JP6081771B2 - Phthalocyanine compound and heat ray absorbing material using the same - Google Patents

Description

  The present invention relates to a phthalocyanine compound and a heat ray absorbing material using the same. In particular, the present invention relates to a phthalocyanine compound having a low solar transmittance (excellent heat ray absorption ability) and a high visible light transmittance (excellent transparency), and a heat ray absorber using the same.

  Therefore, the heat ray absorbing material of the present invention has an excellent effect when used for heat ray absorbing laminated glass, heat ray shielding film, heat ray shielding resin glass, heat ray reflecting glass, etc. for vehicles (for example, automobiles, buses, trains, etc.) and buildings. It is something that demonstrates.

  When it is used as a solar energy heat ray shield for buildings or automobile windows, it must be applied to a large area, and sufficient transparency must be ensured. The spectrum of sunlight is widely distributed in the ultraviolet-visible-infrared region. In the above application, it is important to selectively absorb heat rays having a wavelength of 670 nm or more in order to effectively shield heat rays while ensuring transparency like glass.

  Conventionally, as a heat ray absorbing / shielding glass, a surface of a plate glass coated with a highly reflective metal oxide film is known. This heat ray absorbing / shielding glass is colored by adding a trace amount of metal such as iron, nickel, cobalt, etc. to an ordinary glass raw material to give selective transmission of light depending on the wavelength. However, there is no metal oxide used as a conventional heat ray absorption / screening agent that can selectively absorb the near infrared region of 670 to 850 nm, and in order to sufficiently absorb light in the wavelength region, It is necessary to increase the amount of addition. However, in such a case, the transparency of the glass may be lowered, and the cost is not preferable. In addition, since a technology for uniformly coating the surface of a large-area metal thin film layer using a metal oxide has not been sufficiently developed, the conventional method for coating (coating) a metal oxide requires a large-area surface. It was difficult to form a uniform coated surface.

  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 ray absorption efficiency, excellent near-infrared selective absorption ability, excellent solvent solubility, excellent compatibility with resins, and Excellent properties such as excellent heat resistance, light resistance, and weather resistance. For example, Patent Document 1 discloses that a phthalocyanine in which 4 to 8 substituted or unsubstituted phenoxy groups and 4 to 0 halogen atoms are introduced at the α-position and 8 substituted or unsubstituted phenoxy groups are introduced into the β-position. It is disclosed that the compound and the phthalocyanine compound are used in a heat ray absorbing material.

JP 2011-94127 A

  However, even a phthalocyanine compound as described in Patent Document 1 cannot necessarily be said to have sufficient heat ray absorbing ability, and a better heat ray absorbing ability has been demanded.

  Therefore, the present invention has been made in view of the above circumstances, and an object thereof is to provide a phthalocyanine compound having improved heat ray absorption ability.

  Another object of the present invention is to provide a phthalocyanine compound having excellent heat ray absorption ability and transparency (high visible light transmittance).

  Another object of the present invention is to provide a heat-absorbing material containing the phthalocyanine compound as described above.

  As a result of intensive studies to solve the above problems, the present inventor has found that at least 8 substituted or unsubstituted 2-phenylphenoxy groups and a phthalocyanine compound having a substituted or unsubstituted phenoxy group introduced into the balance, It has been found that the visible light transmittance is high and the solar radiation transmittance is low. For this reason, it discovered that the heat ray absorber containing the said phthalocyanine compound can exhibit the outstanding heat ray absorption ability, especially the outstanding heat ray absorption ability, and transparency, and completed this invention based on the said knowledge.

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

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

In the above formula (2), R is a halogen atom, an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, or an aryl group having 6 to 30 carbon atoms. An aryloxy group (—O—X ₁ , where X ₁ represents an aryl group having 6 to 30 carbon atoms), an ester group having 2 to 21 carbon atoms (—C (═O) OX ₂ or — OC (═O) X ₂ , wherein X ₂ represents an alkyl group having 1 to 20 carbon atoms), an amino group (—N (X ₃ ) ₂ , wherein X ₃ is independently , A hydrogen atom or an alkyl group having 1 to 20 carbon atoms), a thioalkoxy group having 1 to 20 carbon atoms (—S—X ₄ , where X ₄ is an alkyl having 1 to 20 carbon atoms) Group), or —COO (X ₅ O) _p —X ₆ [wherein X ₅ is Represents an alkylene group having 1 to 3 carbon atoms; X ₆ represents an alkyl group having 1 to 6 carbon atoms; p represents an integer of 1 to 5; and n represents an integer of 0 to 5 A substituent represented by (a)
At this time, 8 to ₁₆ of Z _{1 to} Z ₁₆ are each independently represented by the following formula (3):

In the above formula (3), R has the same definition as in the above formula (2); m is an integer of 0-4.
A substituent (b) represented by:
M is vanadyl (VO) or tin halide,
It is achieved by a phthalocyanine compound represented by

  The phthalocyanine compound of the present invention has excellent heat ray absorbing ability, particularly excellent heat ray absorbing ability (low solar transmittance) and transparency (high visible light transmittance). Therefore, since the heat ray absorbing material containing the phthalocyanine compound of the present invention can exhibit excellent heat ray absorbing ability, heat ray absorbing laminated glass for vehicles (for example, automobiles, buses, trains, etc.) and buildings, heat ray shielding films, heat ray shielding resins. It can be suitably used for glass, heat ray reflective glass and the like. Moreover, since the heat-absorbing material containing the phthalocyanine compound of the present invention can exhibit excellent heat-absorbing ability and transparency, it can be suitably used for heat-absorbing glass such as buildings and automobile windows that require high transparency. .

FIG. 1 shows the transmittance (%) when the transmittance of the maximum absorption wavelength (λmax) with respect to the wavelength of 400 to 900 nm of the phthalocyanine compounds (1) to (4) and the comparative phthalocyanine compounds (1) to (4) is 10%. ). FIG. 2 is a graph showing solar transmittance (Te) with respect to visible light transmittance (Tv) of phthalocyanine compounds (1) to (4) and comparative phthalocyanine compounds (1) to (4). FIG. 3 is a graph showing the transmittance (%) of the heat-absorbing materials (1) to (3) with respect to wavelengths of 300 to 2500 nm. FIG. 4 is a graph showing the transmittance (%) of the comparative heat ray absorbing materials (1) to (2) with respect to a wavelength of 300 to 2500 nm.

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

  The phthalocyanine compound of the present invention introduces at least 8 substituted or unsubstituted 2-phenylphenoxy groups and the remaining substituted or unsubstituted phenoxy groups; and the central metal is a vanadyl (VO) or tin halide. It is characterized by having a structure.

As described above, Patent Document 1 introduces 4 to 8 substituted or unsubstituted phenoxy groups and 4 to 0 halogen atoms at the α-position, and 8 substituted or unsubstituted phenoxy groups at the β-position. Phthalocyanine compounds have been reported. However, in this phthalocyanine compound, the substituent that can be introduced into the phenoxy group is a halogen atom, an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, or —COO (R ² O) _m. -R ³ (R ² represents an alkylene group having 1 to 3 carbon atoms, and R ³ represents an alkyl group having 1 to 6 carbon atoms). A phthalocyanine compound having such a substituted phenoxy group introduced has excellent visible light transmittance, but has a slightly smaller maximum absorption wavelength (λmax) and a second absorption peak (sub-peak) below 685 nm. Show. For this reason, the solar radiation transmittance is not necessarily sufficient, and further reduction of the solar radiation transmittance (improvement of heat ray absorption ability) has been desired.

  In contrast, in the phthalocyanine compound of the present invention, as described above, at least 8 out of all 16 phenoxy groups are substituted or unsubstituted 2-phenylphenoxy groups. Thus, it was found that the obtained phthalocyanine compound can further reduce the solar transmittance (can improve the heat ray absorption ability) while maintaining a high visible light transmittance. As described above, the reason why the phthalocyanine compound of the present invention exhibits high visible light transmittance and low solar transmittance is unknown, but is presumed as follows. Note that the present invention is not limited to the following estimation. That is, since all the substituents are —OR (phenoxy group), the obtained phthalocyanine compound exhibits high visible light transmittance. Also, due to the steric hindrance of the bulky 2-phenylphenoxy group, a nearby substituent (for example, when a 2-phenylphenoxy group is present as a substituent at the α-position, a neighboring β-position phenoxy group or a nearby α-position 2-phenylphenoxy groups) overlap at an angle to avoid collision (for example, one is arranged parallel to the phthalocyanine compound surface and the other is arranged perpendicular to the phthalocyanine compound surface). For this reason, when it sees as a whole phthalocyanine compound, a plane part will become large and a conjugated system will expand. Further, by combining the central metal vanadyl (VO) or tin halide with a bulky substituted or substituted 2-phenylphenoxy group, the phthalocyanine compound structure becomes a highly distorted structure, and the conjugated system is Expand more. For this reason, the maximum absorption wavelength (λmax) and the second absorption peak (sub-peak) of the phthalocyanine compound are lengthened, and both the maximum absorption wavelength and the second absorption peak are 670 to 850 nm, preferably 680 to 830 nm. Preferably it exists in the wavelength range of 685-820 nm, especially 690-810 nm. Therefore, the heat-absorbing material containing the phthalocyanine compound of the present invention can selectively absorb light in the wavelength range of 670 to 850 nm, preferably 680 to 830 nm, more preferably 685 to 820 nm, and particularly 690 to 810 nm. For example, when used for heat ray absorbing glass such as a vehicle (for example, an automobile, a bus, a train, etc.) or a window of a building, an increase in temperature in the vehicle or in the room can be effectively suppressed.

  In addition, the phthalocyanine compound of the present invention having such a structure has a high transmittance in the visible light wavelength region, particularly at 500 to 600 nm. In addition, both the maximum absorption wavelength (λmax) and the second absorption peak (sub-peak) exist in the wavelength range of 670 to 850 nm. In the calculation of the visible light transmittance of JIS R3106 (1998), the weight coefficient of 500 to 650 nm is large and the weight coefficient of 700 to 780 nm is small. Therefore, the visible light transmittance (Tv) of the phthalocyanine compound of the present invention is high. . For this reason, since the heat ray absorbing material using the phthalocyanine compound of the present invention is very excellent in transparency, sufficient visibility can be ensured even if it is used for heat ray absorbing glass such as a window of a building or an automobile.

  In addition, the phthalocyanine compound of the present invention is excellent in solvent solubility and compatibility with a resin, and is excellent in various properties such as heat resistance, light resistance, and weather resistance. For this reason, it is excellent in moldability to a plastic film or the like, and can be industrially applied to a large area (mass production), and also has excellent durability even when used for a window glass.

  Therefore, the heat ray absorbing material containing the phthalocyanine compound of the present invention can be suitably used for heat ray absorbing glass such as buildings and automobile windows that require high transparency.

  Embodiments of the present invention will be described below.

