WO2013162017A1 - Composé phtalocyanine, mélange de composés phtalocyanine, et matériau absorbant les rayons thermiques l'utilisant - Google Patents

Composé phtalocyanine, mélange de composés phtalocyanine, et matériau absorbant les rayons thermiques l'utilisant Download PDF

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WO2013162017A1
WO2013162017A1 PCT/JP2013/062456 JP2013062456W WO2013162017A1 WO 2013162017 A1 WO2013162017 A1 WO 2013162017A1 JP 2013062456 W JP2013062456 W JP 2013062456W WO 2013162017 A1 WO2013162017 A1 WO 2013162017A1
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carbon atoms
group
alkyl group
phthalocyanine compound
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Japanese (ja)
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裕規 辰巳
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Nippon Shokubai Co Ltd
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Nippon Shokubai Co Ltd
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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
    • C09B47/00—Porphines; Azaporphines
    • C09B47/04—Phthalocyanines abbreviation: Pc
    • C09B47/06—Preparation from carboxylic acids or derivatives thereof, e.g. anhydrides, amides, mononitriles, phthalimide, o-cyanobenzamide
    • C09B47/067—Preparation from carboxylic acids or derivatives thereof, e.g. anhydrides, amides, mononitriles, phthalimide, o-cyanobenzamide from phthalodinitriles naphthalenedinitriles, aromatic dinitriles prepared in situ, hydrogenated phthalodinitrile
    • C09B47/0675—Preparation from carboxylic acids or derivatives thereof, e.g. anhydrides, amides, mononitriles, phthalimide, o-cyanobenzamide from phthalodinitriles naphthalenedinitriles, aromatic dinitriles prepared in situ, hydrogenated phthalodinitrile having oxygen or sulfur linked directly to the skeleton
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C17/00—Surface treatment of glass, not in the form of fibres or filaments, by coating
    • C03C17/28—Surface treatment of glass, not in the form of fibres or filaments, by coating with organic material
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
    • C09B67/00—Influencing the physical, e.g. the dyeing or printing properties of dyestuffs without chemical reactions, e.g. by treating with solvents grinding or grinding assistants, coating of pigments or dyes; Process features in the making of dyestuff preparations; Dyestuff preparations of a special physical nature, e.g. tablets, films
    • C09B67/0033—Blends of pigments; Mixtured crystals; Solid solutions
    • C09B67/0034—Mixtures of two or more pigments or dyes of the same type
    • C09B67/0035—Mixtures of phthalocyanines

Definitions

  • the present invention relates to a phthalocyanine compound, a mixture of phthalocyanine compounds, and a heat-absorbing material using the same.
  • the present invention relates to a phthalocyanine compound having a low solar radiation transmittance (excellent heat ray absorption ability) and a high visible light transmittance (excellent transparency), a mixture of phthalocyanine compounds, and a heat ray absorber using the same.
  • 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.
  • heat ray absorbing / shielding glass a glass plate surface 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.
  • metal oxides used as conventional heat ray absorption / screening agents can selectively absorb the near infrared region in the range of 670 to 850 nm, particularly more than 750 nm to 830 nm. It is necessary to increase the amount of addition in order to sufficiently absorb. However, in such a case, the transparency of the glass may be lowered, and the cost is not preferable.
  • 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.
  • Japanese Patent Application Laid-Open No. 2011-94127 discloses that in a phthalocyanine skeleton each having a benzene ring on each of its four sides, 4 to 8 substituted or unsubstituted phenoxy groups and 4 to 0 halogen atoms are substituted at the ⁇ -position. It is disclosed that a phthalocyanine compound into which 8 substituted or unsubstituted phenoxy groups are introduced at the position, and the use of the above phthalocyanine compound in a heat ray absorbing material.
  • JP 2011-94127 A cannot always be said to have sufficient heat ray absorption ability, and a better heat ray absorption ability has been demanded.
  • the present invention has been made in view of the above circumstances, and an object thereof is to provide a phthalocyanine compound and a mixture of phthalocyanine compounds having improved heat ray absorption ability.
  • Another object of the present invention is to provide a phthalocyanine compound and a mixture of phthalocyanine compounds having excellent heat ray absorption ability without reducing transparency (high visible light transmittance).
  • Another object of the present invention is to provide a heat ray absorbing material containing a phthalocyanine compound or a mixture of phthalocyanine compounds as described above.
  • the present inventor has found that a part of the phthalocyanine skeleton is substituted with a naphthalene structure, and 7 to 12 of the substituents on the phthalocyanine skeleton are aryloxy groups. It has been found that a phthalocyanine compound having a low solar transmittance and a high visible light transmittance. For this reason, it discovered that the heat ray absorber containing the said phthalocyanine compound or the mixture of a phthalocyanine compound can exhibit the outstanding heat ray absorptivity and transparency, and completed this invention based on the said knowledge.
  • Z 1 to Z 12 are each independently a halogen atom, an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, or the following formula (2) or ( 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, a carbon atom
  • An aryloxy group having 6 to 30 (—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 , where X 2 represents an alkyl group having 1 to 20 carbon atoms, an amino group (—N (X 3 ) 2 , wherein X 3 is Each independently represents a hydrogen atom or an alkyl group having 1 to 20 carbon atoms), a thioalkoxy group having 1 to 20 carbon atoms (-SX 4 , where X 4 is the number of carbon atoms Represents an alkyl group of 1 to 20), or —
  • ⁇ 20 alkoxy groups, Z 13 to Z 18 are each independently a hydrogen atom, a halogen atom, an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, an ester group having 2 to 21 carbon atoms (—C ( ⁇ O) OX 2 ′ or —OC ( ⁇ O) X 2 ′, where X 2 ′ represents an alkyl group having 1 to 20 carbon atoms), an amino group (—N (X 3 ′) 2
  • X 3 ′ each independently represents a hydrogen atom or an alkyl group having 1 to 20 carbon atoms), a thioalkoxy group having 1 to 20 carbon atoms (—SX 4 ′, X 4 ′ represents an alkyl group having 1 to 20 carbon atoms), —COO (X 5 ′ O) q —X 6 ′
  • X 5 ′ represents alkylene having 1 to 3 carbon atoms
  • X 6 ′ represents an alky
  • R ′ represents 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, carbon An aryloxy group having 6 to 30 atoms (—O—X 1 ′′, wherein 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, and an amino group (—N (X 3 ′′) 2
  • X 3 ′′ each independently represents a hydrogen atom or an alkyl group having 1 to 20 carbon atoms, a thioalkoxy group having 1 to 20 carbon atoms (—SX 4 ′′, when, X 4 "represents an alkyl group
  • 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 in the remainder Found that the visible light transmittance was high and the solar radiation transmittance was low. For this reason, it discovered that the heat ray absorber containing the said phthalocyanine compound can exhibit the outstanding heat ray absorption ability and transparency, and completed this invention based on the said knowledge.
  • Z A1 to Z A16 each independently represent the following formula (B):
  • R A represents 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 6 to 30 carbon atoms.
  • An aryloxy group (—O—X A1 , wherein X A1 represents an aryl group having 6 to 30 carbon atoms), an ester group having 2 to 21 carbon atoms (—C ( ⁇ O) OX A2 or —OC ( ⁇ O) X A2 , wherein X A2 represents an alkyl group having 1 to 20 carbon atoms, an amino group (—N (X A3 ) 2 , wherein X A3 is independently A hydrogen atom or an alkyl group having 1 to 20 carbon atoms), a thioalkoxy group having 1 to 20 carbon atoms (-SX A4 , where X A4 is a group having 1 to 20 carbon atoms) represents an alkyl group), or -COO (X A5 O) pA X A6 [this time, X A5 represents an alkylene group having a carbon number of 1 ⁇ 3; X A6 represents an alkyl group having a carbon number of 1 ⁇ 6; p A is
  • R A has the same definition as in the above formula (B); m A is an integer of 0 to 4.
