reaction can be carried out without a solvent, it is preferably carried out using an organic solvent. The organic solvent may be any inert solvent having low reactivity, preferably no reactivity, with the phthalonitrile compound and naphthalonitrile compound as starting materials, for example, benzene, toluene, xylene, nitrobenzene. , monochlorobenzene, o-chlorotoluene, dichlorobenzene, trichlorobenzene, 1-chloronaphthalene, 1-methylnaphthalene, inert solvents such as benzonitrile; methanol, ethanol, 1-propanol, 2-propanol, 1 - alcohols such as butanol, 1-hexanol, 1-pentanol, 1-octanol, ethylene glycol, diethylene glycol monomethyl ether; pyridine, N,N-dimethylformamide, N,N-dimethylacetamide, N-methyl-2-pyrrolidinone, Aprotic polar solvents such as N,N-dimethylacetophenone, triethylamine, tri-n-butylamine, dimethylsulfoxide, sulfolane, and the like. Among these, 1-chloronaphthalene, 1-methylnaphthalene, 1-octanol, dichlorobenzene and benzonitrile are preferred, and 1-octanol and benzonitrile are more preferred. These solvents may be used singly or in combination of two or more. The amount of the organic solvent used when using the organic solvent is not particularly limited, but the phthalonitrile compounds (A) to (C) represented by the formulas (A) to (C) and the formula (D) are represented by The total concentration (total amount) of the phthalonitrile compound derivative (D) or the phthalonitrile compound derivative (D′) represented by formula (D′) is preferably from 2 to 80% by weight, preferably from 10 to 70% by weight. %, and particularly preferably 15 to 60% by weight.

The reaction conditions for the phthalonitrile compounds (A) to (C), the phthalonitrile compound derivative (D) or (D'), and the metal compound are not particularly limited as long as the reaction proceeds. For example, the reaction temperature is preferably 100-240°C, more preferably 130-200°C. The reaction time is also not particularly limited, but is preferably 1 to 72 hours, more preferably 3 to 48 hours, and particularly preferably 5 to 30 hours. The amount of the metal compound added is not particularly limited, but 0.8 per 4 mol in total of the phthalonitrile compounds (A) to (C) and the phthalonitrile compound derivative (D) or (D'). It is preferably up to 2 mol, more preferably 1.0 to 1.5 mol.

The above reaction may be carried out in an air atmosphere, but depending on the type of metal compound, an inert gas or oxygen-containing gas atmosphere (e.g., nitrogen gas, helium gas, argon gas, oxygen/nitrogen mixed gas, etc.) may be used. under circulation).

After the above cyclization reaction, crystallization, filtration, washing and drying may be carried out according to conventionally known methods. By such operation, a phthalocyanine compound can be efficiently obtained. In addition, depending on the type of phthalonitrile compounds (A) to (C) and phthalonitrile compound derivative (D) or (D') used, by-products having different positions of substituents and different number of introduced substituents are produced. An operation of separating the phthalocyanine-based compound from other phthalocyanine-based compounds may be performed. Examples of such separation means include column chromatography and the like.

A mixture containing a phthalocyanine compound and by-products produced by the above method (herein sometimes simply referred to as a “mixture of phthalocyanine compounds” or “mixture”) is obtained by superimposing absorption spectra (absorption bands). The combination broadens the absorption band of the absorption spectrum of the mixture. Therefore, it is presumed that the mixture of phthalocyanine compounds produced by the above method has a further improved heat absorption effect.

[Heat ray absorbing material]
The phthalocyanine-based compound according to the present invention has good heat absorption ability and visible light transmittance, and high light resistance. That is, the phthalocyanine compound according to the present invention selectively absorbs light in the near-infrared region with high light intensity, increases the transmittance in the visible light wavelength region (that is, while ensuring transparency), In addition to being excellent in action and effect of effectively absorbing/blocking heat from sunlight, the action and effect are excellent in sustainability. In addition, the phthalocyanine compound according to the present invention is excellent in heat resistance, and yellowing after light irradiation is also suppressed.

Furthermore, the phthalocyanine-based compound according to the present invention exhibits particularly high visible light transmittance when used in combination with a resin, compared to conventional phthalocyanine-based compounds. Furthermore, the phthalocyanine compound according to the present invention has excellent compatibility with resins, excellent light resistance, heat resistance, and weather resistance, and exhibits excellent effects as a heat ray absorbing material without impairing its properties.

Therefore, the phthalocyanine compound according to the present invention can impart the above effects to the heat ray absorbing material. Therefore, as another aspect of the present invention, there is provided a heat ray absorbing material containing the above phthalocyanine compound. Furthermore, as a more preferable form of the other form, a heat ray absorbing material containing a phthalocyanine compound represented by the above formula (1), (2) or (3) is provided. The phthalocyanine-based compound represented by the above formula (1), the phthalocyanine-based compound represented by the above formula (2), and the phthalocyanine-based compound represented by the above formula (3) are each alone in the heat ray absorbing material. It may be contained, or may be contained in the form of a mixture of two or more. Further, the phthalocyanine compounds represented by the above formulas (1) to (3) may be contained in the heat ray absorbing material in combination of one or more of each.

The heat-absorbing material according to the present invention has high light resistance while maintaining good heat-absorbing ability and transparency. Therefore, the heat-absorbing material of the present invention is used for vehicles (for example, automobiles, buses, trains, etc.) and heat-absorbing laminated glass (heat-shielding interlayer film for laminated glass), heat-shielding films, heat-shielding resin glass, heat-ray It can be suitably used for reflective glass. For example, when it is used as heat-absorbing glass for windows of automobiles and buildings, it is possible to effectively suppress the temperature rise in the interior of the vehicle and to ensure good visibility. The heat-absorbing material according to the present invention has a high transmittance in the range of 400 to 600 nm, and particularly easily transmits light (blue to green light) with wavelengths around 460 nm and 510 nm. Therefore, it is possible to improve the visibility of an LED lamp that emits blue to green light. Therefore, for example, since the visibility of headlights using LEDs is improved, the heat-absorbing material according to the present invention can be suitably used as an intermediate film for vehicle windshields (heat-absorbing laminated glass).

The heat absorbing material according to the present invention contains the phthalocyanine compound according to the present invention (preferably the phthalocyanine compound represented by the above formula (1), (2) or (3)). Therefore, the heat ray absorbing material according to the present invention can be applied as a conventional heat ray absorbing material except for using the phthalocyanine compound.

The form of the heat-absorbing material according to the present invention is not particularly limited, and may be any known form. In addition to the phthalocyanine compound represented by formula (1) or (2) or (3)), it contains a resin. Therefore, the heat-absorbing material according to the present invention preferably further contains a resin in addition to the phthalocyanine-based compound according to the present invention. Hereinafter, a composition containing a phthalocyanine-based compound and a resin may also be referred to as a "resin composition".

In particular, it was found that the phthalocyanine-based compound according to the present invention has a significantly higher visible light transmittance than the phthalocyanine-based compound according to the prior art, even when mixed with a resin. Although the detailed reason for this is unknown, it is considered as follows. Conventional phthalocyanine compounds tend to have a broadened absorption spectrum (absorption band) in the resin, resulting in a decrease in visible light transmittance. However, it is believed that the phthalocyanine compound according to the present invention has a structure that satisfies (i) or (ii) above, thereby suppressing broadening of the absorption spectrum (absorption band) in the resin.

Furthermore, the phthalocyanine compound according to the present invention is excellent in solvent solubility and compatibility with resins, and is excellent in various properties such as light resistance, heat resistance and weather resistance. Therefore, it has excellent applicability to plastic films and the like, and industrial application to a large area (mass production) is possible. Similarly, since it can be directly kneaded into resin, large-scale molding (mass production) is also possible.

The content of the phthalocyanine-based compound in the heat-absorbing material is appropriately selected depending on the application or the thickness of the resin. More preferably, it is up to 10 parts by weight. By setting the amount in such a range, it is possible to obtain a heat absorbing material having heat absorbing power and visible light transmittance suitable for the application and excellent light resistance. The visible light transmittance of the heat-absorbing material according to the present invention is preferably 70% or more, more preferably 80% or more. Moreover, the transmittance of light of 460 nm is preferably 70% or more, more preferably 80% or more. In addition, the said transmittance|permeability employ|adopts the value measured by the method of Example description.