  The phthalocyanine compound of the present invention has the following formula (1):

Indicated by

In the above formula (1), M representing the central metal is vanadyl (VO) or a halide of tin (Sn (L) ₂ , where L is independently a fluorine atom, a chlorine atom, a bromine atom or Is an iodine atom). Thus, by making the central metal a vanadyl or tin halide, the maximum absorption wavelength (λmax) and the second absorption peak (sub-peak) of the phthalocyanine compound are 670 to 850 nm, preferably 680 to 830 nm, more preferably It can be present at 685-820 nm, especially 690-810 nm. Therefore, the phthalocyanine compound of the present invention can selectively absorb light in the specific wavelength range described above. For this reason, the heat ray absorbing material containing the phthalocyanine compound of the present invention can exhibit excellent heat ray absorptivity (heat ray shielding property). Preferably, M is preferably vanadyl (VO), tin chloride (SnCl ₂ ), tin bromide (SnBr ₂ ), tin iodide (SnI ₂ ), vanadyl (VO), tin chloride (SnCl ₂ ). Is more preferable, and vanadyl (VO) is particularly preferable.

In the above formula (1), Z _{1 to} Z ₁₆ are represented by the following formula (2):

(Hereinafter, also simply referred to as “substituent (a)”), of which 8 to 16 are represented by the following formula (3):

(B) (hereinafter, also simply referred to as “substituent (b)”). Here, Z _{1 to} Z ₁₆ may be the same or different. Thus, visible light transmittance can be increased by occupying all phthalocyanine skeleton substituents with substituted or unsubstituted phenoxy groups. For this reason, the heat ray absorbing material containing a phthalocyanine compound can exhibit excellent transparency. Moreover, by taking such a substituent arrangement, both the maximum absorption wavelength (λmax) and the second absorption peak (sub-peak) of the phthalocyanine compound can exist at 670 to 850 nm. Therefore, the phthalocyanine compound of the present invention can selectively absorb light in the specific wavelength region described above, and can exhibit an excellent heat ray shielding effect. Moreover, since the phthalocyanine compound which has such a substituent is excellent in light resistance and a weather resistance, even if it uses it for heat ray absorbers, such as a window of a building or a motor vehicle, it exhibits the outstanding durability.

Here, as long as 8 to 16 substituents (b) are introduced into the phthalocyanine skeleton, they may be arranged at any position of Z _{1 to} Z ₁₆ , but preferably Z ₁ , Z ₄ , Z Preferably, a substituted or unsubstituted 2-phenylphenoxy group is introduced at ₅ , Z ₈ , Z ₉ , Z ₁₂ , Z ₁₃ and Z ₁₆ (α position). That is, Z ₁ , Z ₄ , Z ₅ , Z ₈ , Z ₉ , Z ₁₂ , Z ₁₃ and Z ₁₆ are each independently preferably a substituent (b) represented by the above formula (3). . In the phthalocyanine compound having such a structure, the visible light transmittance can be further increased, and the heat ray absorbing material containing the phthalocyanine compound can exhibit excellent transparency. In addition, when the substituent (b) is present at the α-position, the 2-phenylphenoxy groups are adjacent to each other at a short distance, so that the adjacent 2-phenylphenoxy groups overlap at an angle in order to avoid collision (for example, one side Are arranged parallel to the phthalocyanine compound surface, and the other is arranged perpendicular to the phthalocyanine compound surface. For this reason, when viewed as a whole phthalocyanine compound, since the planar portion becomes larger, the associability increases, and the conjugated system is further expanded, both the maximum absorption wavelength (λmax) and the second absorption peak (subpeak) are 670 to 850 nm. , Preferably 680-830 nm, more preferably 685-820 nm, especially 690-810 nm. Therefore, the phthalocyanine compound of the present invention can selectively absorb light in the specific wavelength region described above, and can exhibit a more excellent heat ray shielding effect. Moreover, since the phthalocyanine compound which has such a substituent is excellent in light resistance and a weather resistance, even if it uses it for heat ray absorbers, such as a window of a building or a motor vehicle, it exhibits the outstanding durability. In addition, since the phthalocyanine compound having such a structure can be produced in one step, it is advantageous in terms of simplification of the production process and cost of the phthalocyanine compound.

In the present invention, the introduction position and type of the substituent (a) to Z _{1 to} Z ₁₆ may be uniform or non-uniform, but the substituent (a) is uniform at the α-position or β-position. It is preferable to be introduced into. _Therefore, the constituent unit containing _{Z 1 ~Z 4, Z 5 ~Z} 8, Z 9 ~Z 12, Z 13 ~Z 16, respectively, the structural units A, B, C, and is D, each of the structural units A, B, C, and D are each preferably composed of the same combination of substituents (a). By such uniform introduction / arrangement, an improvement in visible light transmittance, an improvement in light absorption selectivity in the wavelength range, durability, and the like can be achieved.

In the above formula (2), R is a halogen atom, an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, or an aryl group having 6 to 30 carbon atoms. An aryloxy group (—O—X ₁ , where X ₁ represents an aryl group having 6 to 30 carbon atoms), an ester group having 2 to 21 carbon atoms (—C (═O) OX ₂ or — OC (═O) X ₂ , wherein X ₂ represents an alkyl group having 1 to 20 carbon atoms), an amino group (—N (X ₃ ) ₂ , wherein X ₃ is independently , A hydrogen atom or an alkyl group having 1 to 20 carbon atoms), a thioalkoxy group having 1 to 20 carbon atoms (—S—X ₄ , where X ₄ is an alkyl having 1 to 20 carbon atoms) Group), or —COO (X ₅ O) _p —X ₆ [where X ₅ represents an alkylene group having 1 to 3 carbon atoms; X ₆ represents an alkyl group having 1 to 6 carbon atoms; p is an integer of 1 to 5]. Here, when a plurality of R are present in the same phenoxy group (n is an integer of 2 to 5), each R may be the same or different.

Among these, considering transparency (high visible light transmittance) and solubility, R is a halogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, or the number of carbon atoms. 2-21 of the ester group, -COO _{(X 5 O)} is preferably a p -X _6. In consideration of the selective absorptivity [the existence of the maximum absorption wavelength (λmax) and the second absorption peak (subpeak) in the specific wavelength range] in the wavelength range, R is a halogen atom, the number of carbon atoms An aryl group having 6 to 30 carbon atoms and an ester group having 2 to 21 carbon atoms are preferable.

In consideration of light resistance, R is preferably a halogen atom, an aryl group having 6 to 30 carbon atoms, an ester group having 2 to 21 carbon atoms, or —COO (X ₅ O) _p —X ₆ . When these substituents are introduced into the phenoxy group, the maximum absorption wavelength (λmax) of the phthalocyanine compound can be shifted to a long wavelength region due to the steric hindrance and electron donating property of the introduction. In addition, electronic stability in the molecule is increased. For this reason, even when a medium is used for the heat ray absorbing material, it is difficult to be attacked by the medium, and the decomposition of the phthalocyanine compound by light (particularly ultraviolet rays) can be effectively suppressed / prevented. For this reason, the heat ray absorbing material using such a phthalocyanine compound is excellent in light resistance, especially light resistance to ultraviolet rays (UV). The above effects can be more prominent when these substituents coexist in the same number and in different axes in each structural unit. For this reason, it is particularly preferable that two of these substituents are introduced at each of the α-position and β-position. In addition, the above is estimation and does not limit this invention.

  In the above formula (2), n is an integer of 0 to 5, and the number of R introduced into the phenoxy group is not particularly limited. For example, n is preferably an integer of 1 to 4, and more preferably 1 or 2. Further, the bonding position of the substituent to the phenoxy group is not particularly limited. For example, when n is 1, the substituent may be arranged at any position of the phenoxy group in the ortho position (2 position), the meta position (3 position), or the para position (4 position). Among these, the 2nd and 4th positions are preferable and the 2nd position is more preferable in consideration of selective absorption and solubility in a specific wavelength region. In consideration of light resistance, particularly light resistance to ultraviolet rays (UV), the second and fourth positions are preferable, and the fourth position is more preferable. When the number of substituents is 2, the substituent is any of the 2,3-position, 2,4-position, 2,5-position, 2,6-position, 3,4-position, 3,5-position of the phenoxy group. It can be arranged at any position. Among these, considering the visible transmittance and the like, the 2,5th, 2,6th, and 2,4th positions are preferable, and the 2,5th, 2,6th positions are more preferable.

  Here, examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. Among these, considering heat resistance, durability, etc., a fluorine atom and a chlorine atom are preferable, and a fluorine atom is more preferable.

  Although there is no restriction | limiting in particular as a C1-C20 alkyl group, For example, a methyl group, an 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-octylnonyl group, n-octadecyl group Group, n-nonadecyl group, n-icosyl group or other linear or branched alkyl group; cyclohexyl group, cyclooctyl group, etc. Including cyclic alkyl group can be mentioned. Of these, taking into consideration the maximum absorption wavelength and the presence of the second peak (sub-peak) in a specific wavelength range, durability, and the like, a linear or branched alkyl group having 1 to 8 carbon atoms, particularly a methyl group, ethyl Group is preferred, and a methyl group is more preferred.

  It does not restrict | limit especially as a C1-C20 alkoxy group, A C1-C20 linear or branched alkoxy group is mentioned. More specifically, methoxy group, ethoxy group, n-propoxy group, isopropoxy group, n-butoxy group, isobutoxy group, sec-butoxy group, tert-butoxy group, n-pentyloxy group, isopentyloxy group, Neopentyloxy group, 1,2-dimethyl-propoxy group, n-hexyloxy group, cyclohexyloxy group, 1,3-dimethylbutoxy group, 1-isopropylpropoxy group, n-octyloxy group, n-decyloxy group, n -Dodecyloxy group, n-hexadecyloxy group, 2-ethylhexyloxy group, 2-hexyldecyloxy group and the like. Among these, taking into consideration the maximum absorption wavelength, the presence of the second peak (sub-peak) in a specific wavelength region, durability, etc., straight-chain or branched alkoxy groups having 1 to 8 carbon atoms, particularly methoxy groups and ethoxy groups. Group is preferred, and a methoxy group is more preferred.

  The aryl group having 6 to 30 carbon atoms is not particularly limited, and examples thereof include non-condensed hydrocarbon groups such as a phenyl group, a biphenyl group and a terphenyl group; Group, biphenylenyl group, fluorenyl group, acenaphthylenyl group, preadenenyl group, acenaphthenyl group, phenalenyl group, phenanthryl group, anthryl group, fluoranthenyl group, acephenanthrenyl group, aceanthrylenyl group, triphenylenyl group, pyrenyl group, Examples thereof include condensed polycyclic hydrocarbon groups such as a chrycenyl group and a naphthacenyl group. Among these, a phenyl group and a naphthyl group are preferable, and a phenyl group is more preferable in consideration of the existence of the maximum absorption wavelength and the second peak (subpeak) in a specific wavelength range, durability, and the like.

The aryloxy group having 6 to 30 carbon atoms is not particularly limited and is represented by the formula: —O—X ₁ . In this case, X ₁ represents an aryl group having 6 to 30 carbon atoms. Here, the aryl group having 6 to 30 carbon atoms is not particularly limited, and an aryl group similar to the above can be used, and thus description thereof is omitted here. Among these, a phenyl group and a naphthyl group are preferable, and a phenyl group is more preferable in consideration of the existence of the maximum absorption wavelength and the second peak (subpeak) in a specific wavelength range, durability, and the like.