  • a substituent represented by (b A ) M A is vanadyl (VO) or a tin compound, It is achieved by a phthalocyanine compound represented by
  • FIG. 1 is a graph showing retention time and absorbance of a mixture containing a phthalocyanine compound (1-4) by liquid chromatography.
  • FIG. 2 is a graph showing the absorbance of a compound belonging to each peak in FIG. 1 at a wavelength of 300 to 900 nm.
  • FIG. 3 is a graph showing the transmittance (%) of the phthalocyanine compound (1-1) and the comparative phthalocyanine compound (1-1) with respect to a wavelength of 300 to 1100 nm.
  • FIG. 4 is a graph showing the transmittance (%) of phthalocyanine compounds (1-2) to (1-6) with respect to wavelengths of 300 to 1100 nm.
  • FIG. 1 is a graph showing retention time and absorbance of a mixture containing a phthalocyanine compound (1-4) by liquid chromatography.
  • FIG. 2 is a graph showing the absorbance of a compound belonging to each peak in FIG. 1 at a wavelength of 300 to 900 nm.
  • FIG. 3
  • FIG. 5 is a graph showing the transmittance (%) of phthalocyanine compounds (1-7) to (1-10) with respect to wavelengths of 300 to 1100 nm.
  • FIG. 6 is a graph showing the solar transmittance (Te) with respect to the visible light transmittance (Tv) of the phthalocyanine compounds (1-1) to (1-6) and the comparative phthalocyanine compound (1-1).
  • FIG. 7 is a graph showing the solar transmittance (Te) with respect to the visible light transmittance (Tv) of the phthalocyanine compounds (1-7) to (1-10).
  • FIG. 8 is a graph showing the transmittance (%) of the heat-absorbing materials (1-1) and (1-2) with respect to a wavelength of 300 to 2500 nm.
  • FIG. 9 shows that the transmittance of the maximum absorption wavelength ( ⁇ max) of the phthalocyanine compounds (2-1) to (2-4) and the comparative phthalocyanine compounds (2-1) to (2-4) with respect to wavelengths of 400 to 900 nm is 10 It is a graph which shows the transmittance
  • FIG. 10 is a graph showing the solar transmittance (Te) with respect to the visible light transmittance (Tv) of the phthalocyanine compounds (2-1) to (2-4) and the comparative phthalocyanine compounds (2-1) to (2-4). It is.
  • FIG. 10 is a graph showing the solar transmittance (Te) with respect to the visible light transmittance (Tv) of the phthalocyanine compounds (2-1) to (2-4) and the comparative phthalocyanine compounds (2-1) to (2-4). It is.
  • FIG. 10 is a graph showing the solar transmittance (Te) with respect to the visible light transmittance (Tv
  • FIG. 11 is a graph showing the transmittance (%) of the heat ray absorbing materials (2-1) to (2-3) with respect to a wavelength of 300 to 2500 nm.
  • FIG. 12 is a graph showing the transmittance (%) of the comparative heat ray absorbing materials (2-1) to (2-2) 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).
  • 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”.
  • Z 2 , Z 3 , Z 6 , Z 7 , Z 10 and Z 11 in the above formula (1) are also collectively referred to as “ ⁇ -position”.
  • the substituent is also simply referred to as “substituent at the ⁇ -position”.
  • Z 1 , Z 4 , Z 5 , Z 8 , Z 9 and Z 12 are collectively referred to as “ ⁇ -position”.
  • the substituent is also simply referred to as “ ⁇ -position substituent”.
  • substituents of Z 15 and Z 16 in the above formula (1) are also simply referred to as “substituents at the ⁇ -position”, or Z 15 and Z 16 are collectively referred to as “ ⁇ -position”. Also called.
  • substituents of Z 13 and Z 18 are also referred to as “ ⁇ 1- position substituent” for convenience, or Z 13 and Z 18 are collectively referred to as “ ⁇ 1- position”. More Similarly, for convenience substituents Z 14 and Z 17, also referred to as “alpha 2-position substituent” or collectively the Z 14 and Z 17 is also referred to as "alpha 2-position.”
  • the phthalocyanine compound represented by the formula (1) of the present invention has a structure in which a part of the phthalocyanine skeleton is introduced into a naphthalene structure; and a structure in which the central metal is vanadyl (VO) or a tin compound.
  • the phthalocyanine compound represented by the formula (1) of the present invention 7 to 12 of the substituents on the phthalocyanine skeleton have the substituent (a) represented by the formula (2) or (2 ′). ing. In addition, any one may be sufficient as the substituent (a) represented by Formula (2) and Formula (2 '), and the combination of Formula (2) and Formula (2') may be sufficient.
  • the phthalocyanine compound represented by the formula (1) when the formula (2) and the formula (2 ′) are a combination, the total number thereof is 7 to 12. Thereby, it was found that the obtained phthalocyanine compound can further reduce the solar transmittance while maintaining a high visible light transmittance.
  • the phthalocyanine compound represented by the formula (1) of the present invention exhibits a high visible light transmittance and a low solar transmittance is unknown, but is presumed as follows. Note that the present invention is not limited to the following estimation. That is, the phthalocyanine compound represented by the formula (1) of the present invention has a naphthalene structure in the phthalocyanine skeleton, so that the conjugated system is expanded.
  • aryloxy groups since it has 7 to 12 bulky aryloxy groups represented by the formula (2) or (2 ′) (hereinafter sometimes simply referred to as “aryloxy groups”), these steric hindrances
  • neighboring substituents for example, when an aryloxy group is present as a substituent at the ⁇ -position, adjacent ⁇ -position aryloxy groups and neighboring ⁇ -position aryloxy groups
  • Overlapping 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.
  • the phthalocyanine compound structure becomes a highly distorted structure, and the conjugated system is further expanded.
  • the phthalocyanine compound of the present invention since the phthalocyanine compound of the present invention has a structure of the formula (1) and the conjugated system is expanded, the absorption wavelength becomes longer. Therefore, the obtained phthalocyanine compound has an excellent heat ray absorption ability (low solar radiation ability). Transmittance) and transparency (high visible light transmittance).
  • the maximum absorption wavelength ( ⁇ max) of the phthalocyanine compound is increased, and the maximum absorption wavelength ( ⁇ max) exceeds 900 nm and is 900 nm or less, preferably 760 to 860 nm, particularly 765 to 850 nm.
  • the heat-absorbing material containing the phthalocyanine compound represented by the formula (1) of the present invention selectively emits light in the wavelength region of more than 750 nm and not more than 900 nm, preferably 760 to 860 nm, particularly 765 to 850 nm. It can absorb and excels in heat ray absorption ability.
  • the phthalocyanine compound represented by the formula (1) of the present invention having such a structure has a high transmittance in the visible light wavelength region, particularly at 500 to 600 nm. Further, the maximum absorption wavelength ( ⁇ max) exists in a wavelength region exceeding 750 nm and not more than 900 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, the heat ray absorbing material using the phthalocyanine compound of the present invention is very excellent in transparency.
  • the phthalocyanine compound represented by the formula (1) of the present invention has excellent solvent solubility and compatibility with the 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 and the like, and can be applied to a large area industrially. Also, it is excellent in durability even when used for heat ray absorbing glass such as a window.
  • the phthalocyanine compound represented by the formula (1) of the present invention and the mixture of the phthalocyanine compounds have excellent heat ray absorption ability (low solar transmittance) and transparency (high visible light transmittance). Therefore, the heat ray absorbing material containing the phthalocyanine compound represented by the formula (1) or the mixture of the phthalocyanine compounds of the present invention is a vehicle (for example, an automobile, a bus, a train, etc.) or a heat ray absorbing laminated glass of a building, a heat ray shielding film. It can be suitably used for heat ray shielding resin glass, heat ray reflective glass and the like.