The resin contained in the heat-absorbing material is not particularly limited as long as it can be used in general optical materials, but highly transparent resins are preferred, and specific examples include polyethylene, polypropylene, carboxylated polyolefin, and chlorinated polyolefin. , polyolefin resins such as cycloolefin polymers; polystyrene resins; (meth) acrylic acid ester resins; vinyl acetate resins; vinyl halide resins; vinyl resins such as polyvinyl alcohol; polyamide resins such as nylon; polyester resins such as polyethylene terephthalate (PET) and polyarylate (PAR); polycarbonate resins; epoxy resins; polyether sulfone resins; polyaryl ether resins such as polyether ether ketone; Examples include polyvinyl acetal resins such as polyvinyl formal resins. The above resins may be used singly or in combination of two or more.

Among these, those that can be melted or dissolved are preferably used. At this time, a resin composition that can be molded can be obtained by using a meltable resin and kneading the phthalocyanine compound into the resin. Here, since the phthalocyanine compound according to the present invention is also excellent in heat resistance, it is possible to adopt a molding method excellent in productivity such as injection molding and extrusion molding using a thermoplastic resin.

Among them, resins contained in the heat-absorbing material according to the present invention include (meth)acrylic acid ester-based resin; vinyl acetate-based resin; polyester-based resin; polycarbonate-based resin; polyethersulfone-based resin; It is preferable to include at least one selected from polyvinyl acetal-based resins. Furthermore, the resin contained in the heat-absorbing material preferably has an ether bond because it has excellent compatibility with the phthalocyanine-based compound according to the present invention and a particularly high visible light transmittance can be obtained. Furthermore, from the same point of view, it is particularly preferable that the resin contained in the heat-absorbing material contains a polyvinyl acetal-based resin. In particular, when the heat-absorbing material contains a phthalocyanine compound represented by the above formula (1) or (2) or (3), the ether bond or hydroxyl group contained in the polyvinyl acetal resin is replaced by the phenoxy group in the phthalocyanine compound. Since it easily interacts with (substituent (a)) and the like, it is presumed that the above effect can be obtained more effectively.

Also, by dissolving the phthalocyanine compound in a resin that can be dissolved, a resin composition that can be coated can be obtained. Examples of such resins include (meth)acrylic acid ester-based resins and polyester-based resins.

The molecular weight of the resin is not particularly limited, but the polystyrene-equivalent weight-average molecular weight is preferably 10,000 or more, more preferably 20,000 or more. On the other hand, although the upper limit of the molecular weight is not particularly limited, it is preferably about 500,000 or less.

The polymer structure of the resin is not limited and may be linear or branched, but the branched type is preferable to the linear type because the resin is less likely to crack and has higher durability. When the branched structure is used, the viscosity of the resin is low even when the molecular weight is increased, and the handling becomes easy. Macromonomers, polyfunctional monomers, polyfunctional initiators, and polyfunctional chain transfer agents can be used to obtain branched resins.

Also, the resin may be a pressure-sensitive adhesive or adhesive, or a mixture thereof. When a pressure-sensitive adhesive or adhesive is used, the heat ray absorbing material can be produced easily and economically because it can be attached to other functional films.

Examples of resins suitable for the pressure-sensitive adhesive include acrylic, silicone, and SBR. Particularly preferred are polymers obtained by polymerizing ethyl acrylate, butyl acrylate, 2-ethylhexyl acrylate, n-octyl acrylate, etc. as a main component. mentioned. Furthermore, a suitable adhesive is an acrylic resin obtained by copolymerizing a (meth)acrylic acid ester having an alicyclic alkyl group such as a cyclohexyl group or an isobornyl group. It is also possible to copolymerize a (meth)acrylic acid ester having an acidic group such as a carboxyl group.

Examples of resins suitable for the above adhesive include polyolefins such as general silicon, urethane, acrylic, ethylene-vinyl acetate copolymer, carboxylated polyolefin, and chlorinated polyolefin.

The heat-absorbing material may further contain a solvent. Such a solvent is not limited as long as it can dissolve or disperse the phthalocyanine compound and resin according to the present invention. For example, aliphatics such as cyclohexane and methylcyclohexane; aromatics such as toluene and xylene; ketones such as acetone, methyl ethyl ketone and methyl isobutyl ketone; esters such as ethyl acetate and butyl acetate; nitriles such as acetonitrile; , ethanol, isopropyl alcohol, 2-methoxyethanol; ethers such as tetrahydrofuran and dibutyl ether; glycol ethers such as butyl cellosolve, propylene glycol n-propyl ether, propylene glycol n-butyl ether, propylene glycol monomethyl ether acetate; Ether esters such as triethylene glycol di-(2-ethyl) butyrate and triethylene glycol di-(2-ethyl) hexanoate; amides such as formamide and N,N-dimethylformamide; halogens such as methylene chloride and chloroform is mentioned. These may be used alone or in combination. Solvents having a boiling point of 100° C. or less, such as methyl ethyl ketone, ethyl acetate, and tetrahydrofuran, are suitable for improving durability. Solvents having a boiling point of 100 to 150° C., such as toluene, methyl isobutyl ketone, and butyl acetate, are suitable for improving the coating film appearance during coating. Solvents having a boiling point of 150 to 200° C. such as butyl cellosolve, propylene glycol n-propyl ether, propylene glycol n-butyl ether and propylene glycol monomethyl ether acetate are suitable for improving the crack resistance of the coating film.

The heat-absorbing material according to the present invention may further contain a visible light-absorbing dye, a near-infrared absorbing agent, and an ultraviolet absorbing agent (hereinafter collectively referred to as "other absorbents"). By further using other absorbers in this way, it is possible to absorb light in the wavelength range that the phthalocyanine compound according to the present invention cannot absorb or does not sufficiently absorb. Among them, it is more preferable to contain a near-infrared absorbing agent in order to improve heat absorption efficiency.

Here, the visible light absorbing dye is not particularly limited, and includes cyanine-based, tetraazaporphyrin-based, azulenium-based, squarylium-based, diphenylmethane-based, triphenylmethane-based, oxazine-based, azine-based, thiopyrylium-based, viologen-based, azo system, azo metal complex salt system, bisazo system, anthraquinone system, perylene system, indanthrone system, nitroso system, metal thiol complex system, indico system, azomethine system, xanthene system, oxanol system, indoaniline system, quinoline system, etc. of dyes can be widely used. For example, Adeka Arkles (registered trademark, hereinafter the same) TW-1367, Adeka Arkles SG-1574, Adeka Arkles TW1317, Adeka Arkles FD-3351, Adeka Arkles Y944 (all manufactured by ADEKA Co., Ltd.), NK -5451, NK-5532, NK-5450 (all manufactured by Hayashibara Biochemical Laboratories) and the like. The visible light absorbing colorant may be a dye that dissolves in a solvent, or may be a pigment that is finely divided to such an extent that haze does not pose a problem.

Further, the near-infrared absorbing agent is not particularly limited, and a known near-infrared absorbing agent can be appropriately selected according to the desired maximum absorption wavelength depending on the application. Here, the maximum absorption wavelength of the near-infrared absorbent is preferably 750 nm or longer, more preferably 800 nm or longer. Here, the maximum value of the maximum absorption wavelength is not particularly limited, but is preferably 1500 nm or less, particularly preferably 1000 nm or less. By using a near-infrared absorbent that absorbs light in this wavelength range, it is possible to absorb light in a wavelength range that the phthalocyanine compound according to the present invention cannot absorb or does not sufficiently absorb, so that the heat ray shielding effect can be further improved. . The near-infrared absorber as another absorber is a dye different from the phthalocyanine compound according to the present invention. The near-infrared absorbing dye as such other absorber is not particularly limited and can be appropriately selected so as to obtain a desired absorption spectrum. More specifically, described in JP-A-2000-26748, JP-A-2001-106689, JP-A-2004-018561, JP-A-2007-56105, JP-A-2011-116918, etc. A near-infrared absorbing dye using a phthalocyanine compound is included. Further, a commercially available near-infrared absorbing dye may be used as another absorber. Commercially available products include IR-915, IR-12, IR-14, IR-20 and HA-1 (all of which are phthalocyanine compounds manufactured by Nippon Shokubai Co., Ltd.).

Further, the ultraviolet absorber is not particularly limited, and known ultraviolet absorbers can be used. Specifically, salicylic acid-based, benzophenone-based, benzotriazole-based, hindered amine-based, and cyanoacrylate-based compounds are preferably used. Hindered amines are particularly preferred.

The above-mentioned other absorbents may be used alone, or two or more of them may be mixed and used, and can be appropriately selected depending on the application. Preferably, the heat-absorbing material according to the present invention further contains a near-infrared absorbing dye, more preferably a near-infrared absorbing dye having a maximum absorption wavelength of 800 nm or more.