The ester group having 2 to 21 carbon atoms is not particularly limited and is represented by the formula: —C (═O) OX ₂ or —OC (═O) X ₂ . In this case, X 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 an alkyl group similar to the above can be used. Of these, taking into consideration the maximum absorption wavelength and the presence of the second peak (sub-peak) in a specific wavelength range, durability, and the like, a linear or branched alkyl group having 1 to 8 carbon atoms, particularly a methyl group, ethyl Group is preferred, and a methyl group is more preferred.

The amino group is not particularly limited, the formula: represented by -N _{(X 3) 2.} In this case, X ₃ each independently represents a hydrogen atom or an alkyl group having 1 to 20 carbon atoms. Here, X ₃ may be the same or different. In addition, the alkyl group having 1 to 20 carbon atoms is not particularly limited, and an alkyl group similar to the above can be used, and thus description thereof is omitted here. Of these, taking into consideration the maximum absorption wavelength and the presence of the second peak (sub-peak) in a specific wavelength range, durability, and the like, a linear or branched alkyl group having 1 to 8 carbon atoms, particularly a methyl group, ethyl Group is preferred, and a methyl group is more preferred.

The thioalkoxy group having 1 to 20 carbon atoms is not particularly limited and is represented by the formula: —S—X ₄ . In this case, X ₄ 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 an alkyl group similar to the above can be used. Of these, taking into consideration the maximum absorption wavelength and the presence of the second peak (sub-peak) in a specific wavelength range, durability, and the like, a linear or branched alkyl group having 1 to 8 carbon atoms, particularly a methyl group, ethyl Group is preferred, and a methyl group is more preferred.

Formula: -COO The _{(X 5 O)} substituent p -X _6, it is not particularly limited. In the above formula, X ₅ represents an alkylene group having 1 to 3 carbon atoms. Here, as a C1-C3 alkylene group, there exist a methylene group, ethylene group, and a propylene group. Among these, considering durability and the like, X ₅ is preferably an ethylene group or a propylene group, and more preferably an ethylene group. P represents the number of repeating units of the oxyalkylene group (X ₅ O) and is an integer of 1 to 5. In consideration of durability and the like, p is preferably an integer of 1 to 3, and more preferably 1 or 2. X ₆ represents an alkyl group having 1 to 6 carbon atoms. Here, it does not restrict | limit especially as a C1-C6 alkyl group, A C1-C6 linear, branched or cyclic alkyl group is mentioned. More specifically, examples of the alkyl group having 1 to 6 carbon atoms include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert-butyl group, n -A linear, branched or cyclic alkyl group such as a pentyl group, an isopentyl group, a neopentyl group, an n-hexyl group and a cyclohexyl group. Among these, in view of durability, solubility and the like, a linear or branched alkyl group having 1 to 3 carbon atoms, particularly a methyl group and an ethyl group are preferable, and in consideration of crystallinity of the phthalocyanine compound, the methyl group is More preferred.

Moreover, as mentioned above, in the phthalocyanine compound of the present invention, 8 to ₁₆ of Z _{1 to} Z ₁₆ are the substituent (b) of the above formula (3). Here, the 8 to 16 substituents (b) may be the same or different. Since R in the above formula (3) has the same definition as the substituent R in the above formula (2), description thereof is omitted here. In the above formula (3), m is an integer of 0 to 4, and the number of R introduced into the 2-phenylphenoxy group is not particularly limited. For example, m is preferably an integer of 0 to 2, and more preferably 0 or 1. Further, the bonding position of the substituent to the 2-phenylphenoxy group is not particularly limited. For example, when n is 1, the substituent can be arranged at any position from the 3 to 6 positions of the 2-phenylphenoxy group. Among these, considering the visible transmittance and the like, the fourth, fifth and sixth positions are preferable, and the fifth and sixth positions are more preferable.

Accordingly, preferred examples of the phthalocyanine compound according to the present invention include the following compounds. In the abbreviations of the phthalocyanine compounds in the present specification, eight substituents substituted at the β-position are first represented, and then eight substituents substituted at the α-position are represented, Ph represents a phenyl group, and Pc Represents a phthalocyanine nucleus, and immediately before Pc represents a central metal. Moreover, in this specification, the phthalocyanine compound of the following structure is prescribed | regulated by the following number. For example, a phthalocyanine compound of the formula: (2- (Ph) PhO) ₈ (2- (Ph) PhO) ₈ VOPc is referred to as “phthalocyanine compound (1)”.

  The method for producing the phthalocyanine compound of the present invention is not particularly limited, and conventionally known methods such as those described in JP 2000-26748 A, JP 2001-106869 A, and JP 2005-220060 A, for example. Can be applied alone or with appropriate modification. That is, the method for producing the phthalocyanine compound of the present invention is preferably a method in which a phthalonitrile compound and a metal compound are cyclized in a molten state or in an organic solvent. Hereafter, the preferable manufacturing method of the phthalocyanine compound of this invention is described. However, the present invention is not limited to the following preferred embodiments.

  Following formula (4):

A vanadium or tin metal, metal oxide, metal carbonyl, metal halide or organic acid metal (in the case of vanadyl, vanadium halides such as vanadium oxide and vanadium trichloride) , Carbonyl vanadium, or organic acid / salt of vanadium; in the case of tin, tin halides such as stannous chloride and stannic chloride) (also collectively referred to as “metal compounds” in this specification) And the phthalocyanine compound of the present invention can be produced.

In the above formula (4), Y _{1 to} Y ₄ each independently correspond to the substituent (a) or the substituent (b) according to the present invention and can be appropriately determined depending on the structure of the desired phthalocyanine compound. Therefore, in the above description, the phthalonitrile compound is described by one formula regardless of the structure of the phthalocyanine compound of the present invention. However, depending on the structure of the target phthalocyanine compound, there are 2 to 4 types of phthalonitrile compounds. Sometimes.

  Here, the phthalonitrile compound of the formula (4) as a starting material can be synthesized by a conventionally known method such as the method disclosed in JP-A No. 64-45474, or a commercially available product can be used. Preferably, the halogenated phthalonitrile derivative is represented by the following formula (5):

It is obtained by reacting with In the above formula (5), R and n are the same as the definition of the above formula (2), and thus the description thereof is omitted here. Here, examples of the halogenated phthalonitrile derivative include, but are not limited to, tetrafluorophthalonitrile and tetrachlorophthalonitrile. Of these, tetrafluorophthalonitrile is preferably used. When tetrafluorophthalonitrile is used as a starting material, the compound of the above formula (5) reacts preferentially with the fluorine atoms at the 4- and 5-positions of tetrafluorophthalonitrile. Therefore, by using tetrafluorophthalonitrile as a starting material, the substituents (a) and (b) can be selectively introduced into the β-position of the phthalocyanine skeleton. For this reason, the obtained phthalocyanine compound tends to have a structure in which substituents are uniformly introduced. In addition, when two or more kinds of substituents are introduced into the phthalocyanine skeleton, a halogenated phthalonitrile derivative (preferably tetrafluorophthalonitrile) is first substituted with a substituent for introducing at the β-position (5) The desired phthalonitrile compound can be produced by reacting with the compound of formula (5) and then reacting with the compound of formula (5) having a substituent for introduction at the α-position.

  In the above embodiment, the cyclization reaction can be carried out in the absence of a solvent, but is preferably carried out using an organic solvent. The organic solvent may be any inert solvent that has low reactivity with the phthalonitrile compound as a starting material, and preferably does not exhibit reactivity. For example, benzene, toluene, xylene, nitrobenzene, monochlorobenzene, o -Inert solvents such as chlorotoluene, dichlorobenzene, trichlorobenzene, 1-chloronaphthalene, 1-methylnaphthalene, ethylene glycol, and benzonitrile; methanol, ethanol, 1-propanol, 2-propanol, 1- Alcohols such as butanol, 1-hexanol, 1-pentanol, 1-octanol; and pyridine, N, N-dimethylformamide, N, N-dimethylacetamide, N-methyl-2-pyrrolidinone, N, N-dimethylacetophenone, Triethylamine, tri n- butylamine, dimethyl sulfoxide, aprotic polar solvents such as sulfolane. Of these, 1-chloronaphthalene, 1-methylnaphthalene, 1-octanol, dichlorobenzene and benzonitrile are preferably used, and more preferably 1-octanol, dichlorobenzene and benzonitrile are used. These solvents may be used alone or in combination of two or more. The amount of the organic solvent used when the organic solvent is used is not particularly limited, but the concentration of the phthalonitrile compound of the formula (4) is usually 2 to 50% by weight, preferably 10 to 40% by weight. Amount.

  The reaction conditions for the phthalonitrile compound of formula (4) and the metal compound are not particularly limited as long as the reaction proceeds. For example, the reaction temperature is usually 100 to 240 ° C, preferably 130 to 200 ° C. The reaction time is not particularly limited, but is usually 1 to 20 hours, preferably 3 to 10 hours. Further, the metal compound is preferably charged in the range of 0.8 to 2.0 mol, more preferably 1.0 to 1.5 mol, with respect to 4 mol of the phthalonitrile compound of the formula (4). The above reaction may be performed in an air atmosphere, but depending on the type of metal compound, an inert gas or oxygen-containing gas atmosphere (for example, nitrogen gas, helium gas, argon gas, or oxygen / nitrogen mixed gas) It is preferably carried out under distribution).

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

  In view of the heat ray absorption (shielding) effect, the phthalocyanine compound according to the present invention produced by the above or the above method preferably has a high visible light transmittance (Tv) and a low solar radiation transmittance (Te). Specifically, when the visible light transmittance (Tv) of the phthalocyanine compound of the present invention is 90%, the solar radiation transmittance (Te) is preferably less than 78.5%, and is preferably 78% or less. More preferably, it is more preferably 77.5% or less. With the above characteristics, excellent effects can be exhibited when used for vehicles (for example, automobiles, buses, trains, etc.) and building heat ray absorbing laminated glass, heat ray shielding film, heat ray shielding resin glass, heat ray reflecting glass and the like. In the present specification, the “visible light transmittance (Tv) (%)” and “sunlight transmittance (Te) (%)” of the phthalocyanine compound were calculated according to the standard of JIS R3106 (1998). Specifically, it means a value measured according to the method of the following example.

  In addition, the phthalocyanine compound produced by the above or the method according to the present invention has a maximum absorption wavelength (λmax) in the wavelength range of 670 to 850 nm, preferably 680 to 830 nm, more preferably 685 to 820 nm, particularly 690 to 810 nm, and It is preferable to have both of the second absorption peaks (sub-peaks) that usually appear on the shorter wavelength side than λmax. When the phthalocyanine compound has a maximum absorption wavelength (λmax) and a second absorption peak (sub-peak) in such a range, the phthalocyanine compound can selectively absorb light in the above-mentioned wavelength range. Therefore, the heat ray containing the phthalocyanine compound according to the present invention. The absorber selectively absorbs light in the above wavelength range in sunlight, and is very excellent in heat ray absorption / shielding effect. In the present specification, “maximum absorption wavelength (λmax) (nm)” and “second absorption peak (subpeak) (nm)” of the phthalocyanine compound mean values measured according to the methods of the following examples.