  • the phthalocyanine compound according to the first aspect of the present invention has the following formula (1):
  • M representing the central metal is vanadyl (VO) or a tin compound (Sn (L) 2 , where L is independently a fluorine atom, a chlorine atom, a bromine atom, or an iodine atom.
  • L is independently a fluorine atom, a chlorine atom, a bromine atom, or an iodine atom.
  • the maximum absorption wavelength ( ⁇ max) of the phthalocyanine compound can be more than 750 nm and 900 nm or less, preferably 760 to 860 nm, particularly 765 to 850 nm.
  • the phthalocyanine compound of the present invention can selectively absorb light in the specific wavelength range described above.
  • the heat ray absorbing material containing the phthalocyanine compound of the present invention has excellent heat ray absorbing ability and transparency.
  • M is preferably vanadyl (VO) or a halide of tin, more preferably vanadyl, tin chloride (SnCl 2 ), tin bromide (SnBr 2 ) or tin iodide (SnI 2 ).
  • vanadyl and tin chloride are particularly preferable.
  • Z 1 to Z 12 are each independently a halogen atom, an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, or the following formula (2) or ( 2 '):
  • substituent (a) 7 to 12 of Z 1 to Z 12 are substituents (a), and the remainder is A halogen atom, an alkyl group having 1 to 20 carbon atoms, or an alkoxy group having 1 to 20 carbon atoms.
  • Z 13 to Z 18 are each independently a hydrogen atom, a halogen atom, an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, an ester group having 2 to 21 carbon atoms ( —C ( ⁇ O) OX 2 ′ or —OC ( ⁇ O) X 2 ′, where X 2 ′ represents an alkyl group having 1 to 20 carbon atoms, an amino group (—N (X 3 ′ 2 , wherein X 3 ′ each independently represents a hydrogen atom or an alkyl group having 1 to 20 carbon atoms), a thioalkoxy group having 1 to 20 carbon atoms (—SX 4 ′) In this case, X 4 ′ represents an alkyl group having 1 to 20 carbon atoms), —COO (X 5 ′ O) q —X 6 ′ [where X 5 ′ represents 1 to 3 carbon atoms X 6 ′ represents an alkyl group having 1 to 6 carbon
  • 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 heat resistance, light resistance, and a weather resistance, even if it uses it for heat ray absorbers, such as a building and a motor vehicle, it exhibits the outstanding durability.
  • 9 to 12 of Z 1 to Z 12 are each independently a substituent (a), and the balance is a halogen atom, an alkyl group having 1 to 20 carbon atoms, or a carbon atom.
  • An alkoxy group having a number of 1 to 20 is preferable.
  • the position and type of the substituent (a) introduced into Z 1 to Z 12 may be uniform or non-uniform, but the substituent (a) is uniform at the ⁇ -position or ⁇ -position. It is preferable to be introduced into.
  • the position and type of the substituent (b) introduced into Z 13 to Z 18 may be uniform or non-uniform, but the substituent (b) is in the ⁇ 1 position, ⁇ 2 position or It is preferable that each be introduced uniformly at the ⁇ -position.
  • Z 1 to Z 12 substituted on the phthalocyanine skeleton are each independently a halogen atom, an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, or It is a substituent (a) represented by the above formula (2) or (2 ′).
  • Examples of the halogen atom substituted with Z 1 to Z 12 include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom.
  • a fluorine atom and a chlorine atom are preferable, and a fluorine atom is more preferable.
  • the alkyl group having 1 to 20 carbon atoms substituted with Z 1 to Z 12 is not particularly limited, and examples thereof include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, and an isobutyl group.
  • a linear or branched alkyl group having 1 to 8 carbon atoms particularly a methyl group, an ethyl group, an n-propyl group, an isopropyl group. Is preferred.
  • the alkoxy group having 1 to 20 carbon atoms to be substituted with Z 1 to Z 12 is not particularly limited, and examples thereof include linear or branched alkoxy groups having 1 to 20 carbon atoms. 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.
  • a linear or branched alkoxy group having 1 to 8 carbon atoms, particularly a methoxy group and an ethoxy group are preferable.
  • R in the substituent (a) substituted by Z 1 to Z 12 and represented by the above formula (2) or (2 ′) is a halogen atom, an alkyl group having 1 to 20 carbon atoms, or 1 to 20 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), amino A group (—N (X 3 ) 2 , wherein X 3 each independently represents 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 , wherein X 4 is an alkyl group having 1
  • R is a halogen atom, an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, or 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.
  • R is a halogen atom, an alkyl group having 1 to 8 carbon atoms, a carbon atom
  • An alkoxy group having 1 to 8 carbon atoms, an aryl group having 6 to 10 carbon atoms, an ester group having 2 to 9 carbon atoms (—C ( ⁇ O) OX 2 or —OC ( ⁇ O) X 2 , 2 is preferably an alkyl group having 1 to 8 carbon atoms.
  • 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 .
  • the maximum absorption wavelength ( ⁇ max) of the phthalocyanine compound can be shifted to a long wavelength region by extending the conjugated system by this introduction.
  • the electronic stability of the phthalocyanine compound 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 decomposition of the phthalocyanine compound by 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.
  • the above effect can be more prominent when the substituent (a) is present in the same number and in different axes in each structural unit. Therefore, it is preferable that the substituent (a) is introduced in an amount of more than 1 to 2, more preferably 2 at each of the ⁇ -position and ⁇ -position.
  • the above is estimation and does not limit this invention.
  • k is an integer from 0 to 5
  • l is an integer from 0 to 7, and is not particularly limited, but k is from 0 to 3
  • the integer, l is preferably an integer of 0-3.
  • the bonding position of R to the phenoxy group is not particularly limited.
  • n is 1, the second and fourth positions are preferable and the second position is more preferable in consideration of selective absorption and solubility in a specific wavelength range.
  • n considering the visible light transmittance and the like, the 2nd, 5th, 2, 6th, 2nd and 4th positions are preferable, and the 2nd, 5th, 2nd and 6th positions are more preferable.
  • the oxygen atom (—O—) and R bonded to the phthalocyanine skeleton may be substituted with any hydrogen atom of the naphthalene ring.
  • the bonding position of the oxygen atom (—O—) bonded to the phthalocyanine skeleton to the naphthalene ring is not particularly limited and may be derived from 1-naphthol or 2-naphthol. Preferably, it is derived from 2-naphthol.
  • the bonding position of R to the naphthalene ring is not particularly limited.
  • R when R is adjacent to an oxygen atom, the absorption wavelength region tends to be longer or the solubility is improved, which is preferable.
  • R is preferably in the 2,3,7,8 positions, and more preferably in the 2,8 positions.
  • R is preferably in the 1,3,4,8 position, more preferably in the 1,3 position.
  • examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.
  • a fluorine atom and a chlorine atom are preferable, and a fluorine atom is more preferable.
  • the alkyl group having 1 to 20 carbon atoms is not particularly limited, and the same alkyl group as described above can be used. Therefore, detailed description is omitted here, but the existence and durability of the maximum absorption wavelength in a specific wavelength region are omitted.
  • a linear or branched alkyl group having 1 to 8 carbon atoms particularly a methyl group, an ethyl group, an n-propyl group, and an isopropyl group are preferable.
  • a methyl group, n-propyl group, and isopropyl group are preferable, and a methyl group and isopropyl group are particularly preferable.
  • the alkoxy group having 1 to 20 carbon atoms is not particularly limited, and an alkoxy group similar to the above can be used. Therefore, detailed description is omitted here, but the existence and durability of the maximum absorption wavelength in a specific wavelength region are omitted.
  • a linear or branched alkoxy group having 1 to 8 carbon atoms, particularly a methoxy group and an ethoxy group are preferable, and a methoxy group is more preferable.
  • 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; And condensed polycyclic hydrocarbon groups such as a group, a fluorenyl group, an acenaphthylenyl group, an acenaphthenyl group, a phenalenyl group, a phenanthryl group, an anthryl group, an aceanthrylenyl group, and a triphenylenyl group.