The content of the other absorbents in the heat-absorbing material is not particularly limited, and cannot be determined unconditionally because the required absorption wavelength range, visible light transmittance, and solar transmittance differ depending on the application. An example of the content of the other absorbent is preferably 0.001 to 10 parts by weight, more preferably 0.005 to 8 parts by weight, per 100 parts by weight of the solid content of the resin. Also, the mixing ratio with the phthalocyanine compound according to the present invention is not particularly limited, but it is assumed that 1 to 1000 parts by weight of other absorbent is contained with respect to 100 parts by weight of the phthalocyanine compound according to the present invention. More preferably, it is contained in an amount of 10 to 500 parts by weight. Within this range, the solar transmittance can be reduced without affecting the visible light transmittance. The visible light transmittance is preferably 70% or more, more preferably 80% or more.

Moreover, the heat-absorbing material according to the present invention may further contain a heat-absorbing inorganic compound (inorganic heat-absorbing material) having a maximum absorption wavelength of 800 nm or more. By using the heat-absorbing inorganic compound (inorganic heat-absorbing material) in this way, the heat-absorbing ability in the near-infrared region, in which the absorption ability of the phthalocyanine-based compound according to the present invention is low, can be improved. That is, in the above-described heat-absorbing material, a form further including a heat-absorbing inorganic compound (inorganic heat-absorbing material) having a maximum absorption wavelength of 800 nm or more is also one of preferred embodiments of the present invention. In addition, a mode in which the heat-absorbing material further contains at least one of a near-infrared absorbing dye having a maximum absorption wavelength of 800 nm or more and a heat-absorbing inorganic compound (inorganic heat-absorbing material) having a maximum absorption wavelength of 800 nm or more is also of the present invention. This is one of the preferred forms.

As the heat-absorbing inorganic compound (inorganic heat-absorbing material), those having heat-absorbing ability or ultraviolet-ray absorbing ability are preferable. Specifically, zinc oxide, titanium oxide, tin oxide, indium oxide, indium tin oxide, alkali metal-doped tungsten oxide such as cesium-doped tungsten oxide ( _CsWO3 ), antimony oxide, antimony-doped tin oxide (ATO), antimonic acid zinc, lanthanum hexaboride, and the like. The heat-absorbing inorganic compound (inorganic heat-absorbing material) having a heat-absorbing ability has a wavelength range of 900 nm or more, preferably 1100 nm or more, more preferably 1200 nm or more, which is a wavelength range that cannot be absorbed by the phthalocyanine-based compound or organic dye according to the present invention. can be absorbed, and the solar transmittance can be reduced while maintaining the visible light transmittance. More preferred are alkali metal-doped tungsten oxide, indium tin oxide and antimony-doped tin oxide. Specifically, examples of alkali metal-doped tungsten oxide include SG-IRC90SPM (manufactured by Sukgyung). Examples of indium tin oxide include PI-3 (manufactured by Mitsubishi Materials). Examples of antimony-doped tin oxide include SNS-10M, SNS-10T, SN100P, SN-100D, FS-10P, and FS-10D (all manufactured by Ishihara Sangyo). These are fine particles and preferably have an average dispersed particle diameter of 0.001 to 0.2 μm, more preferably 0.005 to 0.15 μm. Such a range is preferable because it does not impair the transparency.

The content of the heat-absorbing inorganic compound (inorganic heat-absorbing material) in the heat-absorbing material is not particularly limited. unable to decide. An example of the content of the heat-absorbing inorganic compound (inorganic heat-absorbing material) is preferably 1 to 1000 parts by weight, more preferably 10 to 500 parts by weight, with respect to 100 parts by weight of the phthalocyanine compound according to the present invention. is. Within this range, the solar transmittance can be reduced without affecting the visible light transmittance.

In addition, resin curing agents such as isocyanate compounds, thiol compounds, epoxy compounds, amine compounds, imine compounds, oxazoline compounds, silane coupling agents, UV curing agents, etc. are used for the heat absorbing material as long as they do not lose their performance. You may However, a resin composition that does not use a curing agent is more preferable because the coating liquid has a longer pot life and does not require aging.

Furthermore, known additives used in films, coating agents, etc. can be used for the heat absorbing material. Examples include tackifiers, antistatic agents, antioxidants, light stabilizers, quenching agents, curing agents, antiblocking agents, plasticizers, and slip agents.

The form of use of the heat-absorbing material according to the present invention is not particularly limited, and may be any known form. Specifically, a form in which a coating or film containing a phthalocyanine compound is formed on an object (transparent substrate) that preferably absorbs/shields heat rays (form (a)); two objects Mode (mode (b)) of a laminate in which an intermediate layer containing a phthalocyanine compound is provided between objects (transparent substrates); mode (mode (c)) in which the above object contains a phthalocyanine compound etc. Among these, the above forms (a) and (b) are preferred, and the above form (b) is particularly preferred. Furthermore, as the form (b), a form in which two transparent substrates are adhered with a resin composition is preferable.

The thickness of the heat-absorbing material according to the present invention is not particularly limited, and is appropriately determined according to the purpose and application. The thickness (dry film thickness) of the heat-absorbing material is preferably 0.1 μm to 20 mm, more preferably 0.1 μm to 10 mm. Also, the content of the phthalocyanine compound contained in the heat ray absorbing material is appropriately determined according to the purpose and application. If the content of the phthalocyanine-based compound is indicated regardless of the thickness of the heat-absorbing material, the amount is preferably 0.01 to 2.0 g/m ² considering the mass in the projected area from above. , more preferably 0.05 to 1.0 g/m ² . By setting it as such a range, the transmittance|permeability of a visible ray is high, and a sufficient heat ray absorption effect is acquired. Although the visible light transmittance varies depending on the application, the preferable visible light transmittance is 70% or more. More preferably, it is 80% or more.

The object (transparent substrate) that preferably absorbs/shields heat rays is generally usable for optical materials, and is not particularly limited as long as it is substantially transparent. Specific examples include glass, olefin polymers such as cyclopolyolefin and amorphous polyolefin, (meth)acrylic ester resins such as polymethyl methacrylate, vinyl resins such as polystyrene, polycarbonate resins, PET and PAR. Polyester-based resins, polyethersulfone-based resins, polyarylether-based resins, and the like are included. When an inorganic substrate such as glass is used as the transparent substrate, one having a low alkali content is preferable from the viewpoint of dye durability.

When a resin-based material is used as the transparent base material, known additives, heat-resistant antiaging agents, lubricants, antistatic agents, etc. can be added to the resin, and known injection molding, T-die molding, calendar molding can be used. It is formed into a desired shape by a method such as compression molding, or a method of casting after being melted in an organic solvent. Such a transparent base material may be stretched or laminated with other resins, if necessary. In addition, the transparent base material is subjected to surface treatment by conventionally known methods such as corona discharge treatment, flame treatment, plasma treatment, glow discharge treatment, surface roughening treatment, chemical treatment, etc., or to coating such as an anchor coating agent or primer. good too.

A known coating machine can be used to apply the resin composition to the transparent substrate. Examples include knife coaters such as comma coaters, fountain coaters such as slot die coaters and lip coaters, kiss coaters such as micro gravure coaters, roll coaters such as gravure coaters and reverse roll coaters, flow coaters, spray coaters, bar coaters, and spin coaters. be done. Prior to coating, the substrate may be surface-treated by a known method such as corona discharge treatment or plasma treatment. As drying and curing methods, known methods such as hot air, far infrared rays, and UV curing can be used. After drying and curing, it may be wound up together with a known protective film.

When the resin composition is applied, the thickness of the coating film is not limited, but is appropriately determined according to the purpose. The thickness of the coating film is preferably 0.1 μm to 20 mm, more preferably 0.1 μm to 10 mm, still more preferably 1 μm to 10 mm.

In the above form (a), when the heat-absorbing material according to the present invention is in the form of a film, a PET film is preferable as the transparent base material, and a PET film subjected to an adhesion-facilitating treatment is particularly preferable. Specifically, Cosmoshine (registered trademark) A4300 (manufactured by Toyobo Co., Ltd.), Lumirror U34 (manufactured by Toray Industries), Melinex 705 (manufactured by Teijin DuPont), and the like can be mentioned.