  In addition to the above-mentioned advantages, the phthalocyanine compound produced by the above or the method according to the present invention has excellent compatibility with the resin, and excellent heat resistance, light resistance, and weather resistance. Excellent effect as a heat-absorbing material without impairing the heat resistance.

  For this reason, by using the phthalocyanine compound according to the present invention having a high visible light transmittance for the heat ray absorbing material in this way, the obtained heat ray absorbing material is very excellent in transparency while maintaining the heat ray absorbing (shielding) ability. . That is, the second of the present invention relates to a heat ray absorbing material containing the phthalocyanine compound of the present invention. The heat ray absorbing material of the present invention is very excellent in transparency while maintaining the heat ray absorbing (shielding) ability. Therefore, the heat ray absorbing material of the present invention has an excellent effect when used for heat ray absorbing laminated glass, heat ray shielding film, heat ray shielding resin glass, heat ray reflecting glass, etc. for vehicles (for example, automobiles, buses, trains, etc.) and buildings. Can demonstrate.

  Moreover, the heat ray absorbing material containing the phthalocyanine compound of the present invention can selectively and efficiently absorb light in the above-mentioned wavelength region in sunlight, and can exhibit an excellent heat ray shielding effect. For this reason, when the heat ray absorbing material using the phthalocyanine compound according to the present invention is used for, for example, heat ray absorbing glass such as an automobile or a window of a building, an increase in the temperature in the vehicle or in the room can be effectively suppressed.

  The heat ray absorbing material of the present invention essentially contains the phthalocyanine compound according to the present invention. For this reason, except using the phthalocyanine compound which concerns on this invention, the heat ray absorber of this invention is applicable as a heat ray absorber similar to the past. Here, the phthalocyanine compound according to the present invention may be used alone or in the form of a mixture of two or more. In particular, the phthalocyanine compound selectively absorbs light in the near-infrared region with high light intensity in the specific range, and increases the transmittance in the visible light wavelength region (that is, while ensuring transparency) The effect of effectively absorbing / shielding heat from light can be imparted to the heat ray absorbing material. This is because the phthalocyanine compound according to the present invention has a specific structure as described above. Further, the phthalocyanine compound according to the present invention is excellent in compatibility with a resin in addition to the above-mentioned advantages of selective absorption in a specific wavelength range and high transmittance in a visible light wavelength range, and also has heat resistance and light resistance. And excellent weather resistance. For this reason, the heat ray absorbing material of the present invention can also exhibit the same excellent effects. Furthermore, the phthalocyanine compound according to the present invention can be provided as an inexpensive organic material constituting the heat ray absorbing material, and can be widely used for various heat ray shielding applications. In addition, the phthalocyanine compound has many excellent characteristics that it can be produced by a molding method having excellent productivity such as injection molding and extrusion molding using a thermoplastic resin because of its excellent heat resistance. It can be demonstrated. Therefore, the heat ray absorbing material of the present invention can be suitably used as a heat ray absorbing laminated glass for vehicles (for example, automobiles, buses, trains, etc.) and buildings, a heat ray shielding film, a heat ray shielding resin glass, a heat ray reflecting glass and the like. Furthermore, since the phthalocyanine compound according to the present invention can be produced by a one-step process, the production process is easy, can be produced in a short time, is economical, and is friendly to the environment.

  The usage form of the heat ray absorbing material of the present invention is not particularly limited, and any known form may be used. Specifically, a form that is separately formed as a coating film, film, or the like on an object that preferably absorbs / shields heat rays; a form such as a laminate that provides a phthalocyanine compound-containing intermediate layer between two objects And the form contained in the object. Among these, it is preferable to mix the phthalocyanine compound according to the present invention in a coating film, a film, and an intermediate layer. Here, the coating film, the film and the intermediate layer generally contain a resin in addition to the phthalocyanine compound according to the present invention. That is, the heat ray absorbing material of the present invention includes the phthalocyanine compound and the resin according to the present invention. Hereinafter, a composition containing a phthalocyanine compound and a resin may be referred to as a resin composition.

  Although the compounding quantity of the phthalocyanine compound in the said heat ray absorber can be suitably selected according to a use or the thickness of resin, it is 0.0005-20 mass parts with respect to 100 mass parts of resin solid content, Preferably it is 0.001. -10 parts by mass. By mix | blending in such a range, it can be set as the heat ray absorber which has the moderate visible light transmittance suitable for the use.

  The resin is not particularly limited as long as it is generally usable for optical materials, but is preferably as highly transparent as possible. More specifically, polyethylene, polypropylene, carboxylated polyolefin, chlorinated polyolefin, cycloolefin Polyolefin resins such as 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, polyurethane resins, Polyester resins such as polyethylene terephthalate (PET) and polyarylate (PAR), polycarbonate resins, epoxy resins, polyvinyl acetal resins such as polyvinyl butyral, and the like. Among these, those that can be melted or made into a solution are preferably used. At this time, a resin composition that can be molded is obtained by kneading a phthalocyanine compound using a meltable resin. Suitable as such resins are (meth) acrylate resins such as polyacrylic acid, polymethyl methacrylate, α-hydroxymethyl acrylate copolymer, polycarbonate resins, polyester resins, polyvinyl acetals. Resin, vinyl acetate resin (for example, ethylene / vinyl acetate copolymer (EVA)), Arton (registered trademark) (manufactured by JSR Corporation), Zeonoa (registered trademark) (manufactured by Nippon Zeon Corporation), Sumipex (registered) Trademark) (manufactured by Sumitomo Chemical Co., Ltd.), Optretz (manufactured by Hitachi Chemical Co., Ltd.).

  Moreover, it can be set as the resin composition which can be coat | covered by making a phthalocyanine compound into solution in resin which can be made into solution. Suitable examples of such resins include (meth) acrylic acid ester resins, polyester resins, Arton (registered trademark) (manufactured by JSR Corporation), and Zeonore (registered trademark) (manufactured by Nippon Zeon Corporation). It is done. Particularly preferably, a methacrylate having a linear, branched, alicyclic or polycyclic alicyclic alkyl group having 1 to 10 carbon atoms, such as methyl methacrylate, tert-butyl methacrylate, cyclohexyl methacrylate, isobornyl methacrylate and the like. Is a polymer obtained by copolymerization. This may be a polymer composed of one kind of methacrylic acid ester monomer, or a copolymer composed of a plurality of methacrylic acid ester monomers.

  Moreover, the polymer copolymerized with monomers other than said methacrylate ester may be sufficient. Other monomers include aromatic monomers such as styrene and methylstyrene, maleimide monomers such as phenylmaleimide and cyclohexylmaleimide, monomers having a carboxyl group such as (meth) acrylic acid, Monomers having a hydroxy group such as (meth) acrylic acid ester having 15 alkyl groups and hydroxyethyl (meth) acrylate can also be used. The amount of the monomer other than the (meth) acrylic ester is less than 50% by weight, preferably less than 30% by weight, and more preferably less than 10% by weight. Specific examples include Sumipex (manufactured by Sumitomo Chemical), Optrez (manufactured by Hitachi Chemical Co., Ltd.), and Hals Hybrid IR (manufactured by Nippon Shokubai).

  The molecular weight of the resin is preferably 50,000 or more, more preferably 100,000 or more in terms of polystyrene. The polymer structure is not limited and may be linear or branched. However, the branched type is more preferable than the linear type because the resin is less likely to break and has higher durability. When the branched structure is used, even when the molecular weight is increased, the viscosity of the resin is low and the handling becomes easy. In order to obtain a branched resin, a macromonomer, a polyfunctional monomer, a polyfunctional initiator, and a polyfunctional chain transfer agent can be used. As the macromonomer, AA-6, AA-2, AS-6, AB-6, AK-5 (all manufactured by Toa Gosei Co., Ltd.) and the like can be used. Examples of the polyfunctional monomer include LIGHT EG EG, LIGHT SEL 1,4BG, LIGHT ESTER NP, LIGHT ESTER TMP (all manufactured by Kyoeisha Chemical Co., Ltd.) and the like. Examples of the polyfunctional initiator include Pertetra A, BTTB-50 (all manufactured by NOF Corporation), Trigonox 17-40MB, and Parkadox 12-XL25 (all manufactured by Kayaku Akzo Corporation). As the polyfunctional chain transfer agent, pentaerythritol tetrakis (3-mercaptopropionate), trimethylolpropane tris (3-mercaptopropionate), pentaerythritol tetrakis (thioglycolate) (all manufactured by Sakai Chemical Industry Co., Ltd.) ) Etc. can be used. In order to obtain a branched resin, it is particularly preferable to use a polyfunctional initiator because polymerization is easy. Pertetra A, Parkardox 12-XL25, which has a large number of branches and reacts at a mild temperature, is particularly preferable.

  On the other hand, the resin may be a pressure-sensitive adhesive or an adhesive, or a mixture thereof. When a pressure-sensitive adhesive or an adhesive is used, it can be bonded to another functional film, so that the heat-absorbing material can be produced simply and economically.

  Resins suitable as the above-mentioned pressure-sensitive adhesive include acrylic, silicon and SBR resins. Particularly preferred is a polymer obtained by polymerizing ethyl acrylate, butyl acrylate, 2-ethylhexyl acrylate, n-octyl acrylate or the like as a main component, and specifically, Acryset (registered trademark) AST (manufactured by Nippon Shokubai Co., Ltd.) Can be mentioned. Tg is preferably −80 ° C. or higher and 0 ° C. or lower. Further, a suitable pressure-sensitive adhesive is a (meth) acrylic acid ester resin obtained by copolymerizing a (meth) acrylic acid ester having an alicyclic alkyl group such as a cyclohexyl group or an isobornyl group. The amount of the ester used when copolymerizing the (meth) acrylic acid ester having an alicyclic alkyl group is not particularly limited, but should be such that the Tg of the resin is -80 ° C or higher and 0 ° C or lower. Is preferred. It is also possible to copolymerize a (meth) acrylic acid ester having an acidic group such as a carboxyl group. In such a case, the copolymer of (meth) acrylic acid ester is used for the purpose of improving moisture resistance. The polymerization amount is preferably such that the acid value of the resin is preferably 30 or less, more preferably 15 or less, and most preferably 5 or less. In the present specification, “acid value” refers to the amount of potassium hydroxide required to neutralize 1 g of resin solids.