  • a phenyl group and a naphthyl group are preferable, and a phenyl group is more preferable in consideration of the existence and durability of the maximum absorption wavelength in a specific wavelength region.
  • the aryloxy group having 6 to 30 carbon atoms is not particularly limited and is represented by the formula: —O—X 1 .
  • X 1 represents an aryl group having 6 to 30 carbon atoms.
  • 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.
  • a phenyl group and a naphthyl group are preferable, and a phenyl group is more preferable in consideration of the existence and durability of the maximum absorption wavelength in a specific wavelength region.
  • 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 .
  • X 2 represents an alkyl group having 1 to 20 carbon atoms.
  • the alkyl group having 1 to 20 carbon atoms is not particularly limited, and an alkyl group similar to the above can be used.
  • a linear or branched alkyl group having 1 to 8 carbon atoms, particularly a methyl group and an ethyl group are preferable, and a methyl group is more preferable. .
  • the amino group is not particularly limited and is represented by the formula: —N (X 3 ) 2 .
  • X 3 each independently represents a hydrogen atom or an alkyl group having 1 to 20 carbon atoms.
  • X 3 may be the same or different.
  • 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 the description thereof is omitted here.
  • a linear or branched alkyl group having 1 to 8 carbon atoms, particularly a methyl group and an ethyl group are preferable, and a methyl group is more preferable. .
  • the thioalkoxy group having 1 to 20 carbon atoms is not particularly limited and is represented by the formula: —SX 4 .
  • X 4 represents an alkyl group having 1 to 20 carbon atoms.
  • the alkyl group having 1 to 20 carbon atoms is not particularly limited, and an alkyl group similar to the above can be used.
  • a linear or branched alkyl group having 1 to 8 carbon atoms, particularly a methyl group and an ethyl group are preferable, and a methyl group is more preferable. .
  • X 5 represents an alkylene group having 1 to 3 carbon atoms.
  • the alkylene group having 1 to 3 carbon atoms includes a methylene group, an ethylene group, and a propylene group.
  • 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.
  • 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.
  • the alkyl group having 1 to 6 carbon atoms is not particularly limited, and examples thereof include straight-chain, branched or cyclic alkyl groups having 1 to 6 carbon atoms.
  • 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 -Linear, branched or cyclic alkyl groups such as -pentyl group, isopentyl group, neopentyl group, n-hexyl group and cyclohexyl group.
  • a linear or branched alkyl group having 1 to 3 carbon atoms particularly a methyl group or an ethyl group is preferable, and a methyl group is more preferable.
  • the substituent (a) 7 to 12 of Z 1 to Z 12 are the substituent (a).
  • the remaining 5 to 0 substituents are a halogen atom, an alkyl group having 1 to 20 carbon atoms, or an alkoxy group having 1 to 20 carbon atoms.
  • the substituent (a) and the remainder may be the same or different.
  • 9 to 12 of Z 1 to Z 12 are preferably the substituent (a), and more preferably all 12 are the substituent (a).
  • the remainder is all halogen atoms.
  • the substituent (a) may be arranged at any position of Z 1 to Z 12 as long as 7 to 12 substituents are introduced into the phthalocyanine skeleton.
  • an unsubstituted 2-phenylphenoxy group is preferable, and further, the number of substituted or unsubstituted 2-phenylphenoxy groups is preferably 3 or more, more preferably 6 or more. More preferably, at least Z 1 , Z 4 , Z 5 , Z 8 , Z 9 and Z 12 ( ⁇ position) are preferably substituted or unsubstituted 2-phenylphenoxy groups.
  • the phthalocyanine compound having such a structure can exhibit higher visible light transmittance and heat ray absorption, and the heat ray absorbing material containing the phthalocyanine compound can exhibit excellent transparency and heat ray absorption ability.
  • Z 13 to Z 18 substituted on the naphthalene structure are each independently a hydrogen atom, a halogen atom, an alkyl group having 1 to 20 carbon atoms, or an alkoxy having 1 to 20 carbon atoms.
  • a thioalkoxy group having 1 to 20 carbon atoms (—SX 4 ′, where X 4 ′ represents an alkyl group having 1 to 20 carbon atoms), —COO (X 5 ′ O) q —X 6 ′ [where X 5 ′ is an alkylene group having 1 to 3 carbon atoms] X 6 ′ represents an alkyl group having 1 to 6 carbon atoms; q is an integer of 1 to 5], or a substituent represented by the above formula (3) or (3 ′) ( b).
  • Halogen atoms substituted with Z 13 to Z 18 alkyl groups having 1 to 20 carbon atoms, alkoxy groups having 1 to 20 carbon atoms, aryl groups having 6 to 30 carbon atoms, esters having 2 to 21 carbon atoms
  • the group amino group, thioalkoxy group having 1 to 20 carbon atoms, or —COO (X 5 ′ O) q —X 6 ′, those similar to the above can be used, and thus detailed description thereof is omitted here.
  • Z 13 to Z 18 may be the same or different from each other.
  • R ′ of the substituent (b) substituted by Z 13 to Z 18 and represented by the above formula (3) or (3 ′) is a halogen atom, an alkyl group having 1 to 20 carbon atoms, or 1 to 20 alkoxy groups, aryl groups having 6 to 30 carbon atoms, aryloxy groups having 6 to 30 carbon atoms (—O—X 1 ′′, where X 1 ′′ is an aryl group having 6 to 30 carbon atoms.
  • an amino group (—N (X 3 ′′) 2 , wherein X 3 ′′ each independently represents a hydrogen atom or an alkyl group having 1 to 20 carbon atoms), the number of carbon atoms 1 to 20 thioalkoxy groups (—S—X 4 ′′, wherein X 4 ′′ represents a carbon atom Or a —COO (X 5 ′′ O) r —X 6 ′′ [wherein X 5 ′′ represents an alkylene group having 1 to 3 carbon atoms; X 6 ′′ Represents an alkyl group having 1 to 6 carbon atoms; r is an integer of 1 to 5].
  • m is an integer from 0 to 5
  • n is an integer from 0 to 7, and is not particularly limited, but m is an integer from 0 to 3.
  • N is preferably an integer of 0 to 3.
  • each R ′ may be the same or different. Since R ′ of the substituent (b) can be the same as R, detailed description thereof is omitted here.
  • Z 13 to Z 18 are each a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, an amino group ( -N (R 3 ') 2 , wherein R 3 ' each independently represents a hydrogen atom or an alkyl group having 1 to 20 carbon atoms), a thioalkoxy group having 1 to 20 carbon atoms,
  • the substituent (b) is preferable, and a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, and a substituent (b) are more preferable.
  • preferred examples of the phthalocyanine compound represented by the formula (1) according to the present invention include the following compounds.
  • the 3rd and 6th positions are substituted with the ⁇ position of the phthalocyanine nucleus, and the 4th and 5th positions are substituted with the ⁇ position of the phthalocyanine nucleus.
  • the chemical formulas exemplified for the phthalocyanine compound are described in one kind, but when two different ⁇ -positions (or ⁇ -positions) on one benzene ring are substituted with different substituents (for example, phthalocyanine, for example)
  • substituents for example, phthalocyanine, for example
  • the ⁇ -position (or ⁇ -position) closer to the naphthalene ring and the far-side ⁇ -position (or ⁇ -position) substituent may be interchanged.
  • Ph represents a phenyl group
  • Pc represents a phthalocyanine nucleus
  • Np represents a naphthalene ring
  • the central metal is shown immediately before Pc.
  • naphthalene ring occupies a part of the phthalocyanine nucleus, and strictly speaking, the naphthalene ring is not separately bonded to the phthalocyanine nucleus, but for the sake of convenience, the central metal is used to show that the naphthalene ring is included. It describes as Np immediately before.
  • the phthalocyanine compound of the following structure is prescribed
  • a phthalocyanine compound of the formula: [ ⁇ 4- (COOCH 3 ) PhO ⁇ 6 ⁇ 4- (OCH 3 ) PhO ⁇ 6 NpVOPc] is referred to as “phthalocyanine compound (1-1)”.