In the case of the above film form, the resin used for the heat ray absorbing material is preferably an adhesive resin or a UV curable resin. When a pressure-sensitive adhesive resin or a UV curable resin is used, the coating may be formed on one side or both sides of the film, preferably on one side. When forming a coating film on a film, the coating liquid of the resin composition may be directly applied on the transparent substrate, or the coating liquid of the resin composition applied on the substrate having releasability may be applied to the transparent substrate. It may be transferred onto a substrate. Also, a UV curable coating may be formed on the opposite side of the film. In that case, it is preferable to apply a coating liquid containing the phthalocyanine compound, the UV-curable monomer or oligomer, and the photopolymerization initiator onto the transparent substrate. Moreover, you may apply|coat an adhesive to the opposite surface of a film.

In the above form (b), when the heat-absorbing material is formed by bonding two sheets of transparent substrates with the above resin composition, the transparent substrates are preferably glass or PET film. From the viewpoint of adhesiveness, it is preferable to use a polyvinyl acetal resin (especially a polyvinyl butyral resin) as the resin contained in the resin composition for bonding two glass substrates. Polyvinyl acetal resin (particularly polyvinyl butyral resin) is also preferable from the viewpoint of improving the visible light transmittance as described above.

The method for producing the heat-absorbing material is not particularly limited, but for example, (1) a method of kneading and heat-molding a resin composition, (2) a phthalocyanine-based compound, a curable monomer or oligomer, and a polymerization initiator together with a mold. A method of polymerizing and molding in a frame or the like can be used.

The molding conditions for kneading and heat-molding the resin composition differ depending on the type of resin, but usually, the phthalocyanine compound is melted into a thermoplastic resin powder, kneaded, and then pelletized to form a masterbatch having a high concentration of the phthalocyanine compound. do. A method of further diluting, melting, kneading, and molding the masterbatch with the thermoplastic resin can be mentioned.

The phthalocyanine-based compound used in the heat-absorbing material according to the present invention has excellent heat resistance compared to conventional infrared-absorbing agents. It is possible to adopt a molding method that raises the temperature to a high temperature of 200 to 350° C., and it is possible to obtain a molded article that is excellent in transparency and heat ray shielding performance.

Examples of the thermoplastic resin include olefin resins such as cyclopolyolefin and amorphous polyolefin, (meth)acrylic resins such as polymethyl methacrylate, vinyl resins such as polystyrene, polycarbonate resins, and polyesters such as PET and PAR. resins, polyethersulfone-based resins, polyarylether-based resins, and the like.

Further, the curable monomer or oligomer used in the method of polymerizing and molding in a mold (method (2) above) with a phthalocyanine compound, a curable monomer or oligomer, and a polymerization initiator includes (meth) Examples thereof include monomers or oligomers that generate acrylic acid ester resins, epoxy resins, silicon resins, polyimides, and the like. A suitable polymerization initiator can be used depending on the monomer or oligomer.

When molding the resin composition, the shape of the heat-absorbing material is not limited, and can be appropriately formed according to the application. Various shapes such as plate-like, film-like, corrugated plate-like, spherical, and dome-like are included. Although the thickness is not particularly limited, it is preferably 0.05 to 20 mm. Within such a range, sufficient strength and safety as a heat ray absorbing material can be obtained.

The heat-absorbing material according to the present invention is suitable for window films for buildings and vehicles, heat-absorbing laminated glass (heat-shielding interlayer film for laminated glass), heat-absorbing resin glazing, lighting building materials, and the like. A heat-absorbing material obtained by forming a coating film of the resin composition according to the present invention on a film-like transparent substrate can be used as a window film. Window films can be applied to the inside or outside of a building. When used as a window film, it is preferable to provide an ultraviolet absorbing layer on the solar radiation side of the layer containing the phthalocyanine compound. Also, when used as a sheet-like molded body such as a lighting building material, it is preferable to add an ultraviolet absorber to the outermost layer by a multi-layer extrusion method and use the heat ray absorber according to the present invention in the inner layer.

The effects of the present invention will be described using the following examples and comparative examples. However, the technical scope of the present invention is not limited only to the following examples. In the following, unless otherwise specified, room temperature means 25±5°C.

[Synthesis Example 1-1: Synthesis of dimerized phthalonitrile intermediate (a) (intermediate for synthesis of phthalocyanine compound (i))]
First, according to the method described in Example 1 of JP-A-2002-302477, 3-(2,6-dimethylphenoxy)-4,5-bis(2,5-dimethylphenoxy)-6-fluorophthalo I got the nitrile.

A 50 ml reactor was then charged with 4 g of 3-(2,6-dimethylphenoxy)-4,5-bis(2,5-dimethylphenoxy)-6-fluorophthalonitrile, 0.91 g of bisphenol A and 1.22 g of potassium carbonate. and 25 g of acetonitrile were added and reacted at 80° C. for about 12 hours. The reaction solution was filtered while hot, and after removing inorganic components, the solvent was distilled off from the filtrate under reduced pressure. Thereafter, column purification (filler: silica gel 60N, manufactured by Kanto Kagaku Co., Ltd.) was performed using chloroform as a solvent to obtain the desired dimerized phthalonitrile intermediate (a). When the product was subjected to fluorescent X-ray analysis (apparatus name: ZSX Primus, manufactured by Rigaku Corporation), residual fluorine atoms were not detected. In addition, high-performance liquid chromatography analysis (device name: La Chrom, manufactured by Hitachi High-Tech Co., Ltd.; column: ODS-4, solvent: acetonitrile: water = 9: 1) also confirmed the disappearance of the raw material peak, and the intermediate ( The purity of a) was confirmed to be 99% or higher.

[Synthesis Example 1-2: Synthesis of dimerized phthalonitrile intermediate (b) (phthalocyanine compound (ii), (iii) intermediate for synthesis)]
A dimerized phthalonitrile intermediate (b) was obtained in the same manner as in Synthesis Example 1-1, except that 0.91 g of bisphenol A was changed to 0.44 g of hydroquinone. Analysis was performed in the same manner as in Synthesis Example 1-1, and residual fluorine atoms were not detected in the product. Moreover, disappearance of the raw material peak was also confirmed by high-performance liquid chromatography analysis, and it was confirmed that the purity of intermediate (b) was 99% or more.

[Synthesis Example 1-3: Synthesis of dimerized phthalonitrile intermediate (c) (intermediate for synthesis of phthalocyanine compound (iv))]
A 50 ml reactor was charged with 1.6 g of 3,4,5,6-tetrafluorophthalonitrile, 2.72 g of 2-phenylphenol, and 25 g of acetonitrile. While the mixture was maintained at 5°C, 2.43 g of potassium carbonate was added successively, then the temperature was raised to 50°C and the reaction was allowed to proceed for about 2 hours. After that, 0.75 g of phenol and 1.22 g of potassium carbonate were added, the temperature was raised to 80° C., and the reaction was further performed for 4 hours. After that, 0.44 g of catechol and 1.22 g of potassium carbonate were added and reacted at 80° C. for about 17 hours. The reaction solution was filtered while hot, and after removing inorganic components, the solvent was distilled off from the filtrate under reduced pressure. Thereafter, column purification was performed using chloroform as a solvent (filler: silica gel 60N, manufactured by Kanto Kagaku Co., Ltd.) to obtain the desired dimerized phthalonitrile intermediate (c). Analysis was conducted in the same manner as in Synthesis Example 1-1, and residual fluorine atoms were not detected in the product. In addition, disappearance of the raw material peak was also confirmed by high-performance liquid chromatography analysis, and it was confirmed that the purity of intermediate (c) was 99% or more.

[Synthesis Example 1-4: Synthesis of dimerized phthalonitrile intermediate (d) (intermediate for synthesis of phthalocyanine compound (v))]
A 50 ml reactor was charged with 1.5 g of 3,4,5,6-tetrafluorophthalonitrile, 0.84 g of 4-fluorophenol, and 25 g of acetonitrile. While the mixture was maintained at 5°C, 1.14 g of potassium carbonate was added successively, then the temperature was raised to 50°C and the reaction was allowed to proceed for about 2 hours. After that, 2.55 g of 2-phenylphenol and 2.28 g of potassium carbonate were added, the temperature was raised to 80° C., and the reaction was further performed for 4 hours. After that, 0.413 g of hydroquinone and 1.14 g of potassium carbonate were added and reacted at 80° C. for about 15 hours. The reaction solution was filtered while hot, and after removing inorganic components, the solvent was distilled off from the filtrate under reduced pressure. Thereafter, column purification (filler: silica gel 60N, manufactured by Kanto Kagaku Co., Ltd.) was performed using chloroform as a solvent. The resulting dimerized phthalonitrile intermediate (d) was analyzed in the same manner as in Synthesis Example 1-1, and 8 fluorine atoms were detected in one molecule. Further, high-performance liquid chromatography analysis confirmed the disappearance of the raw material peak, and the purity of the intermediate (d) was 99% or more.