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

  The solvent that may be contained in the heat ray absorbing material is not limited as long as it is a solvent that can dissolve or disperse the phthalocyanine compound and the resin. Examples of solvents that can be used in this case include aliphatic systems such as cyclohexane and methylcyclohexane, aromatic systems such as toluene and xylene, ketone systems such as acetone, methyl ethyl ketone, and methyl isobutyl ketone, ester systems such as ethyl acetate and butyl acetate, Nitriles such as acetonitrile, alcohols such as methanol, ethanol, isopropyl alcohol and 2-methoxyethanol, ethers such as tetrahydrofuran and dibutyl ether, butyl cellosolve, propylene glycol n-propyl ether, propylene glycol n-butyl ether, propylene glycol monomethyl ether Glycol ethers such as acetate, triethylene glycol di- (2-ethyl) butyrate, triethylene glycol di- (2-ethyl) hexano Over preparative like ether ester, formamide, N, N-dimethylformamide and the like amide-based, methylene chloride, halogen-based, such as chloroform can be used. These may be used alone or in combination. In order to improve the durability of the dye, a solvent having a boiling point of 100 ° C. or less, such as methyl ethyl ketone and ethyl acetate, is suitable. Moreover, in order to improve the coating film appearance at the time of coating, a solvent having a boiling point of 100 to 150 ° C. such as toluene, methyl isobutyl ketone, and butyl acetate is suitable. In order to improve the crack resistance of the coating film, a solvent 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 is preferable.

  In addition to the phthalocyanine compound, the resin composition according to the present invention may contain a visible absorbing dye, a near infrared absorber, and an ultraviolet absorber (hereinafter collectively referred to as “other absorber”). As described above, by further using another absorbent, it is possible to absorb light in a wavelength region where the phthalocyanine compound of the present invention cannot absorb or is not sufficiently absorbed.

  Here, visible absorption dyes include cyanine, tetraazaporphyrin, azurenium, squarylium, diphenylmethane, triphenylmethane, oxazine, azine, thiopyrylium, viologen, azo, azo metal complex Bisazo, anthraquinone, perylene, indanthrone, nitroso, metal thiol complex, indico, azomethine, xanthene, oxanol, indoaniline, quinoline, etc. be able to. For example, Adeka Arcles TW-1367, Adeka Arcles SG-1574, Adeka Arcles TW1317, Adeka Arcles FD-3351, Adeka Arcles Y944 (all manufactured by ADEKA Corporation), NK-5451, NK-5532, NK-5450 (both manufactured by Hayashibara Biochemical Laboratories) and the like. The visible light absorbing dye may be a dye that dissolves in a solvent, or may be a pigment that is atomized to such an extent that haze does not become a problem.

  Moreover, it does not restrict | limit especially as a near-infrared absorber, A well-known near-infrared absorber can be suitably selected by the maximum absorption wavelength desired by a use. Here, the maximum absorption wavelength of the near-infrared absorber is preferably 800 nm or more, more preferably 800 to 1500 nm, and particularly preferably 800 to 1000 nm. By using the near-infrared absorber in the wavelength range, light in a wavelength range where the phthalocyanine compound of the present invention cannot absorb or is not sufficiently absorbed can be absorbed, so that the heat ray shielding effect can be further improved. Such a near-infrared absorber is not particularly limited, and can be appropriately selected depending on a desired maximum absorption wavelength. More specifically, phthalocyanines described in JP-A No. 2000-26748, JP-A No. 2001-106869, JP-A No. 2004-018561, JP-A No. 2007-56105, and JP-A No. 2011-116918. Examples include a near-infrared absorbing dye using a compound. Moreover, the near-infrared absorption pigment | dye as another absorber may be marketed. Examples of commercially available products include IR-915, IR-12, IR-14, IR-20, and HA-1 (all are phthalocyanine compounds manufactured by Nippon Shokubai Co., Ltd.).

  Moreover, it does not restrict | limit especially as an ultraviolet absorber which may be used, A well-known ultraviolet absorber can be used. Specifically, salicylic acid, benzophenone, benzotriazole, and cyanoacrylate compounds are preferably used.

  The other absorbents may be used alone or in the form of a mixture of two or more, and can be appropriately selected depending on the application. Preferably, the resin composition according to the present invention preferably further includes a near infrared absorbing dye, and more preferably includes a near infrared absorbing dye having a maximum absorption wavelength of 800 nm or more.

  The blending amount of the other absorbent is not particularly limited, and cannot be determined unconditionally because the absorption wavelength range, visible light transmittance and solar radiation transmittance required depending on the application are different. The blending amount of the other absorbent is preferably 0.001 to 10 parts by mass, more preferably 0.005 to 8 parts by mass with respect to 100 parts by mass of the solid content of the resin. Also, the mixing ratio with the phthalocyanine compound of the present invention is not particularly limited. 1-1000 mass parts is preferable with respect to 100 mass parts of phthalocyanine compounds of this invention, and, as for the mixing ratio (mass ratio) of the phthalocyanine compound of this invention, and said other absorber, 10-500 mass parts is more preferable. Within this range, the solar radiation transmittance can be lowered without affecting the visible light transmittance. The visible light transmittance is preferably 55% or more, more preferably 60% or more. The solar radiation transmittance is preferably 65% or less, more preferably 60% or less, and further preferably 55% or less.

  Furthermore, 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 as heat ray absorbing materials as long as the performance is not lost. May be. However, a resin composition that does not use a curing agent is more preferable because the pot life of the coating liquid is long and aging is unnecessary.

  In addition, known additives used for films, coating agents and the like can be used for the heat-absorbing material. Examples of the additive include dispersants, leveling agents, antifoaming agents, viscosity modifiers, matting agents, adhesives. Examples include an imparting agent, an antistatic agent, an antioxidant, a light stabilizer, a quencher, a curing agent, an antiblocking agent, a plasticizer, and a slipping agent.

  The heat ray absorbing material of the present invention may be one in which a coating film made of the above resin composition is formed, or may be one obtained by molding the above resin composition. Preferably, (A) a resin composition coated on a transparent substrate, (B) a resin composition obtained by bonding two transparent substrates, and (C) a resin composition molded.

Although there is no restriction | limiting in the thickness of the heat ray absorber of this invention, It determines suitably according to the objective and a use. Preferably, it is 0.1 μm to 20 mm. The content of the phthalocyanine compound contained in the heat ray absorbing material is also appropriately determined according to the purpose and application. If the content of the phthalocyanine compound is displayed regardless of the thickness of the heat ray absorbing material, the blending amount of 0.01 to 2.0 g / m ² is preferable, more preferably, considering the mass in the projected area from above. 0.05 to 1.0 g / m ² . Within this range, the visible light transmittance is high, the solar radiation transmittance is small, and the heat ray absorption effect is high, which is preferable. The visible light transmittance varies depending on the application, but a preferable visible light transmittance is 55% or more. More preferably, it is 60% or more. The solar radiation transmittance is preferably 95% or less, more preferably 90% or less.

  The transparent substrate is generally usable as an optical material, and is not particularly limited as long as it is substantially transparent. Specific examples include olefin resins such as glass, cyclopolyolefin and amorphous polyolefin, methacrylic resins such as polymethyl methacrylate, polystyrene resins, polycarbonate resins, polyester resins such as PET and PAR, and polyethersulfone. Resin, polyaryl ether resin and the like. When an inorganic base material such as glass is used as the transparent base material, a material having a small alkali component is preferable from the viewpoint of the durability of the dye.

  When using a resin-based material as a transparent substrate, known additives, heat aging inhibitors, lubricants, antistatic agents, etc. can be blended into the resin, and known injection molding, T-die molding, calendar molding, etc. Then, it is molded into a desired shape by a method such as compression molding or a method of melting and casting in an organic solvent. Such a transparent substrate may be stretched or laminated with other resins as necessary. In addition, the transparent substrate is subjected to surface treatment by a conventionally known method such as corona discharge treatment, flame treatment, plasma treatment, glow discharge treatment, surface roughening treatment, chemical treatment, or coating with an anchor coating agent or a primer. Also good.

  A known coating machine can be used when applying 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. It is 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, UV curing and the like can be used. You may wind up with a well-known protective film after drying and hardening.

  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 is preferably 0.1 μm to 10 mm.

  When the heat-absorbing material of the present invention is in the form of a film, the transparent substrate is preferably a PET film, and particularly preferably a PET film that has been subjected to an easy adhesion treatment. Specifically, Cosmo Shine A4300 (manufactured by Toyobo), Lumirror U34 (manufactured by Toray), Melinex 705 (manufactured by Teijin DuPont) and the like can be mentioned.

  In the case of the film form described above, the resin used for the heat ray shielding material is preferably an adhesive resin or a UV curable resin. When an adhesive resin or a UV curable resin is used, the coating film may be formed on one side of the film or on both sides, but is preferably applied on one side. When forming a coating film on the film, the coating liquid of the resin composition may be applied directly on the transparent substrate, or the coating film of the resin composition applied on the substrate having releasability is transparent. You may transfer on a base material. Further, a UV curable coating film may be formed on the opposite surface of the film. In that case, it is preferable to apply a coating liquid containing the phthalocyanine compound, UV curable monomer or oligomer, and photopolymerization initiator on the transparent substrate. Moreover, you may apply | coat an adhesive to the other surface of a film.

  When the heat ray absorbing material is a heat ray absorbing material obtained by bonding two transparent substrates with the resin composition, glass and PET film are preferable as the transparent substrate. As the resin composition for bonding two glass substrates, one using polyvinyl butyral as a resin is preferable from the viewpoint of adhesiveness.

  The method for producing the heat-absorbing material is not particularly limited. For example, (a) a method in which the resin composition is kneaded and heat-molded, (b) a formwork together with a phthalocyanine compound, a curable monomer or oligomer, and a polymerization initiator. A method of polymerizing and molding can be used.

  Molding conditions for kneading and thermoforming the resin composition vary depending on the type of resin. Usually, a phthalocyanine compound is melted in a thermoplastic resin powder and pelletized after kneading to obtain a master batch having a high phthalocyanine compound concentration. A method of further diluting, melting, kneading and molding this master batch with the thermoplastic resin can be mentioned.

  Since the phthalocyanine compound used in the heat ray absorbing material of the present invention is superior in heat resistance as compared with a commercially available infrared absorber, the resin temperature for injection molding and extrusion molding is as high as 200 to 350 ° C. Molding can be performed by an ascending molding method, and a molded product having good transparency and excellent heat ray shielding performance can be obtained.

  Examples of the thermoplastic resin include olefin polymers such as cyclopolyolefin and amorphous polyolefin, methacrylic resins such as polymethyl methacrylate, polystyrene resins, polycarbonate resins, polyester resins such as PET and PAR, and polyethersulfone. Resin, polyaryl ether resin and the like.

  Moreover, as a curable monomer or oligomer used in a method of polymerizing and molding in a mold together with a phthalocyanine compound, a curable monomer or oligomer, and a polymerization initiator, (meth) acrylic resin, epoxy resin, silicone resin, Examples thereof include monomers or oligomers that produce polyimide and the like. A suitable polymerization initiator can be used depending on the monomer or oligomer.

  When shape | molding a resin composition, the said heat ray absorber does not have a restriction | limiting in a shape, It can form suitably according to a use. Various shapes such as a flat plate shape, a film shape, a corrugated plate shape, a spherical shape, and a dome shape are included. The thickness is not particularly limited, but is preferably 0.05 to 20 mm. If it is such a range, sufficient intensity | strength and safety | security as a heat ray absorber will be acquired.

  The heat ray absorbing material of the present invention may be one in which a coating film made of the above resin composition is formed on a transparent substrate, or may be one obtained by molding the above resin composition, but is further heat ray absorbing inorganic compound (inorganic heat ray) Absorbing material) may be included. Thus, by using a heat ray absorbing inorganic compound (inorganic heat ray absorbing material), the heat ray absorbing ability in the near infrared region where the absorbing ability by the phthalocyanine compound of the present invention is low can be improved.