  • the method for producing the phthalocyanine compound represented by the formula (1) of the present invention is not particularly limited, and is described in, for example, JP-A No. 2000-26748, JP-A No. 2001-106689, and JP-A No. 2005-220060.
  • a conventionally known method such as the above method can be appropriately modified and applied. That is, the method for producing the phthalocyanine compound of the present invention is preferably a method in which a phthalonitrile compound, a 2,3-dicyanonaphthalene derivative (naphthalonitrile compound) and a metal compound are cyclized in a molten state or in an organic solvent. .
  • the preferable manufacturing method of the phthalocyanine compound of this invention is described.
  • metal compound a dicyanonaphthalene derivative
  • Z 1 to Z 4 , Z 5 to Z 8 and Z 9 to Z 12 are each independently a halogen atom, an alkyl group having 1 to 20 carbon atoms, or an alkoxy group having 1 to 20 carbon atoms.
  • Z 1 to Z 12 7 to 12 are substituents (a), and the balance is a halogen atom, an alkyl group having 1 to 20 carbon atoms, or carbon.
  • Z 1 - Z 12 in the formula (4) to (6) are the same as Z 1 - Z 12 in the formula (1), description thereof is omitted.
  • R, k, and l in the above formulas (8) and (8 ′) are the same as the definitions in the above formulas (2) and (2 ′), and thus the description thereof is omitted.
  • Z 13 to Z 18 are each independently a hydrogen atom, a halogen atom, an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, or the number of carbon atoms. ester group having 2 to 21 amino group, a thioalkoxy group having a carbon number of 1 ⁇ 20, -COO (X 5 'O) q -X 6', or the following formula (9) or (9 '):
  • a halogenated phthalonitrile derivative is Q 1 -L 2 (where Q 1 represents an alkyl group having 1 to 20 carbon atoms; L 2 represents a hydroxyl group, a fluorine atom, , A chlorine atom, a bromine atom or an iodine atom) and / or the following formula (10) or (10 ′):
  • the alkyl group represented by Q 1 is the same as defined in the above formula (1), and thus the description thereof is omitted here.
  • R, k, and l are the same as the definitions in the above formulas (2) and (2 ′), and thus the description thereof is omitted here.
  • examples of the halogenated phthalonitrile derivative include, but are not limited to, tetrafluorophthalonitrile and tetrachlorophthalonitrile. Of these, tetrafluorophthalonitrile is preferably used.
  • the halogenated phthalonitrile derivative is first substituted with Q 1 -L 2 having a substituent for introduction at the ⁇ -position, or the formula (10) or ( 10 ′) and the desired phthalonitrile compound by reacting with Q 1 -L 2 having a substituent for introduction into the ⁇ -position or the compound of formula (10) or (10 ′) Can be manufactured.
  • the starting material naphthalonitrile compound of formula (7) (2,3-dicyanonaphthalene derivative) is prepared by the method disclosed in JP-A-2009-132623 or the same halogen as the phthalonitrile compound described above. It can be synthesized by a conventionally known method such as a substitution reaction, or a commercially available product can be used.
  • the cyclization reaction can be carried out in the absence of a solvent, but it is preferably carried out using an organic solvent.
  • the organic solvent may be any inert solvent that has low reactivity with the phthalonitrile compound and naphthalonitrile compound as starting materials, and preferably exhibits no reactivity.
  • Inert solvents such as chlorobenzene, o-chlorotoluene, dichlorobenzene, trichlorobenzene, 1-chloronaphthalene, 1-methylnaphthalene and benzonitrile
  • alcohols such as 1-hexanol, 1-pentano
  • 1-chloronaphthalene, 1-methylnaphthalene, 1-octanol and benzonitrile are preferably used, and 1-octanol, dichlorobenzene and benzonitrile are more preferably 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 formulas (4) to (6) is the total amount of the phthalonitrile compound of the formulas (4) to (6).
  • the amount is usually 2 to 80% by weight, preferably 10 to 70% by weight, more preferably 30 to 68% by weight.
  • the reaction conditions for the phthalonitrile compound of the formulas (4) to (6), the dicyanonaphthalene derivative represented by the formula (7) and the metal compound are not particularly limited as long as the reaction proceeds.
  • the reaction temperature is usually 100 to 240 ° C., preferably 130 to 200 ° C.
  • the reaction time is not particularly limited, but is 1 to 72 hours, preferably 3 to 48 hours, and more preferably 5 to 30 hours.
  • the metal compound is preferably 0.9 to 2 mol, more preferably 1 to 1.9 mol, and still more preferably 1.1 to 3 mol of the total amount of the phthalonitrile compounds of the formulas (4) to (6). Charge in the range of ⁇ 1.8 mol.
  • the substituted or unsubstituted dicyanonaphthalene derivative is 0.3 to 3 mol, more preferably 0.5 to 2, and still more preferably with respect to 3 mol of the total amount of the phthalonitrile compounds of the formulas (4) to (6). It is charged in the range of 0.6 to 1.5 mol, particularly preferably 0.7 to 1.3.
  • 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).
  • an inert gas or oxygen-containing gas atmosphere for example, nitrogen gas, helium gas, argon gas, or oxygen / nitrogen mixed gas
  • the phthalocyanine compound represented by the formula (1) of the present invention is synthesized by the above method, the phthalocyanine compound cyclized only by the phthalonitrile compound without reacting with the naphthalonitrile compound (hereinafter referred to as the phthalocyanine compound of the formula (1))
  • the phthalocyanine compound of the formula (1) cyclized only by the phthalonitrile compound without reacting with the naphthalonitrile compound
  • a phthalocyanine compound that does not contain a naphthalene ring may also be obtained as a by-product.
  • by-products are also collectively referred to as “by-products”.
  • a mixture containing the phthalocyanine compound of the formula (1) of the present invention and the by-product is obtained. That is, depending on the type of substituent selected, a phthalocyanine compound represented by the formula (A) described in detail below can also be obtained.
  • the phthalocyanine compound of the formula (1) when the phthalocyanine compound of the formula (1) is obtained alone, an operation of separating the phthalocyanine compound of the formula (1) and the phthalocyanine compound as a by-product by column or crystallization may be performed.
  • the use of a column is preferable because the phthalocyanine compound of the formula (1) can be easily obtained.
  • the phthalocyanine compound not containing the naphthalene ring is represented by the following formula (I).
  • M ′ representing the central metal is vanadyl (VO) or a tin compound, like M in the above formula (1).
  • substituents represented by Z 1 ′ to Z 16 ′ are the same as the substituents represented by Z 1 to Z 12 in the above formula (1), detailed description thereof is omitted here.
  • the maximum absorption wavelength ( ⁇ max) of the phthalocyanine compound of the above formula (I) is more than 750 nm and not more than 850 nm, preferably 760 to 810 nm, particularly preferably 765 to 800 nm.
  • a mixture comprising the phthalocyanine compound represented by the formula (1) of the present invention and the by-product produced by the above method (in the present specification, it may be simply referred to as “mixture of phthalocyanine compounds” or “mixture”) Has a low solar transmittance (Te).
  • Te solar transmittance
  • the maximum absorption wavelength ( ⁇ max) of the phthalocyanine compound not containing a naphthalene ring in the main skeleton exceeds 850 nm to 850 nm
  • it is preferably in the range of 760 to 810 nm, particularly 765 to 800 nm.
  • the present invention also provides the following phthalocyanine compounds. That is, the third of the present invention relates to a phthalocyanine compound represented by the formula (A).
  • the compound represented by the formula (A) is also simply referred to as “phthalocyanine compound” or “phthalocyanine compound according to the present invention”.
  • Z A2 , Z A3 , Z A6 , Z A7 , Z A10 , Z A11 , Z A14 and Z A15 are also collectively referred to as “ ⁇ -position”.