[Synthesis Example 1-5: Synthesis of trimerized phthalonitrile intermediate (e) (phthalocyanine compound (vi), intermediate for synthesis of (ix))]
A trimerized phthalonitrile intermediate (e) was obtained in the same manner as in Synthesis Example 1-1, except that 0.91 g of bisphenol A was changed to 0.336 g of phloroglucinol. Analysis was performed in the same manner as in Synthesis Example 1-1, and residual fluorine atoms were not detected in the product. Moreover, disappearance of the raw material peak was also confirmed by high-performance liquid chromatography analysis, and it was confirmed that the purity of intermediate (e) was 99% or more.

[Synthesis Example 1-6: Synthesis of dimerized phthalonitrile intermediate (f) (intermediate for synthesis of phthalocyanine compound (vii))]
A dimerized phthalonitrile intermediate (f) was obtained in the same manner as in Synthesis Example 1-1, except that 0.91 g of bisphenol A was changed to 0.465 g of 1,4-cyclohexanediol. Analysis was performed in the same manner as in Synthesis Example 1-1, and residual fluorine atoms were not detected in the product. Moreover, disappearance of the raw material peak was also confirmed by high-performance liquid chromatography analysis, confirming that the purity of the intermediate (f) was 99% or more.

[Synthesis Example 1-7: Synthesis of dimerized phthalonitrile intermediate (g) (intermediate for synthesis of phthalocyanine compound (viii))]
A dimerized phthalonitrile intermediate (g) was obtained in the same manner as in Synthesis Example 1-1, except that 0.91 g of bisphenol A was changed to 0.304 g of 1,3-propanediol. Analysis was performed in the same manner as in Synthesis Example 1-1, and residual fluorine atoms were not detected in the product. Moreover, disappearance of the raw material peak was confirmed by high performance liquid chromatography analysis, and the purity of the intermediate (g) was confirmed to be 99% or more.

[Synthesis Example 1-8: Synthesis of trimerized phthalonitrile intermediate (h) (intermediate for synthesis of phthalocyanine compound (ix))]
In the same manner as in Synthesis Example 1-1, except that 0.91 g of bisphenol A was changed to 0.817 g of 1,1,1-tris(4-hydroxyphenyl)ethane and the amount of potassium carbonate was changed to 1.22 g. Trimerized phthalonitrile intermediate (h) was obtained. Analysis was performed in the same manner as in Synthesis Example 1-1, and residual fluorine atoms were not detected in the product. Moreover, disappearance of the raw material peak was also confirmed by high performance liquid chromatography analysis, confirming that the purity of the intermediate (h) was 99% or more.

[Synthesis Example 2-1: Synthesis of Monomeric Phthalonitrile Intermediate (a′) (Intermediate for Synthesis of Phthalocyanine Compounds (i) to (iii) and (vi) to (ix))]
A monomeric phthalonitrile intermediate (a′) was obtained in the same manner as in Synthesis Example 1-1, except that 0.91 g of bisphenol A was changed to 0.98 g of 2,5-dimethylphenol. Analysis was performed in the same manner as in Synthesis Example 1-1, and residual fluorine atoms were not detected in the product. In addition, disappearance of the raw material peak was also confirmed by high-performance liquid chromatography analysis, confirming that the purity of the intermediate (a') was 99% or more.

[Synthesis Example 2-2: Synthesis of Monomeric Phthalonitrile Intermediate (b′) (Intermediate for Synthesis of Phthalocyanine Compound (iv))]
A monomeric phthalonitrile intermediate (b') was obtained in the same manner as in Synthesis Example 1-3, except that 0.44 g of catechol was changed to 1.36 g of 2-phenylphenol. Analysis was conducted in the same manner as in Synthesis Example 1-1, and residual fluorine atoms were not detected in the product. Moreover, disappearance of the raw material peak was also confirmed by high-performance liquid chromatography analysis, confirming that the purity of the intermediate (b') was 99% or more.

[Synthesis Example 2-3: Synthesis of Monomeric Phthalonitrile Intermediate (c′) (Intermediate for Synthesis of Phthalocyanine Compound (v))]
A monomeric phthalonitrile intermediate (c′ ). Analysis was conducted in the same manner as in Synthesis Example 1-1, and residual fluorine atoms were not detected in the product. In addition, disappearance of the raw material peak was also confirmed by high-performance liquid chromatography analysis, and it was confirmed that the purity of the intermediate (c') was 99% or more.

[Synthesis Example 2-4: Synthesis of monomeric phthalonitrile intermediate (d') (intermediate for synthesis of comparative phthalocyanine compound (i))]
A monomeric phthalonitrile intermediate (d') was obtained in the same manner as in Synthesis Example 1-1, except that 0.91 g of bisphenol A was changed to 0.75 g of phenol. Analysis was performed in the same manner as in Synthesis Example 1-1, and residual fluorine atoms were not detected in the product. Moreover, disappearance of the raw material peak was also confirmed by high-performance liquid chromatography analysis, and it was confirmed that the purity of the intermediate (d') was 99% or more.

[Synthesis Example 3-1: Monomer phthalonitrile intermediate (a″) {(2,2′-PhOPhO) (2-PhOPhO) (PhO) PN} (intermediate for synthesis of phthalocyanine compound (x) (xii) )]
2 g of 3,4,5,6-tetrafluorophthalonitrile, 1.86 g of 2,2'-dihydroxybiphenyl, and 30 g of acetonitrile are added to a 50 ml reactor, and 2.9 g of potassium carbonate is added while maintaining the temperature at about 5°C. and stirred for 30 minutes. After that, the temperature was raised to 60° C. and after reacting for 1 hour, 1.7 g of 2-phenylphenol and 1.52 g of potassium carbonate were added and reacted at 80° C. for about 6 hours. After that, 0.94 g of phenol and 1.52 g of potassium carbonate were added and reacted at 80° C. for about 6 hours. The reaction solution was filtered while hot, and after removing inorganic components, the solvent was distilled off from the filtrate under reduced pressure. Thereafter, column purification (filler: silica gel 60N, manufactured by Kanto Kagaku Co., Ltd.) was performed using chloroform as a solvent to obtain the target phthalonitrile intermediate (a″).

[Synthesis Example 3-2: Monomeric phthalonitrile intermediate (b″) {(2,2′-PhOPhO)(2,6-(CH ₃ ) ₂ PhO)(PhO)PN} (phthalocyanine compound (xi) Synthesis of synthetic intermediates)]
In Synthesis Example 3-1, the desired phthalonitrile intermediate ( b'') was obtained.

[Synthesis Example 3-3: Dimerized phthalonitrile intermediate (c″) {(2,2′-PhOPhO) ₂ (2-PhOPhO) ₂ (2,4-OPhO) PN} (for synthesis of phthalocyanine compound (x) Synthesis of intermediates)]
In Synthesis Example 3-1, the intended dimerized phthalonitrile intermediate (c″) was obtained in the same manner as in Synthesis Example 3-1, except that 0.55 g of hydroquinone was used instead of phenol. .

[Synthesis Example 3-4: Dimerized phthalonitrile intermediate (d″) {(2,2′-PhOPhO) ₂ (2,6-(CH ₃ ) ₂ PhO) ₂ (2,4-OPhO)PN} ( Synthesis of phthalocyanine compound (xi) intermediate for synthesis)]
A reaction was carried out in the same manner as in Synthesis Example 3-2 except that 0.55 g of hydroquinone was used instead of phenol in Synthesis Example 3-2. After completion of the reaction, the reaction solution was poured into 70 g of water to precipitate crystals. After suction filtration, the mixture was washed with 70 g of water with stirring again and dried at 80° C. overnight to obtain the target dimerized phthalonitrile intermediate (d″).

[Synthesis Example 3-5: Trimerized phthalonitrile intermediate (e″) [(2,2′-PhOPhO) ₃ (2-PhPhO) ₃ {(4-CH ₃ PhO)CH ₂ (4-CH ₃ PhO) Synthesis of CH ₂ (4-CH ₃ PhO)}PN] (intermediate for synthesis of phthalocyanine compound (xii))]
Synthesis Example 3-1, except that 1.16 g of 2,6-bis[(2-hydroxy-5-methylphenyl)methyl]-4-methylphenol was used instead of phenol in Synthesis Example 3-1. By operating in the same manner, the desired trimerized phthalonitrile intermediate (e″) was obtained.