  The heat ray absorbing inorganic compound (inorganic heat ray absorbing material) may be added to a resin composition containing a phthalocyanine compound to form a molded or coated film. Moreover, it may be combined with the heat ray absorbing material of the present invention using a transparent substrate containing a heat ray absorbing inorganic compound (inorganic heat ray absorbing material), or the surface of the heat ray absorbing material that is molded or applied is heat ray absorbing inorganic compound. You may apply | coat the coating material containing (inorganic type heat ray absorption material). That is, the heat ray absorbing material further containing a heat ray absorbing inorganic compound (inorganic heat ray absorbing material) is one of the preferred embodiments of the present invention. Moreover, it is a preferable embodiment of the present invention that the heat ray 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 ray absorbing inorganic compound (inorganic heat ray absorbing material).

As the heat ray absorbing inorganic compound (inorganic heat ray absorbing material), those having heat ray 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 (CsWO ₃ ), antimony oxide, antimony doped tin oxide (ATO), antimonic acid Zinc etc. are mentioned. The heat ray absorbing inorganic compound (inorganic heat ray absorbing material) having heat ray absorbing ability absorbs 900 nm or more, preferably 1100 nm or more, more preferably 1200 nm or more, which is a wavelength region that cannot be absorbed by the phthalocyanine compound or organic dye. The solar radiation transmittance can be lowered while maintaining the visible light transmittance. More preferably, alkali metal doped tungsten oxide, indium tin oxide or antimony doped tin oxide. Specifically, examples of the alkali metal doped tungsten oxide include SG-IRC90SPM (manufactured by Sukkyung). Examples of indium tin oxide include PI-3 (Mitsubishi Materials). Examples of the antimony-doped tin oxide include SNS-10M, SNS-10T, SN100P, SN-100D, FS-10P, and FS-10D (all manufactured by Ishihara Sangyo). The metal oxide is in the form of fine particles, and the average dispersed particle size is 0.001 to 0.2 μm. Preferably it is 0.005-0.15 micrometer. This range is preferable because the transparency is not impaired.

  The blending amount of the heat ray absorbing inorganic compound (inorganic heat ray absorbing material) is not particularly limited, and cannot be determined unconditionally because the absorption wavelength range, visible light transmittance, and solar radiation transmittance required by the application are different. . Specifically, the blending amount of the heat ray absorbing inorganic compound (inorganic heat ray absorbing material) is preferably 1 to 1000 parts by mass, and 10 to 500 parts by mass with respect to 100 parts by mass of the solid content of the resin. It is more preferable. Also, the mixing ratio with the phthalocyanine compound of the present invention is not particularly limited. The mixing ratio (mass ratio) of the phthalocyanine compound of the present invention and the other absorbent is preferably 20 to 5000 parts by mass, and 50 to 4000 parts by mass with respect to 100 parts by mass of the phthalocyanine compound of the present invention. More preferred. Within this range, the solar radiation transmittance can be lowered without affecting the visible light transmittance. The visible light transmittance is preferably 55% or more, more preferably 60% or more. The solar radiation transmittance is preferably 65% or less, more preferably 60% or less, and further preferably 55% or less.

  The heat ray absorbing material of the present invention is suitable for building and vehicle window films, heat ray absorbing laminated glass, heat ray absorbing resin glazing, daylighting building materials, and the like. The heat ray absorbing material in which a coating film of the resin composition of the present invention is formed on a film-like transparent substrate can be used as a window film. The window film may be applied to the inside or outside of the 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. Moreover, when using as a sheet-like molded object, such as a lighting construction material, it is preferable to add a ultraviolet absorber to an outermost layer by a multilayer extrusion system, and to use the heat ray absorber of this invention for an 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. Unless otherwise specified, “Ph” represents a phenyl group.

Synthesis Example 1: Synthesis of 3,4,5,6-tetrakis (2-phenylphenoxy) phthalonitrile In a 500 ml eggplant flask, 30 g of tetrafluorophthalonitrile, 91 g of potassium carbonate, 103 g of 2-phenylphenol and 180 g of acetonitrile were added. The mixture was stirred at 70 ° C. for 7 hours.

  After cooling to room temperature, the reaction solution was filtered, acetonitrile was distilled off from the filtrate under reduced pressure, and methanol was added for crystallization. The precipitate was collected by filtration and dried under reduced pressure to obtain 115 g of 3,4,5,6-tetrakis (2-phenylphenoxy) phthalonitrile (yield: 96 mol% with respect to tetrafluorophthalonitrile).

Synthesis Example 2: Synthesis of 3,6-bis (2-phenylphenoxy) -4,5-bis (2-methyloxycarbonylphenoxy) phthalonitrile In a 500 ml eggplant flask, 70 g of tetrafluorophthalonitrile, 116 g of potassium carbonate, salicylic acid Methyl (108 g) and acetonitrile (140 g) were added, and the mixture was stirred at 70 ° C. for 7 days.

  After cooling to room temperature, the reaction solution was filtered, acetonitrile was distilled off from the filtrate under reduced pressure, and methanol was added for crystallization. The precipitate was collected by filtration and then dried under reduced pressure to obtain 110 g of 3,6-difluoro-4,5-bis (2-methyloxycarbonylphenoxy) phthalonitrile (yield: 68 mol% based on tetrafluorophthalonitrile). It was.

  The resulting 3,6-difluoro-4,5-bis (2-methyloxycarbonylphenoxy) phthalonitrile (10 g), potassium carbonate (7 g), 2-phenylphenol (7 g) and acetonitrile (30 g) were mixed and stirred at 70 ° C. for 4 hours. It was.

  After cooling to room temperature, the reaction solution was filtered, acetonitrile was distilled off from the filtrate under reduced pressure, and methanol was added for crystallization. The precipitate was collected by filtration and dried under reduced pressure to give 16 g of 3,6-bis (2-phenylphenoxy) -4,5-bis (2-methyloxycarbonylphenoxy) phthalonitrile (yield: 3,6-difluoro-4). , 5-bis (2-methyloxycarbonylphenoxy) phthalonitrile).

Synthesis Example 3: Synthesis of 3,6-bis (2-phenylphenoxy) -4,5-bis (2-fluorophenoxy) phthalonitrile In a 200 ml eggplant flask, 22 g of tetrafluorophthalonitrile, 15 g of potassium fluoride and 44 g of acetone And mixed at 0 ° C. A mixed liquid prepared with 25 g of 2-fluorophenol and 25 g of acetone was dropped at a liquid temperature of 0 ° C., and the mixture was stirred for 2 hours.

  After raising the temperature to room temperature, the reaction solution was filtered, acetone was distilled off from the filtrate under reduced pressure, and methanol was added for crystallization. The precipitate was collected by filtration and dried under reduced pressure to obtain 20 g of 3,6-difluoro-4,5-bis (2-fluorophenoxy) phthalonitrile (yield: 48 mol% with respect to tetrafluorophthalonitrile).

  The resulting 3,6-difluoro-4,5-bis (2-fluorophenoxy) phthalonitrile (3 g), potassium carbonate (3 g), 2-phenylphenol (3 g) and acetonitrile (9 g) were mixed and stirred at 70 ° C. for 4 hours.

  After cooling to room temperature, the reaction solution was filtered, acetonitrile was distilled off from the filtrate under reduced pressure, and methanol was added for crystallization. The precipitate was collected by filtration and then dried under reduced pressure to give 5 g of 3,6-bis (2-phenylphenoxy) -4,5-bis (2-fluorophenoxy) phthalonitrile (yield: 3,6-difluoro-4,5). -93 mol% with respect to bis (2-fluorophenoxy) phthalonitrile).

Synthesis Example 4: Synthesis of 3,6-bis (2-phenylphenoxy) -4,5-bis (4-fluorophenoxy) phthalonitrile In a 200 ml eggplant flask, 22 g of tetrafluorophthalonitrile, 15 g of potassium fluoride and 44 g of acetone And mixed at 0 ° C. A mixed liquid prepared with 25 g of 4-fluorophenol and 25 g of acetone was dropped at a liquid temperature of 0 ° C., and the mixture was stirred for 2 hours.

  After raising the temperature to room temperature, the reaction solution was filtered, acetone was distilled off from the filtrate under reduced pressure, and methanol was added for crystallization. The precipitate was collected by filtration and dried under reduced pressure to obtain 22 g of 3,6-difluoro-4,5-bis (4-fluorophenoxy) phthalonitrile (yield: 52 mol% with respect to tetrafluorophthalonitrile).

  3 g of the obtained 3,6-difluoro-4,5-bis (4-fluorophenoxy) phthalonitrile, 3 g of potassium carbonate, 3 g of 2-phenylphenol and 9 g of acetonitrile were mixed and stirred at 70 ° C. for 4 hours.

  After cooling to room temperature, the reaction solution was filtered, acetonitrile was distilled off from the filtrate under reduced pressure, and methanol was added for crystallization. The precipitate was collected by filtration and dried under reduced pressure to give 5 g of 3,6-bis (2-phenylphenoxy) -4,5-bis (4-fluorophenoxy) phthalonitrile (yield: 3,6-difluoro-4,5). -98 mol% with respect to bis (4-fluorophenoxy) phthalonitrile).

Comparative Synthesis Example 1: Synthesis of 4,5-bis (4-methoxycarbonylphenoxy) -3,6-bis (4-methoxyphenoxy) phthalonitrile In a 500 ml eggplant flask, 20 g of tetrafluorophthalonitrile, potassium fluoride 12. 8 g and 20 g of acetone were added and mixed at 5 ° C. A mixture prepared by 31.0 g of methyl 4-hydroxybenzoate and 30 g of acetone was added dropwise over about 3 hours at a liquid temperature of 5 ° C., and the mixture was stirred overnight while slowly raising the reaction temperature to room temperature.

Next, this flask was charged with 25.3 g of 4-methoxyphenol and 12 potassium fluoride.
. 8 g and 30 g of acetone were charged and stirred for 2 hours under reflux. After cooling, the reaction solution was filtered, and the filtrate was recrystallized by distilling off acetone with a rotary evaporator and adding methanol. The obtained crystals were filtered and dried under reduced pressure to give 55.2 g of 4,5-bis (4-methoxycarbonylphenoxy) -3,6-bis (4-methoxyphenoxy) phthalonitrile (yield: tetrafluorophthalonitrile). 82.1 mol%).

Comparative Synthesis Example 2: Synthesis of 3,4,5,6-tetrakis (3-phenylphenoxy) phthalonitrile Into a 50 ml eggplant flask, 1 g of tetrafluorophthalonitrile, 4 g of potassium carbonate, 5 g of 3-phenylphenol and 7 g of acetonitrile are placed. , And stirred at 70 ° C. for 4 hours.

  After cooling to room temperature, the reaction solution was filtered, acetonitrile was distilled off from the filtrate under reduced pressure, and methanol was added for crystallization. The precipitate was collected by filtration and dried under reduced pressure to obtain 5 g of 3,4,5,6-tetrakis (3-phenylphenoxy) phthalonitrile (yield: 90 mol% with respect to tetrafluorophthalonitrile).