  • the substituent is also simply referred to as “substituent at the ⁇ -position”.
  • Z A1 , Z A4 , Z A5 , Z A8 , Z A9 , Z A12 , Z A13 and Z A16 is also collectively referred to as “ ⁇ -position”.
  • the substituent is also simply referred to as “substituent at the ⁇ -position”.
  • the phthalocyanine compound represented by the formula (A) 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 vanadyl (VO ) Or a tin compound.
  • R 2 represents an alkylene group having 1 to 3 carbon atoms
  • 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 ( ⁇ max) 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.
  • the phthalocyanine compound represented by the formula (A) of the present invention at least 8 out of the total 16 phenoxy groups are substituted or unsubstituted 2-phenylphenoxy groups. Thereby, it was found that the obtained phthalocyanine compound can further reduce the solar transmittance while maintaining a high visible light transmittance.
  • the reason why the phthalocyanine compound represented by the formula (A) of the present invention exhibits high visible light transmittance and low solar transmittance is unknown, but is estimated as follows. Note that the present invention is not limited to the following estimation.
  • the obtained phthalocyanine compound exhibits high visible light transmittance. Further, by combining the steric hindrance of the bulky 2-phenylphenoxy group and the central metal vanadyl (VO) or tin halide with the bulky substituted or unsubstituted 2-phenylphenoxy group, By the same mechanism as the phthalocyanine compound represented by (1), the conjugated system is further expanded in the phthalocyanine compound represented by the formula (A).
  • the maximum absorption wavelength ( ⁇ max) and the second absorption peak (subpeak) of the phthalocyanine compound represented by the formula (A) are lengthened, and both the maximum absorption wavelength and the second absorption peak are 670 to 850 nm.
  • the heat ray absorbing material containing the phthalocyanine compound represented by the formula (A) of the present invention emits light in the wavelength region of 670 to 850 nm, preferably 680 to 830 nm, more preferably 685 to 820 nm, and particularly 690 to 810 nm.
  • maximum absorption wavelength ( ⁇ max) (nm)” and “second absorption peak (nm)” of the phthalocyanine compound mean values measured according to the methods of the following examples.
  • the phthalocyanine compound represented by the formula (A) of the present invention has a particularly high transmittance at 500 to 600 nm.
  • the visible light transmittance (Tv) of the phthalocyanine compound represented by the formula (A) of the present invention is high.
  • the heat ray absorbing material using the phthalocyanine compound of the present invention is very excellent in transparency.
  • the phthalocyanine compound represented by the formula (A) of the present invention is excellent in solvent solubility and compatibility with the resin, and excellent in various properties such as heat resistance, light resistance, and weather resistance.
  • the heat ray absorbing material containing the phthalocyanine compound represented by the formula (A) of the present invention can exhibit excellent heat ray absorbing ability, heat ray absorbing laminated glass for vehicles and buildings, heat ray shielding film, heat ray shielding resin glass, It can be suitably used for heat ray reflective glass.
  • the phthalocyanine compound of the present invention has the following formula (A):
  • M A representing the central metal is the same as M in the above formula (1), and thus description thereof is omitted.
  • the maximum absorption wavelength ( ⁇ max) and the second absorption peak of the phthalocyanine compound are 670 to 850 nm, preferably 680 to 830 nm, more preferably 685 to 820 nm, particularly It can exist at 690-810 nm. Therefore, the phthalocyanine compound represented by the formula (A) of the present invention can selectively absorb light in the specific wavelength region described above.
  • M is preferably vanadyl (VO) or a halide of tin, more preferably vanadyl, tin chloride (SnCl 2 ), tin bromide (SnBr 2 ) or tin iodide (SnI 2 ).
  • VO vanadyl
  • SnCl 2 tin chloride
  • SnBr 2 tin bromide
  • SnI 2 tin iodide
  • Vanadyl and tin chloride are more preferable, and vanadyl is particularly preferable.
  • Z A1 to Z A16 represent the following formula (B):
  • substituents (b A ) may be arranged at any position of Z A1 to Z A16 , but are preferably introduced at the ⁇ -position. It is preferable. That is, the ⁇ -position is preferably each independently a substituent (b A ) represented by the above formula (C).
  • the visible light transmittance can be further increased, and the heat ray absorbing material containing the phthalocyanine compound can exhibit excellent transparency.
  • the 2-phenylphenoxy group is adjacent to a short distance, so that the adjacent 2-phenylphenoxy groups overlap at an angle in order 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.
  • ⁇ max maximum absorption wavelength
  • the second absorption peak exist in the above-described preferable range.
  • the phthalocyanine compound represented by the formula (A) of the present invention can selectively absorb light in the specific wavelength range described above, and is excellent in heat resistance, light resistance, and weather resistance.
  • 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.
  • Z A1 introduction position and the type of substituent (a A) to ⁇ Z A16 may be also uneven be uniform but, substituent (a A) is ⁇ -position or ⁇ -position It is preferable that it be introduced uniformly.
  • RA is the same as R in the above formula (1), and thus detailed description thereof is omitted.
  • the symbol indicating the structure corresponds to the same symbol in the description of the above formula (1) unless there is a separate detailed description.
  • “X A1 ” in the description of R A corresponds to “X 1 ” in the description of R in the above formula (1), from which the subscript “ A ” is deleted.
  • R A is a halogen atom, an alkyl group having 1 to 20 carbon atoms, or 6 to 30 carbon atoms. And an aryl group having 2 to 21 carbon atoms, and —COO (X A5 O) p —X A6 are preferred.
  • R is a halogen atom or a carbon atom number of 6 to 30. And an aryl group having 2 to 21 carbon atoms is preferred.
  • R A is a halogen atom, an aryl group having 6 to 30 carbon atoms, an ester group having 2 to 21 carbon atoms, —COO (X), for the same reason as in the phthalocyanine compound represented by the above formula (1).
  • A5 O) pA -X A6 is preferred.
  • n A is an integer of 0 to 5, and the number of RA introduced into the phenoxy group is not particularly limited.
  • n A is preferably an integer of 1 to 4, and more preferably 1 or 2.
  • the bonding position of the substituent to the phenoxy group is not particularly limited.
  • the preferable substitution position of R A is the same as the substitution position of R in the above formula (2).
  • the alkyl group having 1 to 20 carbon atoms is the same as the alkyl group represented by R in the above formula (2), and detailed description thereof is omitted. Among them, the maximum absorption wavelength and the second peak are specified. In view of existence in the wavelength range, durability, and the like, a linear or branched alkyl group having 1 to 8 carbon atoms, particularly a methyl group and an ethyl group are preferable, and a methyl group is more preferable.
  • the alkoxy group having 1 to 20 carbon atoms is the same as the alkoxy group represented by R in the above formula (2), and detailed description thereof is omitted. Among them, the maximum absorption wavelength and the second peak are specified. In view of the presence in the wavelength range, durability, and the like, a linear or branched alkoxy group having 1 to 8 carbon atoms, particularly a methoxy group and an ethoxy group are preferable, and a methoxy group is more preferable.
  • the aryl group having 6 to 30 carbon atoms is the same as the aryl group represented by R in the above formula (2), detailed description thereof is omitted, but the maximum absorption wavelength and the second peak are particularly specified. In consideration of existence in the wavelength range, durability, and the like, a phenyl group and a naphthyl group are preferable, and a phenyl group is more preferable.
  • aryloxy group having 6 to 30 carbon atoms is the same as the aryloxy group represented by R in the above formula (2), detailed description thereof will be omitted.
  • a phenyl group and a naphthyl group are preferable, and a phenyl group is more preferable.
  • ester group having 2 to 21 carbon atoms is the same as the ester group represented by R in the above formula (2), detailed description thereof is omitted. Among them, the maximum absorption wavelength and the second peak are specified. In view of existence in the wavelength range, durability, and the like, a linear or branched alkyl group having 1 to 8 carbon atoms, particularly a methyl group and an ethyl group are preferable, and a methyl group is more preferable.