<Example 1: Phthalocyanine compound (i) [(2,5-Me ₂ PhO) ₁₆ (2,6-Me ₂ PhO) ₈ (2,5-Me ₂ PhO) ₆ (OPhC(Me ₂ )PhO) Synthesis of (CuPc) ₂ ]>
1.2 g of the dimerized phthalonitrile intermediate (a) obtained in Synthesis Example 1-1 and 3.65 g of the monomeric phthalonitrile intermediate (a') obtained in Synthesis Example 2-1 were placed in a 50 ml reactor. , 0.218 g of copper (I) chloride, 5 g of benzonitrile and 3 g of 1-octanol were added and stirred at 190° C. for 12 hours under a nitrogen gas atmosphere. After cooling the mixture to 25° C., the reaction solution was added dropwise to methanol for crystallization. After the precipitate was collected by filtration, it was dried under reduced pressure to obtain a crude product. Thereafter, column purification was performed using chloroform as a solvent (filler: silica gel 60N, manufactured by Kanto Kagaku Co., Ltd.) to obtain 2.79 g of phthalocyanine compound (i) (64 mol % yield based on intermediate (a)).

<Example 2: Phthalocyanine compound (ii) [(2,5-Me ₂ PhO) ₁₆ (2,6-Me ₂ PhO) ₈ (2,5-Me ₂ PhO) ₆ (1,4-OPhO) (CuPc ) ₂ ]>
In the same manner as in Example 1, except that 1.2 g of the dimerized phthalonitrile intermediate (a) was changed to 1.08 g of the dimerized phthalonitrile intermediate (b) obtained in Synthesis Example 1-2. 2.37 g of phthalocyanine compound (ii) (56 mol % yield based on intermediate (b)) were obtained.

<Example 3: Phthalocyanine compound (iii) [(2,5-Me ₂ PhO) ₁₂ (2,6-Me ₂ PhO) ₆ (2,5-Me ₂ PhO) ₄ (Np) ₂ (1,4- Synthesis of OPhO)(CuPc) ₂ ]>
Phthalocyanine was prepared in the same manner as in Example 2, except that the amount of the monomeric phthalonitrile intermediate (a′) was changed to 2.43 g, and 0.356 g of 2,3-dicyanonaphthalene was added as an intermediate raw material. 2.8 g of compound (iii) (71 mol % yield based on intermediate (b)) were obtained.

<Example 4: Synthesis of phthalocyanine compound (iv) [(2-PhPhO) ₁₂ (PhO) ₆ (2-PhPhO) ₄ (Np) ₂ (1,2-OPhO)(CuPc) ₂ ]>
1.08 g of the dimerized phthalonitrile intermediate (b) was changed to 1.22 g of the dimerized phthalonitrile intermediate (c) obtained in Synthesis Example 1-3, and the monomeric phthalonitrile intermediate (a') 2.6 g of phthalocyanine compound (iv) in the same manner as in Example 3, except that 2.43 g of the phthalonitrile intermediate (b') obtained in Synthesis Example 2-2 was changed to 2.9 g (59 mol % yield based on intermediate (c)) was obtained.

<Example 5: Synthesis of phthalocyanine compound (v) [(4-FPhO) ₆ (2-PhPhO) ₆ (2-PhPhO) ₁₀ (Np) ₂ (1,4-OPhO) (CuPc) ₂ ]>
1.08 g of the dimerized phthalonitrile intermediate (b) was changed to 1.26 g of the dimerized phthalonitrile intermediate (d) obtained in Synthesis Example 1-4, and the monomeric phthalonitrile intermediate (a') 2.1 g of the phthalocyanine compound (v) was prepared in the same manner as in Example 3, except that 2.43 g of the phthalonitrile intermediate (c′) obtained in Synthesis Example 2-3 was changed to 2.97 g. (60 mol % yield based on intermediate (d)) was obtained.

<Example 6: Phthalocyanine compound (vi) [(2,5-Me ₂ PhO) ₁₈ (2,6-Me ₂ PhO) ₉ (2,5-Me ₂ PhO) ₆ (Np) ₃ (Ph(O) ₃ ) Synthesis of (CuPc) ₃ ]>
1.08 g of the dimerized phthalonitrile intermediate (b) was changed to 1.59 g of the trimerized phthalonitrile intermediate (e) obtained in Synthesis Example 1-5, and the monomeric phthalonitrile intermediate (a') In the same manner as in Example 3, except that the amount of was changed to 3.65 g, the amount of 2,3-dicyanonaphthalene was changed to 0.535 g, and the amount of copper (I) chloride was changed to 0.327 g. 2.1 g of phthalocyanine compound (vi) was obtained (36 mol % yield based on intermediate (e)).

<Example 7: Phthalocyanine compound (vii) [(2,5-Me ₂ PhO) ₁₂ (2,6-Me ₂ PhO) ₆ (2,5-Me ₂ PhO) ₄ (Np) ₂ (1,4- OCyhO)(CuPc) ₂ ]>
In the same manner as in Example 3, except that 1.08 g of the dimerized phthalonitrile intermediate (b) was changed to 1.09 g of the dimerized phthalonitrile intermediate (f) obtained in Synthesis Example 1-6. 2.7 g of phthalocyanine compound (vii) (68 mol % yield based on intermediate (f)) were obtained.

<Example 8: Phthalocyanine compound (viii) [(2,5-Me ₂ PhO) ₁₂ (2,6-Me ₂ PhO) ₆ (2,5-Me ₂ PhO) ₄ (Np) ₂ (1,3- Synthesis of OPrO)(CuPc) ₃ ]>
In the same manner as in Example 3, except that 1.08 g of the dimerized phthalonitrile intermediate (b) was changed to 1.05 g of the dimerized phthalonitrile intermediate (g) obtained in Synthesis Example 1-7. 2.7 g of phthalocyanine compound (viii) (69 mol % yield based on intermediate (g)) were obtained.

<Example 9: Phthalocyanine compound (ix) [(2,5-Me ₂ PhO) ₂₄ (2,6-Me ₂ PhO) ₁₂ (2,5-Me ₂ PhO) ₉ (C(Me)(Ph) ₃ Synthesis of (O) ₃ )(CuPc) ₂ ]>
1.2 g of the dimerized phthalonitrile intermediate (a) was changed to 1.77 g of the trimerized phthalonitrile intermediate (h) obtained in Synthesis Example 1-8, and the monomeric phthalonitrile intermediate (a') 3.2 g of phthalocyanine compound (ix) (intermediate (a) yield 42 mol % based on) was obtained.

<Example 10: Synthesis of phthalocyanine compound (xvi) [(2,2'-PhOPhO) ₇ (2-PhPhO) ₇ (PhO) ₅ (1,4-OPhO)Np(CuPc) ₂ ]>
Into a 50 ml reactor were charged 0.53 g of the dimerized phthalonitrile intermediate (c″) obtained in Synthesis Example 3-3 above and the monomeric phthalonitrile intermediate (a″) obtained in Synthesis Example 3-1 above. 2.85 g, 0.178 g of 2,3-dicyanonaphthalene, 0.11 g of copper (I) chloride, 5 g of benzonitrile and 3 g of 1-octanol were added and stirred at 190° C. for 12 hours under nitrogen gas atmosphere. After cooling the reaction solution to 25° C., the reaction solution was added dropwise to methanol for crystallization. After the precipitate was collected by filtration, it was dried under reduced pressure to obtain a crude product. Thereafter, column purification (filler: silica gel 60N, manufactured by Kanto Kagaku Co., Ltd.) was performed using chloroform as a solvent to obtain 2.17 g of phthalocyanine compound (xvi).

<Example 11: Phthalocyanine compound (xvii) [(2,2′-PhOPhO) ₂₁ (2,6-(CH ₃ ) ₂ PhO) ₂₁ (PhO) ₁₁ (1,4-OPhO) ₅ (Np) ₃ (CuPc) ₆ ]>
1.42 g of the dimerized phthalonitrile intermediate (d″) obtained in Synthesis Example 3-4 above and the monomeric phthalonitrile intermediate (b″) obtained in Synthesis Example 3-2 above were placed in a 50 ml reactor. 1.69 g, 0.157 g of 2,3-dicyanonaphthalene, 0.11 g of copper (I) chloride, 5 g of benzonitrile and 3 g of 1-octanol were added and stirred at 190° C. for 12 hours under nitrogen gas atmosphere. After the reaction solution was cooled to 25° C., it was added dropwise to methanol for crystallization. After the precipitate was collected by filtration, it was dried under reduced pressure to obtain a crude product. Thereafter, column purification was performed using chloroform as a solvent (filler: silica gel 60N, manufactured by Kanto Kagaku Co., Ltd.) to obtain 1.74 g of phthalocyanine compound (xvii).