Comparative Synthesis Example 3: Synthesis of 3,6-difluoro-4,5-bis (2-phenylphenoxy) phthalonitrile Into a 200 ml eggplant flask, 20 g of tetrafluorophthalonitrile, 14 g of potassium fluoride and 60 g of acetone were added, and the temperature was 0 ° C. Mixed. A mixed liquid prepared with 34 g of 2-phenylphenol and 34 g of acetone was dropped at a liquid temperature of 0 ° C., and the mixture was stirred for 2 hours.

  After raising the temperature to room temperature, the reaction solution was filtered, acetone was distilled off from the filtrate under reduced pressure, and methanol was added for crystallization. The precipitate was collected by filtration and then dried under reduced pressure to obtain 25 g of 3,6-difluoro-4,5-bis (2-phenylphenoxy) phthalonitrile (yield: 50 mol% based on tetrafluorophthalonitrile).

Comparative Synthesis Example 4: Synthesis of 3-fluoro-4,5,6-tris (2-phenylphenoxy) phthalonitrile In the same manner as in Synthesis Example 4, 3,6-difluoro-4,5-bis (2-phenyl) Synthesize phenoxy) phthalonitrile.

  In a 200 ml eggplant flask, 3 g of 3,6-difluoro-4,5-bis (2-phenylphenoxy) phthalonitrile thus obtained, 0.4 g of potassium fluoride, 1 g of 2-phenylphenol and 12 g of acetonitrile were added. The mixture was mixed and stirred at 70 ° C. for 23 hours.

  After cooling to room temperature, the reaction solution was filtered, acetonitrile was distilled off from the filtrate under reduced pressure, and 3.9 g of a concentrated solution of 3-fluoro-4,5,6-tris (2-phenylphenoxy) phthalonitrile thus obtained was added as follows. Used in Comparative Example 4.

Example 1 Synthesis of Phthalocyanine Compound (1) [(2- (Ph) PhO) ₈ (2- (Ph) PhO) ₈ VOPc] In a 50 ml test tube, 3, 4, 4 obtained in Synthesis Example 1 above were added. 5 g of 5,6-tetrakis (2-phenylphenoxy) phthalonitrile, 0.4 g of vanadium (III) chloride, 8 g of benzonitrile and 0.3 g of 1-octanol were added and stirred at 185 ° C. for 8 hours in a nitrogen gas atmosphere. After cooling to room temperature, the reaction solution was dropped into methanol for crystallization. The precipitate was collected by filtration and dried under reduced pressure to obtain 2 g of phthalocyanine compound (1) (yield: 41 mol% with respect to 3,4,5,6-tetrakis (2-phenylphenoxy) phthalonitrile).

Example 2 Synthesis of Phthalocyanine Compound (2) [(2- (COOCH ₃ ) PhO) ₈ (2- (Ph) PhO) ₈ VOPc] 3, 6 obtained in Synthesis Example 2 in a 50 ml test tube Nitrogen gas containing 3 g of bis (2-phenylphenoxy) -4,5-bis (2-methyloxycarbonylphenoxy) phthalonitrile, 0.2 g of vanadium (III) chloride, 5 g of benzonitrile and 0.2 g of 1-octanol The mixture was stirred at 185 ° C. for 8 hours under the atmosphere. After cooling to room temperature, the reaction solution was dropped into methanol for crystallization. The precipitate was collected by filtration and then dried under reduced pressure to give 2 g of phthalocyanine compound (2) (yield: 3,6-bis (2-phenylphenoxy) -4,5-bis (2-methyloxycarbonylphenoxy) phthalonitrile). 56 mol%).

Example 3 Synthesis of Phthalocyanine Compound (3) [(2- (F) PhO) ₈ (2- (Ph) PhO) ₈ VOPc] In a 50 ml test tube, 3,6- Bis (2-phenylphenoxy) -4,5-bis (2-fluorophenoxy) phthalonitrile (3 g), vanadium (III) chloride (0.3 g), benzonitrile (5 g), and 1-octanol (0.2 g) were added, and the nitrogen gas atmosphere was 185. Stir at 0 ° C. for 3 hours. After cooling to room temperature, the reaction solution was dropped into methanol for crystallization. The precipitate was collected by filtration and then dried under reduced pressure to give 2 g of phthalocyanine compound (3) (yield: 3,6-bis (2-phenylphenoxy) -4,5-bis (2-fluorophenoxy) phthalonitrile). 63 mol%).

Example 4: Synthesis of phthalocyanine compound (4) [(4- (F) PhO) ₈ (2- (Ph) PhO) ₈ VOPc] In a 50 ml test tube, 3,6- Bis (2-phenylphenoxy) -4,5-bis (4-fluorophenoxy) phthalonitrile (3 g), vanadium (III) chloride (0.3 g), benzonitrile (5 g) and 1-octanol (0.2 g) were added, and a nitrogen gas atmosphere was added to the pressure 185. Stir at 6 ° C. for 6 hours. After cooling to room temperature, the reaction solution was dropped into methanol for crystallization. The precipitate was collected by filtration and then dried under reduced pressure to give 2 g of phthalocyanine compound (4) (yield: 3,6-bis (2-phenylphenoxy) -4,5-bis (4-fluorophenoxy) phthalonitrile). 62 mol%).

Comparative Example 1: Synthesis of Comparative Phthalocyanine Compound (1) [(4- (COOCH ₃ ) PhO) ₈ (4- (MeO) PhO) ₈ VOPc] 4 obtained in Comparative Synthesis Example 1 above in a 50 ml test tube , 5-bis (4-methoxycarbonylphenoxy) -3,6-bis (4-methoxyphenoxy) phthalonitrile 15 g, vanadium (III) chloride 1.1 g, benzonitrile 22.5 g and 1-octanol 0.9 g The mixture was stirred at 190 ° C. for 3 hours under a nitrogen gas atmosphere. After cooling to room temperature, the reaction solution was dropped into methanol for crystallization. The precipitate was collected by filtration and then dried under reduced pressure to obtain 13.8 g of comparative phthalocyanine compound (1) (yield: 4,5-bis (4-methoxycarbonylphenoxy) -3,6-bis (4-methoxyphenoxy) phthalonitrile. To 89.9 mol%).

Comparative Example 2: Synthesis of Comparative Phthalocyanine Compound (2) [(3- (Ph) PhO) ₈ (3- (Ph) PhO) ₈ VOPc] In a 50 ml test tube, 4,5,6-tetrakis (3-phenylphenoxy) phthalonitrile 5 g, vanadium (III) chloride 0.4 g, benzonitrile 8 g and 1-octanol 0.3 g were added and stirred at 185 ° C. for 3 hours in a nitrogen gas atmosphere. . After cooling to room temperature, the reaction solution was dropped into methanol for crystallization. The precipitate was collected by filtration, and dried under reduced pressure to obtain 4 g of comparative phthalocyanine compound (2) (yield: 85 mol% with respect to 3,4,5,6-tetrakis (3-phenylphenoxy) phthalonitrile).

Comparative Example 3: Synthesis of comparative phthalocyanine compound (3) [(F) ₈ (2- (Ph) PhO) ₈ VOPc] 3,6-difluoro-4 obtained in Comparative Synthesis Example 3 above was added to a 50 ml test tube. , 5-bis (2-phenylphenoxy) phthalonitrile 3 g, vanadium (III) chloride 0.4 g, benzonitrile 5 g and 1-octanol 0.3 g were mixed and reacted at 185 ° C. for 5 hours in a nitrogen gas atmosphere. After cooling to room temperature, the reaction solution was dropped into methanol for crystallization. The precipitate was collected by filtration and then dried under reduced pressure to obtain 3 g of comparative phthalocyanine compound (3) (yield: 85 mol% with respect to 3,6-difluoro-4,5-bis (2-phenylphenoxy) phthalonitrile). It was.

Comparative Example 4: Synthesis of Comparative Phthalocyanine Compound (4) [(F) ₄ (2- (Ph) PhO) ₄ (2- (Ph) PhO) ₈ VOPc] Obtained in Comparative Synthesis Example 4 in a 50 ml test tube 4 g of the obtained 3-fluoro-4,5,6-tris (2-phenylphenoxy) phthalonitrile, 0.4 g of vanadium (III) chloride, 6 g of benzonitrile and 0.3 g of 1-octanol were added, and 185 under a nitrogen gas atmosphere. Stir at 5 ° C. for 5 hours. After cooling to room temperature, the reaction solution was dropped into methanol for crystallization. The precipitate was collected by filtration and then dried under reduced pressure to obtain 3 g of comparative phthalocyanine compound (4) (yield: 83 mol% based on 3-fluoro-4,5,6-tris (2-phenylphenoxy) phthalonitrile). It was.

  For the phthalocyanine compounds (1) to (4) obtained in Examples 1 to 4 and the comparative phthalocyanine compounds (1) to (4) obtained in Comparative Examples 1 to 4, the maximum absorption wavelength (λmax ) (Nm), the solar radiation transmittance (Te) (%) at each visible light transmittance (Tv) (%) was measured, and the results are shown in Table 1 and Table 2 below, and FIG. In FIG. 2, as each plot (and curve) is in the lower right direction, it means that the visible light transmittance is high and the solar radiation transmittance is low, that is, it is excellent as a heat ray shielding material.

  Further, the transmittance (%) when the maximum absorption wavelength (λmax) of these phthalocyanine compounds (1) to (4) and the comparative phthalocyanine compounds (1) to (4) with respect to wavelengths of 400 to 900 nm is 10% is shown in FIG. It is shown in 1.

<Measurement of maximum absorption wavelength (λmax)>
The maximum absorption wavelength (λmax) (nm) is measured using a spectrophotometer (manufactured by Shimadzu Corporation: UV-3100) with a transmittance of 300 to 2500 nm in chloroform of each phthalocyanine compound, and is between 600 and 900 nm. It is a wavelength (nm) which shows the minimum transmittance | permeability.

<Measurement of visible light transmittance (Tv) and solar transmittance (Te)>
The “visible light transmittance (Tv) (%)” and “sunlight transmittance (Te) (%)” of the phthalocyanine compound were calculated according to the standard of JIS R3106 (1998). It is the value measured according to the method. That is, the phthalocyanine compound was diluted with chloroform in a 1 cm quartz cell until the visible light transmittance (Tv) was 95, 90, 85, 80, 75%, and the transmittance (%) at that concentration was measured with a spectrophotometer ( Shimadzu Corporation: UV-3100). Based on the measurement results, the visible light transmittance (Tv) (%) and the solar radiation transmittance (Te) (%) were calculated. In calculating the visible light transmittance (Tv) (%) and the solar radiation transmittance (Te), numerical values in the wavelength range of 300 to 2500 nm were used.

  As apparent from Tables 1 and 2 and FIG. 2, the phthalocyanine compounds (1) to (4) of the present invention have an arbitrary visible light transmittance as compared with the comparative phthalocyanine compounds (1) to (4). It can be seen that the solar radiation transmittance (Te) at (Tv) is significantly low. From this, it is considered that the heat ray absorbing material using the phthalocyanine compound of the present invention can exhibit excellent heat ray absorbing ability.