  • the amino group is the same as the amino group represented by R in the above formula (2), detailed description thereof is omitted. Among them, the presence or durability of the maximum absorption wavelength or the second peak in a specific wavelength range is particularly important. In view of the properties and the like, a linear or branched alkyl group having 1 to 8 carbon atoms, particularly a methyl group and an ethyl group are preferable, and a methyl group is more preferable.
  • the thioalkoxy group having 1 to 20 carbon atoms is the same as the alkoxy group represented by R in the above formula (2), and detailed description thereof will be omitted.
  • the maximum absorption wavelength and the second peak In view of existence 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 and an ethyl group are preferable, and a methyl group is more preferable.
  • X A5 is preferably an ethylene group or a propylene group, and more preferably an ethylene group.
  • p A is preferably an integer of 1 to 3, and more preferably 1 or 2.
  • X A6 is preferably a linear or branched alkyl group having 1 to 3 carbon atoms, particularly a methyl group or an ethyl group in view of durability, solubility, etc., and in consideration of the crystallinity of the phthalocyanine compound, Groups are more preferred.
  • 8 to 16 of Z A1 to Z A16 are the substituent (b A ) of the above formula (C).
  • the 8 to 16 substituents (b A ) may be the same or different.
  • R A in the above formula (C) is the same definition as the substituent R A in the above formula (B), a description thereof will be omitted.
  • m A is an integer of 0 to 4
  • the number of R A is introduced into the 2-phenylphenoxy group is not particularly limited.
  • m A is preferably an integer of 0 to 2, and more preferably 0 or 1.
  • the bonding position of the substituent to the 2-phenylphenoxy group is not particularly limited. For example, if m A is 1, when considering the visible transmittance, 4, 5, preferably 6, 5, 6 is more preferable.
  • phthalocyanine compound represented by the formula (A) includes the following compounds.
  • the description method of the abbreviation of the following phthalocyanine compounds is the same as the above.
  • the phthalocyanine compound of the following structure is prescribed
  • a phthalocyanine compound of the formula: (2- (Ph) PhO) 8 (2- (Ph) PhO) 8 VOPc is referred to as “phthalocyanine compound (2-1)”.
  • the method for producing the phthalocyanine compound represented by the formula (A) of the present invention is basically the same as the method for producing the phthalocyanine compound represented by the above formula (1).
  • the preferable manufacturing method of the phthalocyanine compound represented by Formula (A) of this invention is outlined.
  • the present invention is not limited to the following preferred embodiments.
  • the phthalocyanine compound of the present invention can be produced by cyclizing the phthalonitrile compound represented by the formula (1) with the same metal compound used in the method for producing the phthalocyanine compound represented by the above formula (1).
  • Y 1 to Y 4 each independently correspond to the substituent (a A ) or the substituent (b A ) according to the present invention and are appropriately determined depending on the structure of the desired phthalocyanine compound. sell. 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.
  • the phthalonitrile compound of the formula (D), which is a starting material can be synthesized by the same method as the phthalonitrile compounds represented by the above formulas (4) to (6). Is omitted.
  • the amount of the organic solvent used in the cyclization reaction using the organic solvent is not particularly limited, but the concentration of the phthalonitrile compound of the formula (D) is usually 2 to 50% by weight, preferably 10%. The amount is ⁇ 40% by weight.
  • reaction conditions for the phthalonitrile compound of formula (D) and the metal compound are the same as those described above for the cyclization reaction, detailed description thereof is omitted.
  • the reaction time is not particularly limited, but is 1 to 20 hours, preferably 3 to 10 hours.
  • the metal compound is charged in an amount of preferably 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 (D).
  • the phthalocyanine compound represented by the above formulas (1) and (A) according to the present invention or the mixture of phthalocyanine compounds produced by the above method can selectively absorb light in a specific wavelength region, the phthalocyanine compound or mixture
  • the heat-absorbing material to be included is very excellent in the heat-ray absorption / shielding effect.
  • “maximum absorption wavelength ( ⁇ max) (nm)” of the phthalocyanine compound means a value measured according to the method of the following examples.
  • the phthalocyanine compounds and mixtures represented by the above formulas (1) and (A) according to the present invention have high visible light transmittance (Tv) and solar radiation transmittance (Te) in view of the heat ray absorption (shielding) effect. Is preferably low.
  • the solar radiation transmittance (Te) is preferably 86% or less, and the compound and mixture represented by the formula (1) are 85% or less. It is more preferable that it is 84% or less.
  • the visible light transmittance (Tv) is 90%, it is preferably 80% or less, more preferably 78% or less, still more preferably 77% or less, and 76% or less. It is more preferable.
  • the phthalocyanine compound represented by the formula (A) preferably has a solar transmittance (Te) of 86% or less, and more preferably 85% or less.
  • the solar radiation transmittance (Te) is preferably less than 78.5%, more preferably 78% or less, and 77.5% or less. More preferably.
  • the “sunlight transmittance (Te) (%)” and “visible light transmittance (Tv) (%)” of the phthalocyanine compound and the mixture were calculated according to the standard of JIS R3106 (1998). However, specifically, it means a value measured according to the method of the following example.
  • the phthalocyanine compound and the mixture of the present invention have good visible light transmittance while maintaining low solar transmittance, they can be used as heat ray absorbing materials in various fields as described above.
  • the phthalocyanine compound and the mixture represented by the above formulas (1) and (A) of the present invention are excellent in compatibility with the resin, and excellent in heat resistance, light resistance and weather resistance in addition to the above advantages. And has an excellent effect as a heat-absorbing material without impairing its properties.
  • the heat ray absorber containing the phthalocyanine compound of this invention or the mixture of the said phthalocyanine compound is related with the heat ray absorber containing the phthalocyanine compound of this invention or the mixture of the said phthalocyanine compound.
  • the heat ray absorbing material of the present invention can be suitably used for heat ray absorbing laminated glass such as vehicles and building windows, heat ray shielding film, heat ray shielding resin glass, and heat ray reflecting glass.
  • heat ray absorbing material of the present invention can be suitably used for heat ray absorbing laminated glass such as vehicles and building windows, heat ray shielding film, heat ray shielding resin glass, and heat ray reflecting glass.
  • heat ray absorbing glass such as automobiles and building windows, it is possible to effectively suppress an increase in temperature in the vehicle or in the room.
  • the heat-absorbing material according to the present invention has high transmittance in the visible light wavelength region, particularly in the wavelength region of 500 to 600 nm, because the phthalocyanine compound and the mixture of the present invention have high visible light transmittance.
  • the required visible light transmittance varies depending on the application, but in fields where high visible light transmittance is required, such as heat-absorbing laminated glass such as vehicles and building windows, and heat-reflecting glass, visible heat-absorbing materials are visible.
  • the light transmittance (Tv) is preferably 55% or more, more preferably 60% or more, further preferably 65% or more, and particularly preferably 70% or more (upper limit: 100%). .
  • the heat ray absorbing material according to the present invention preferably has a low solar transmittance (Te) in view of the heat ray absorption (shielding) effect.
  • the solar radiation transmittance (Te) is preferably 90% or less, more preferably 80% or less, further preferably 75% or less, and even more preferably 70% or less.
  • it is still more preferably 60% or less, and particularly preferably 55% or less.
  • the heat ray absorbing material of the present invention essentially contains a phthalocyanine compound represented by the above formula (1) or (A) of the present invention. For this reason, except using the phthalocyanine compound of the present invention, the heat ray absorbing material of the present invention can be applied as a heat ray absorbing material similar to the conventional one.
  • the phthalocyanine compound according to the present invention may be used alone or in the form of a mixture of two or more.
  • 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 with a coating film, a film, and a resin constituting the intermediate layer. That is, the heat ray absorbing material of the present invention includes the phthalocyanine compound and the resin according to the present invention.