<Example 12: Phthalocyanine compound (xviii) [(2,2'-PhOPhO) ₁₁ (2-PhPhO) ₁₁ (PhO) ₈ {(4-CH ₃ PhO)CH ₂ (4-CH ₃ PhO)CH ₂ Synthesis of (4-CH ₃ PhO)}Np(CuPc) ₃ ]>
1.78 g of the trimerized phthalonitrile intermediate (e″) obtained in Synthesis Example 3-5 above and the monomeric phthalonitrile intermediate (a″) obtained in Synthesis Example 3-1 above were placed in a 50 ml reactor. 4.56 g, 0.178 g of 2,3-dicyanonaphthalene, 0.11 g of copper (I) chloride, 5 g of benzonitrile and 3 g of 1-octanol were added and stirred at 190° C. for 12 hours under nitrogen gas atmosphere. After the reaction solution was cooled to 25° C., it was added dropwise to methanol for crystallization. After the precipitate was collected by filtration, it was dried under reduced pressure to obtain a crude product. Thereafter, column purification was performed using chloroform as a solvent (filler: silica gel 60N, manufactured by Kanto Kagaku Co., Ltd.) to obtain 3.86 g of phthalocyanine compound (xviii).

<Comparative Example 1: Synthesis of comparative phthalocyanine compound (i) [(2,5-Me ₂ PhO) ₈ (2,6-Me ₂ PhO) ₄ (PhO) ₄ CuPc]>
A 50 ml reactor was charged with 4 g of the monomer phthalonitrile intermediate (d') obtained in Synthesis Example 2-4 above, 0.19 g of copper (I) chloride, 5 g of benzonitrile and 3 g of 1-octanol, and nitrogen was added. The mixture was stirred at 190° C. for 10 hours under a gas atmosphere. After cooling to 25° C., the reaction solution was added dropwise to methanol for crystallization. After the precipitate was collected by filtration, it was dried under reduced pressure to obtain a crude product. Thereafter, column purification was performed using chloroform as a solvent (filler: silica gel 60N, manufactured by Kanto Kagaku Co., Ltd.), and 3.0 g of the comparative phthalocyanine compound (i) having the following structure (yield based on intermediate (d′): 73 mol %) was obtained.

<Comparative Example 2: Synthesis of comparative phthalocyanine compound (ii) [(2,5-Me ₂ PhO) ₈ (2,6-Me ₂ PhO) ₄ (F) ₄ CuPc]>
A phthalocyanine compound having the following structure obtained according to the method described in Synthesis Example 4 of JP-A-2014-28950 was used as a comparative phthalocyanine compound (ii).

<Comparative Example 3: Synthesis of comparative phthalocyanine compound (iii) [(2-PhPhO) ₆ (2-PhPhO) ₆ NpCuPc]>
A phthalocyanine compound having the following structure obtained according to the method described in Example 15 of JP-A-2014-122205 was used as a comparative phthalocyanine compound (iii).

As described above, the phthalocyanine-based compound according to the present invention contains raw materials (a phthalonitrile compound and/or a naphthalonitrile compound, and a dimerized phthalonitrile intermediate or a trimerized phthalonitrile intermediate) in a desired ratio. Manufactured by mixing. At this time, in the produced phthalocyanine compound, when each substituent is introduced at different positions, or when the cyclization reaction proceeds in the form of incorporating a plurality of dimerized phthalonitrile or trimerized phthalonitrile as a linker Therefore, it can be in the form of a mixture with various structures. For this reason, the number of each substituent may be a fractional number as it is stated as an average of these.

<<Measurement of maximum absorption wavelength (λmax) and visible light transmittance>>
For the phthalocyanine compounds (i) to (xii) obtained in Examples 1 to 9 above and the comparative phthalocyanine compounds (i) to (iii) obtained in Comparative Examples 1 to 3, the maximum absorption wavelength (λmax ), visible light transmittance at 460 nm, 510 nm and 610 nm and light resistance were measured. The results are shown in Table 2 below. In addition, the measurement was performed as follows.

(Preparation of coating solution and preparation of coating film)
The phthalocyanine compounds obtained in Examples and Comparative Examples were mixed with polyvinyl butyral resin (manufactured by Sekisui Chemical Co., Ltd.: S-Lec (registered trademark) BL-S, weight average molecular weight of about 23 , 000). Furthermore, tetrahydrofuran was added as a solvent, adjusted to a solid content concentration of 20% by weight, and dissolved to obtain a coating solution. The resulting coating solution was applied to glass using a No. 60 bar coater (thickness: 90 μm) and dried at room temperature. After that, it was further dried at 100° C. for 10 minutes to form a phthalocyanine compound-containing butyral coating film (thickness: about 20 μm).

(Measurement of maximum absorption wavelength (λmax) and absorbance, and calculation of transmittance correction value)
The maximum absorption wavelength (λmax) of the obtained phthalocyanine compound-containing butyral coating film was measured using a spectrophotometer (U-2910 manufactured by Hitachi High-Technologies Corporation). Further, the transmittance at each wavelength when the transmittance at the maximum absorption wavelength (λmax) was converted to 0% was obtained as a correction value using the following formula:
Transmittance correction value (%) = {(B - A) / B} x 100
In the above formula, let A be the absorbance at each wavelength (460 nm, 510 nm, 610 nm) and B be the absorbance at the maximum absorption wavelength (λmax). The results are shown in Table 2 below.

(Evaluation of light resistance)
The glass plate on which the phthalocyanine compound-containing butyral coating film obtained above was formed was irradiated with light from the glass surface using a light resistance tester (manufactured by Suga Test Instruments Co., Ltd.: SUGA xenon weather meter X75SC). was measured. The light resistance was evaluated by measuring the initial absorbance at the maximum absorption wavelength (λmax) and the absorbance after 150 hours, and evaluating the residual ratio of the absorbance after 150 hours to the initial absorbance. The absorbance after 300 hours was also evaluated in the same manner. The results are shown in Table 2 below. "-" in the table indicates that the measurement was not performed.

From Table 2 above, it was shown that the phthalocyanine compounds according to the present invention have excellent light resistance while maintaining good visible light transmittance. Further, the phthalocyanine-based compound according to the present invention has a maximum wavelength in the long wavelength region (specifically, 740 nm or more), and therefore has good heat ray absorption ability.

Therefore, the phthalocyanine compound according to the present invention can be suitably used for heat-absorbing laminated glass (interlayer film) and the like. For example, when it is used as an interlayer film for the windshield of an automobile, it can effectively shield the heat rays of the sun and improve the cooling efficiency while ensuring high transparency (visible light transmittance). In this case, it is considered that the heat ray shielding effect can be stably maintained over a long period of time because of its high light resistance.

In Table 2 above, by comparing Examples 1, 2 and 9 (not containing a naphthalene skeleton) and Examples 4 to 8 (containing a naphthalene skeleton), the structures containing a naphthalene ring in the phthalocyanine skeleton are more light resistant. It is suggested that the

Further, although Example 3 and Example 6 have common substituents on the phthalocyanine skeleton, the dimer exhibits better light resistance than the trimer. Indicated. Further, Examples 1 and 2 and Example 9 have common substituents on the phthalocyanine skeleton. It showed good lightfastness.