Example 5
About the phthalocyanine compound (1) obtained in the said Example 1, the laminated glass (heat ray absorber) was produced as follows.

<Preparation of resin composition>
Polyvinyl butyral resin (Wako 1st grade, average polymerization degree 2400) 4 g, bis (2-ethylhexanoic acid) triethylene glycol 1.6 g as plasticizer, 2-methoxyethanol 40 g and phthalocyanine compound (1) 3 mg are sufficient at 150 ° C. The mixture was stirred and mixed. 2-methoxyethanol was removed by drying at 90 ° C. under reduced pressure to obtain a resin composition (1).

<Production of laminated glass>
The interlayer film for laminated glass was produced by press-molding the resin composition (1) obtained above at 180 ° C. The thickness of the film was 0.23 mm.

  The obtained interlayer film for laminated glass was cut into a size of 60 mm long × 60 mm wide.

  The laminated film was obtained by sandwiching the interlayer film for laminated glass between two transparent float glasses (length 60 mm × width 60 mm × thickness 1 mm). The obtained laminate was dried under reduced pressure at 90 ° C. for 30 minutes to obtain a laminated glass provided with an interlayer film for laminated glass.

  About the laminated glass obtained in this way, the transmittance | permeability of 300-2500 nm was measured using the spectrophotometer (Shimadzu Corporation make: UV-3100). Based on the obtained values, the visible light transmittance (Tv) (%) and the solar radiation transmittance (Te) (%) were calculated according to the standard of JIS R3106 (1998). The results are shown in Table 3 below together with the maximum absorption wavelength (λmax) (nm).

  As is apparent from Table 3 above, it is understood that the glass using the phthalocyanine compound (1) of the present invention has low solar transmittance (Te) while ensuring sufficient transparency. From this, the heat ray absorbing material using the phthalocyanine compound of the present invention is suitable for vehicles (for example, automobiles, buses, trains, etc.) and building heat ray absorbing laminated glass, heat ray shielding film, heat ray shielding resin glass, heat ray reflecting glass and the like. Considered to be usable.

Example 6
About the phthalocyanine compound (1) obtained in the said Example 1, the heat ray absorber (1) formed by providing a phthalocyanine compound containing intermediate | middle layer between two PET films as follows was produced.

<Preparation of resin composition>
Phthalocyanine compound (1) 3 mg, JP 2011-116918 A Phthalocyanine compound (maximum absorption wavelength: 869 nm) produced in the same manner as described in Comparative Synthesis Example 1 (other absorbent) 2 mg, EVA resin ( Tosoh Corporation, Ultrasen 720) 3 g and toluene 8 g were sufficiently stirred and mixed at 80 ° C. Toluene was removed by drying under reduced pressure at 40 ° C. to obtain a resin composition (2).

<Production of heat ray absorbing material>
The resin composition (2) obtained above is sandwiched between two PET films (thickness 0.1 mm) and press-molded at 100 ° C. for 2 minutes to obtain a film laminate (heat ray) having a thickness of 0.36 mm Absorbent (1)) was produced.

Comparative Example 5
A film laminate (comparative heat ray absorbent (1)) having a thickness of 0.36 mm was produced in the same manner as in Example 6 except that the phthalocyanine compound (1) was not used. .

Example 7
About the phthalocyanine compound (1) obtained in the said Example 1, the heat ray absorber (2) formed by providing a phthalocyanine compound containing film in a PET film as follows was produced.

<Preparation of resin composition>
Phthalocyanine compound (1) 100 mg, 17 wt% CsWO ₃ dispersion (manufactured by Sukkyung, SG-IRC90SPM; average dispersed particle size: 39.2 nm) (heat ray absorbing inorganic compound) 6 g, acrylic monomer (manufactured by Kyoei Chemical Co., light acrylate) DPE-6A) 2 g, photopolymerization initiator (BASF, Irgacure 369) 125 mg, and methyl ethyl ketone 2 g were sufficiently stirred and mixed to obtain a resin composition (3).

<Production of heat ray absorbing material>
The resin composition (3) obtained above was applied onto a PET film (thickness: 0.1 mm) using a spin coater, dried at 80 ° C. for 2 minutes, and then irradiated at an exposure dose of 500 mJ / cm ² . By irradiating with ultraviolet rays for 1 second, a film (heat ray absorbing material (2)) coated with the resin composition (3) having a thickness of 0.101 mm was produced.

Example 8
About the phthalocyanine compound (1) obtained in the said Example 1, the heat ray absorber (3) formed by providing a phthalocyanine compound containing film in a PET film as follows was produced.

<Preparation of resin composition>
Phthalocyanine compound (1) 80 mg, 29.9 wt% antimony-doped tin oxide (ATO) dispersion (manufactured by Ishihara Sangyo Co., Ltd., SNS-10M; average dispersed particle size: 0.107 μm) 10 g, dipentaerystol hexaacrylate (Kyoei) Chemical Co., Light Acrylate DPE-6A) 2 g and Photopolymerization Initiator (BASF, Irgacure 369) 125 mg were sufficiently mixed with stirring to obtain a resin composition (4).

<Production of heat ray absorbing material>
The resin composition (4) obtained above was applied onto a PET film (thickness: 0.1 mm) using a spin coater, dried at 80 ° C. for 2 minutes, and then irradiated at an exposure dose of 500 mJ / cm ² . By irradiating with ultraviolet rays for 1 second, a film (heat ray absorbing material (3)) coated with the resin composition (4) having a thickness of 0.101 mm was produced.

Comparative Example 6
In Example 8 above, except that the phthalocyanine compound (1) was not used, a film coated with an acrylic resin having a thickness of 0.101 mm (Comparative Heat Absorbing Material (2)) according to the same method as in Example 8. ) Was produced.

  With respect to the heat ray absorbing materials (1) to (3) and the comparative heat ray absorbing materials (1) to (2) thus obtained, a transmittance of 300 to 2500 nm was measured with a spectrophotometer (manufactured by Shimadzu Corporation: UV-3100). It measured using. Based on the obtained values, the visible light transmittance (Tv) (%) and the solar radiation transmittance (Te) (%) were calculated according to the standard of JIS R3106 (1998). The results are shown in Table 4 below. Moreover, the transmittance | permeability spectrum of each heat ray absorber is shown in FIG. 3 and FIG.

  As is apparent from Table 4 above, visible light can be obtained by combining the phthalocyanine compound (1) of the present invention with other near-infrared absorbing dyes (Example 6) or heat ray absorbing inorganic compounds (Examples 7 and 8). Although the transmittance (Tv) is slightly lowered, it can be seen that the solar transmittance (Te) can be significantly reduced. This is because the other near-infrared absorbing dye (Example 6) or the heat ray-absorbing inorganic compound (Examples 7 and 8) does not have sufficient absorption in the near-infrared region, so that the phthalocyanine compound (1) of the present invention It is thought that it supplements. From this, it is considered that the heat ray absorbing material of the present invention can be suitably used particularly for vehicles (for example, automobiles, buses, trains, etc.) and heat ray absorbing glass of buildings.

Example 9
About the phthalocyanine compound (1) obtained in the said Example 1, the heat ray absorbers (4)-(6) containing a phthalocyanine compound were produced as follows.

<Preparation of resin composition>
The phthalocyanine compound (1) was added at 35, 50, and 100 mass ppm with respect to the polycarbonate resin (manufactured by Teijin Chemicals Ltd., Panlite L1225WX), respectively, and mixed well with a mixer to obtain resin compositions (5) to (7) was obtained.

<Production of heat ray absorbing material>
Each of the resin compositions (5) to (7) obtained above was put into an injection molding machine adjusted to 250 ° C., and a 1.5 mm-thick molded plate [heat-absorbing material (4) to (6) )].

  With respect to the molded plate thus obtained, a transmittance of 300 to 2500 nm was measured using a spectrophotometer (manufactured by Shimadzu Corporation: UV-3100). Based on the obtained values, the visible light transmittance (Tv) (%) and the solar radiation transmittance (Te) (%) were calculated according to the standard of JIS R3106 (1998). The results are shown in Table 5 below. Moreover, all the obtained molded plates had a maximum absorption wavelength of 789 nm.

  As is apparent from Table 5 above, it can be seen that the heat ray absorbing material using the phthalocyanine compound (1) of the present invention can control the solar transmittance (Te) by changing the concentration of the phthalocyanine compound. Moreover, since the phthalocyanine compound of the present invention is excellent in heat resistance, it can be uniformly dispersed even when blended in a molded body using a thermoplastic resin such as polycarbonate, and a highly transparent heat ray absorbing material can be provided. It is.

  From this, the heat ray absorbing material using the phthalocyanine compound of the present invention is a heat ray absorbing laminated glass, a heat ray shielding film, a heat ray shielding resin glass, a heat ray reflecting glass, etc. that can be used for vehicles (for example, cars, buses, trains, etc.) It is considered that it can be suitably used for heat ray absorbing glass. Moreover, since the external appearance of the obtained heat ray absorbing material (molded article) is good, it can be expected to be used as a lighting building material or a resin glazing for automobiles.

Claims (4)

Following formula (1):
In the above formula (1), Z _{1 to} Z ₁₆ are each independently the following formula (2):
In the above formula (2), R is a halogen atom, an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, or an aryl group having 6 to 30 carbon atoms. An aryloxy group (—O—X ₁ , where X ₁ represents an aryl group having 6 to 30 carbon atoms), an ester group having 2 to 21 carbon atoms (—C (═O) OX ₂ or — OC (═O) X ₂ , wherein X ₂ represents an alkyl group having 1 to 20 carbon atoms), an amino group (—N (X ₃ ) ₂ , wherein X ₃ is independently , A hydrogen atom or an alkyl group having 1 to 20 carbon atoms), a thioalkoxy group having 1 to 20 carbon atoms (—S—X ₄ , where X ₄ is an alkyl having 1 to 20 carbon atoms) Group), or —COO (X ₅ O) _p —X ₆ [wherein X ₅ is Represents an alkylene group having 1 to 3 carbon atoms; X ₆ represents an alkyl group having 1 to 6 carbon atoms; p represents an integer of 1 to 5; and n represents an integer of 0 to 5 Is,
A substituent represented by (a),
At this time, 8 to ₁₆ of Z _{1 to} Z ₁₆ are each independently represented by the following formula (3):
In the above formula (3), R has the same definition as in the above formula (2); m is an integer of 0-4.
A substituent (b) represented by:
M is vanadyl (VO 2 ) ,
A phthalocyanine compound represented by In the above formula (1), Z ₁ , Z ₄ , Z ₅ , Z ₈ , Z ₉ , Z ₁₂ , Z ₁₃ and Z ₁₆ are each independently the substituent (b) represented by the above formula (3). The phthalocyanine compound according to claim 1, wherein   A heat-absorbing material comprising the phthalocyanine compound according to claim 1 or 2.   The heat ray absorbing material according to claim 3, further comprising at least one of a near infrared absorbing dye having a maximum absorption wavelength of 800 nm or more and a heat ray absorbing inorganic compound.