Claims (12)

A phthalocyanine compound in which two or three or more phthalocyanine skeletons are linked via an oxygen atom by a divalent or trivalent organic group,
The oxygen atom is bonded to a carbon atom constituting the phthalocyanine skeleton,
having a maximum absorption wavelength of 700 nm or more,
Formula (1) below:

Or the following formula (2):

Or the following formula (3):

In the above formulas (1), (2) and (3),
A ₁ to A ₁₆ each independently bind to any of the binding sites represented by *, and the remainder each independently represent a hydrogen atom,
Each R ₁ is independently a halogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, an ester group having 2 to 21 carbon atoms (-C(=O) OR ₂ R ₂ represents an alkyl group having 1 to 20 carbon atoms), or —R ₃ —C(=O)OR ₄ (R ₃ is an alkylene group having 1 to 20 carbon atoms, R ₄ is represents an alkyl group having 1 to 20 carbon atoms),
p is each independently an integer of 0 to 5,
m is each independently an integer of 5 to 15,
m' is each independently an integer of 1 to 14,
each X independently represents a halogen atom,
n is each independently an integer of 0 to 4,
k is each independently an integer of 0 to 3,
each q is independently an integer of 0 to 3;
each o is independently an integer of 0 to 6;
a1 is 1 to 6;
each M is independently a metal, metal oxide or metal halide;
Y is a divalent or trivalent organic group which may have an oxygen atom;
The following formula (b) or (b'):

The binding sites represented by * in structure (b) or (b') represented by are A ₁ to A ₄ , A ₅ to A 8 , A ₉ to A 12 , A ₉ to A ₁₂ , bonded as two adjacent substituents of A ₁₃ to A ₁₆ ;
Substituent (a) is represented by the following formula (a);

Among A ₁ to A ₁₆ , 15 are the substituent (a); 11 are the substituent (a) and have one structure (b), and A ₁ to the rest of A ₁₆ are hydrogen atoms; having 5 substituents (a), 1 structure (b) and 3 structures (b′), and A 1 _to A ₁₆ are hydrogen atoms; have 7 of said substituents (a), 0 of said structure (b) and 4 of said structure (b′); 4 of said substituents (a); one structure (b) and three structures (b′), and the remainder of A ₁ to A ₁₆ are hydrogen atoms; or six substituents (a), having 0 structure (b) and 4 of said structure (b') ;
A phthalocyanine compound represented by In the above formulas (1) to (3), each R ₁ independently represents a halogen atom, an alkyl group having 1 to 5 carbon atoms, or an aryl group having 6 to 10 carbon atoms; p is 0; 2. The phthalocyanine compound according to claim 1, which is an integer of ˜3 . 3. The phthalocyanine compound according to claim 1 , wherein the structure (b') has the following structure .

The phthalocyanine compound according to any one of claims 1 to 3, wherein k is 1 in the formulas (1) to ( 3 ). In the above formulas (1) to (3), Y is
A linear or branched alkylene group having 1 to 20 carbon atoms, a cyclic alkylene group having 3 to 20 carbon atoms, the following formula (3-1):

[In the above formula (3-1),
Each R ₁₁ is independently a halogen atom, an alkyl group having 1 to 20 carbon atoms, or an ester group having 2 to 21 carbon atoms (—C(=O)OR ₁₂ ; R ₁₂ is a carbon atom number representing an alkyl group of 1 to 20),
q is an integer of 0 to 3], and the following formula (3-2):

[In the above formula (3-2),
R ₁₃ is —C(R ₁₄ )(R ₁₅ )—(R ₁₄ and R ₁₅ are each independently a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, or an aryl group having 6 to 30 carbon atoms group), or —SO ₂ —,
R ₁₆ and R ₁₇ are each independently a halogen atom, an alkyl group having 1 to 20 carbon atoms, or an ester group having 2 to 21 carbon atoms (—C(=O)OR ₁₈ ; R ₁₈ is an alkyl group having 1 to 20 carbon atoms); r and s are each independently an integer of 0 to 2]. an organic group of; or
A linear or branched trivalent aliphatic hydrocarbon group having 1 to 20 carbon atoms, a cyclic trivalent aliphatic hydrocarbon group having 3 to 20 carbon atoms, the following formula (4-1):

[In the above formula (4-1),
Each R ₂₁ is independently a halogen atom, an alkyl group having 1 to 20 carbon atoms, or an ester group having 2 to 21 carbon atoms (—C(=O)OR ₂₂ , where R ₂₂ is represents an alkyl group having 1 to 20 carbon atoms; t is an integer of 0 to 2], the following formula (4-2):

[In the above formula (4-2),
R ₂₃ represents a hydrogen atom or an alkyl group having 1 to 20 carbon atoms);
R ₂₅ to R ₂₇ are each independently a halogen atom, an alkyl group having 1 to 20 carbon atoms, or an ester group having 2 to 21 carbon atoms (—C(=O)OR ₂₈ ; R ₂₈ is u, v and w are each independently an integer of 0 to 2], and the following formula (4- 3):

[In the above formula (4-3),
R ₂₈ , R ₂₉ and R ₃₀ are each independently a halogen atom, an alkyl group having 1 to 20 carbon atoms, or an ester group having 2 to 21 carbon atoms (—C(=O)OR ₃₂ ; R ₃₂ represents an alkyl group having 1 to 20 carbon atoms);
x1' and x4' are each independently an integer from 1 to 4;
x2' and x5' are each independently 1 or 2;
x3' is an integer from 0 to 3;
y1' and y2' are each independently an integer of 0 to 2], which is a trivalent organic group selected from the group consisting of aromatic ring linking groups represented by any one of claims 1 to 4 . 2. The phthalocyanine compound according to item 1 or 2. The phthalocyanine system according to any one of claims 1 to 5 , wherein in formulas (1) to (3), M is selected from copper, zinc, vanadium, and metal oxides and metal halides thereof. Compound. The phthalocyanine compound according to any one of claims 1 to 6 , represented by formula (1). The phthalocyanine compound according to claim 1, represented by the following formulas (I) to (V):

In the above formulas (I) to (V), A1, A2, C1 and C2 each represent a substituent bonded to the β-position of the phthalocyanine skeleton, and B1, B2, D1 and D2 each represent a substituent bonded to the α-position of the phthalocyanine skeleton. represents a binding substituent, and the substituents as A1, A2, B1, B2, C1, C2, D1 and D2 each independently represent any of R-1 to R12 shown below,

X represents a linker and represents any one of X-1 to X-13 shown below, wherein the linker X in formulas (I) and (II) is X1 to X10 having a divalent organic group wherein the linker X in (III) and (IV) above is selected from X11 to X13 having a trivalent organic group, a, b, c and d are A1 or C1, A2 or C2, B1 or The number of D1, B2 or D2 is indicated respectively, and the combinations of said substituents and their number and said linker are shown in Table 1 below.

A heat ray absorbing material comprising the phthalocyanine compound according to any one of claims 1 to 8. The heat ray absorbing material according to claim 9, further comprising a resin. The heat-absorbing material according to claim 10, wherein said resin has an ether bond. Formulas (A) to (C) below:

In formulas (A) to (C) above, Z ₁ to Z ₁₂ each independently represent a hydrogen atom, a halogen atom, or the following formula (a):

[In the above formula (a), each R ₁ is independently a halogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, an ester group having 2 to 21 carbon atoms ( —C(═O)OR ₂ ; R ₂ represents an alkyl group having 1 to 20 carbon atoms), or —R ₃ —C(═O)OR ₄ (R ₃ has 1 to 20 carbon atoms and R ₄ represents an alkyl group having 1 to 20 carbon atoms),
p is an integer of 0 to 5] or the following formula (b):

[In the above formula (b), * is a site that binds as two adjacent substituents of Z ₁ to Z ₄ , Z ₅ to Z ₈ , and Z ₉ to Z ₁₂ in the above formulas (A) to (C). The structure (b) represented by], or the following formula (b′):

[In formula (b′) above, * is bonded as two adjacent substituents of Z ₁ to Z ₄ , Z ₅ to Z ₈ , and Z ₉ to Z ₁₂ in formulas (A) to (C). represents a site, q is an integer of 0 to 3],
At this time, at least one of Z ₁ to Z ₁₂ is the substituent (a);
Phthalonitrile compounds (A) to (C) represented by
Formula (D) below:

In the above formula (D), Z ₁₃ to Z ₁₈ are each independently a hydrogen atom, a halogen atom, the substituent (a), the structure (b), or the structure (b′), and the formula In (b) and (b′), * represents a site that binds as two adjacent substituents of Z ₁₃ to Z ₁₅ and Z ₁₆ to Z ₁₈ in formula (D) above, and Y is a divalent is an organic group of;

In the above formula (D'), Z ₁₉ to Z ₂₇ each independently represent a hydrogen atom, a halogen atom,
The substituent (a), the structure (b), or the structure (b′), and in the formulas (b) and (b′), * is Z ₁₉ to Z in the formula (D′) ₂₁ , Z ₂₂ to Z ₂₄ , and Z ₂₅ to Z ₂₇ represent the bonding sites as two adjacent substituents, and Y is a trivalent organic group; and,
A method for producing the phthalocyanine compound according to any one of claims 1 to 8, comprising reacting a metal, a metal oxide, a metal alkoxide, a metal carbonyl, a metal halide or an organic acid metal.