  • a composition containing a phthalocyanine compound and a resin may be referred to as a resin composition.
  • the blending amount of the phthalocyanine compound in the heat ray absorbing material can be appropriately selected depending on the use or the thickness of the resin, but is 0.0005 to 20 parts by mass, preferably 0.001 with respect to 100 parts by mass of the resin solid content. ⁇ 10 parts by mass. By mix
  • the resin is not particularly limited as long as it can be generally used for an optical material, but is preferably highly transparent, specifically polyethylene, polypropylene, carboxylated polyolefin, chlorinated polyolefin, cycloolefin polymer, etc.
  • Polyester resin such as polyarylate (PAR), polycarbonate resin, epoxy resin, and polyvinyl acetal resin such as polyvinyl butyral resin.
  • a resin composition that can be molded is obtained by kneading a phthalocyanine compound using a meltable resin.
  • resins include (meth) acrylic resins such as polyacrylic acid, polymethyl methacrylate, and ⁇ -hydroxymethyl acrylate copolymer, polycarbonate resins, polyester resins, and polyvinyl acetal resins.
  • Vinyl acetate resin for example, ethylene / vinyl acetate copolymer (EVA)
  • EVA ethylene / vinyl acetate copolymer
  • Arton registered trademark
  • Zeonoa registered trademark
  • Sumipex registered trademark
  • Optretz manufactured by Hitachi Chemical Co., Ltd.
  • a resin composition that can be coated can be obtained by dissolving a phthalocyanine compound in a resin that can be dissolved.
  • 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.
  • 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.
  • 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.
  • the monomer other than the above methacrylic acid ester may be a polymer copolymerized with a monomer other than the above methacrylic acid ester.
  • 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, hydroxyethyl (meta ) Monomers having a hydroxy group such as 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.
  • 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.
  • the resin may be a pressure-sensitive adhesive, an adhesive, or a mixture thereof.
  • a pressure-sensitive adhesive or an adhesive 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 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.), etc. Can be mentioned. Tg is preferably ⁇ 80 ° C. or higher and 0 ° C. or lower.
  • a suitable adhesive is an acrylic resin copolymerized with 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 (meth) acrylic acid.
  • resins suitable as the above-mentioned adhesive include general silicone-based, urethane-based, acrylic-based, polyolefin-based polyolefins such as 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.
  • 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 and isopropyl alcohol, ethers such as tetrahydrofuran and dibutyl ether, glycol ethers such as butyl cellosolve, propylene glycol n-propyl ether and propylene glycol n-butyl ether, triethylene glycol di Ether esters such as (2
  • a solvent having a boiling point of 100 ° C. or less such as methyl ethyl ketone and ethyl acetate, is suitable.
  • a solvent having a boiling point of 100 to 150 ° C. such as toluene, methyl isobutyl ketone, butyl acetate and the like is preferable.
  • 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, propylene glycol monomethyl ether acetate, is preferable.
  • the resin composition according to the present invention contains a visible light absorber, a near infrared absorber, and an ultraviolet absorber (hereinafter collectively referred to as “other absorbers”). preferable.
  • other absorbers an ultraviolet absorber
  • a near-infrared absorber is included.
  • the visible light absorber cyanine, tetraazaporphyrin, azurenium, squarylium, diphenylmethane, triphenylmethane, oxazine, azine, thiopyrylium, viologen, azo, azo metal complex salt
  • dyes such as bisazo, bisazo, anthraquinone, perylene, indanthrone, nitroso, metal thiol complex, indico, azomethine, xanthene, oxanol, indoaniline, quinoline can do.
  • the visible light absorber may be a dye that dissolves in a solvent, or may be a pigment atomized to such an extent that haze does not become a problem.
  • the near-infrared absorber is not particularly limited, and a known near-infrared absorber can be appropriately selected depending on the maximum absorption wavelength desired depending on the application.
  • the maximum absorption wavelength of the near-infrared absorber is preferably 800 nm or more.
  • the near-infrared absorber as another absorber is a pigment
  • the ultraviolet absorber is not particularly limited, and a known ultraviolet absorber can be used. Specifically, salicylic acid, benzophenone, benzotriazole, and cyanoacrylate compounds are preferably used.
  • absorbents described above may be used alone or in the form of a mixture of two or more, and can be appropriately selected depending on the application.
  • the blending amount of the other absorbents is not particularly limited, and cannot be determined unconditionally because the absorption wavelength range, visible light transmittance, and solar transmittance required by 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.
  • 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 to the other absorbent is preferably 1 to 1000 parts by mass, more preferably 10 to 500 parts by mass with respect to 100 parts by mass of the phthalocyanine compound of the present invention. Within this range, the solar radiation transmittance can be lowered without affecting the visible light transmittance.
  • 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.
  • additives used for films, coating agents and the like can be used for the heat-absorbing material.
  • 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.
  • the resin composition is applied to a transparent substrate, the resin composition is bonded to two transparent substrates, and the resin composition is molded.
  • the thickness of the heat ray absorber of this invention determines suitably according to the objective and a use. Preferably, it is 0.1 ⁇ m 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 .
  • 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, it is preferably 55% or more, more preferably 60% or more.
  • the solar radiation transmittance is preferably 95% or less, more preferably 90% or less.
  • the transparent substrate is generally usable for optical materials, and is not particularly limited as long as it is substantially transparent.
  • Specific examples include olefin polymers such as glass, cyclopolyolefin and amorphous polyolefin, (meth) acrylic ester resins such as polymethyl methacrylate, vinyl resins such as polystyrene, polycarbonate resins, polyester resins, poly Examples include ether sulfone resins and polyaryl ether resins.
  • 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.
  • 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.
  • a known coating machine When applying the resin composition to the transparent substrate, a known coating machine can be used. Examples include knife coaters, fountain coaters, kiss coaters, roll coaters, flow coaters, spray coaters, bar coaters, and spin coaters. As drying and curing methods, known methods such as hot air, far infrared rays, UV curing and the like can be used.
  • the thickness of the coating film is not limited, but is appropriately determined according to the purpose.
  • the thickness is preferably 0.1 ⁇ m to 10 mm.
  • the transparent substrate is preferably a PET film, and particularly a PET film that has been subjected to easy adhesion treatment.
  • a PET film e.g., Cosmo Shine (registered trademark) A4300 (manufactured by Toyobo), Lumirror U34 (manufactured by Toray), Melinex (registered trademark) 705 (manufactured by Teijin DuPont) and the like can be mentioned.
  • the resin used for the heat ray absorbing material is preferably an adhesive resin or a UV curable resin.
  • the coating film may be formed on one side of the film or on both sides, but is preferably applied on one side.
  • 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.
  • a coating liquid containing the phthalocyanine compound, UV curable monomer or oligomer, and photopolymerization initiator on the transparent substrate.
  • the transparent substrate is preferably glass or PET film.
  • the resin composition for bonding two glass substrates one using a polyvinyl butyral resin as the resin is preferable from the viewpoint of adhesiveness.
  • the method for producing the heat-absorbing material is not particularly limited.
  • a method of kneading and thermoforming the resin composition (ii) a mold frame together with a phthalocyanine compound, a curable monomer or oligomer, and a polymerization initiator.
  • a method of polymerizing and molding can be used.
  • the 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 being kneaded 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.
  • 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.
  • thermoplastic resin examples include olefin resins such as cyclopolyolefin and amorphous polyolefin, (meth) acrylic resins such as polymethyl methacrylate, vinyl resins such as polystyrene, polycarbonate resins, polyester resins, poly Examples include ether sulfone resins and polyaryl ether resins.
  • the heat-absorbing material is not limited in shape and can be appropriately formed depending on the application. 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
  • 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 in which the above resin composition is molded. It may be included.
  • the heat ray absorption capability in the near infrared region where the absorption capability by the phthalocyanine compound of the present invention is low can be improved.
  • the inorganic compound may be added to a resin composition containing a phthalocyanine compound to form a molded or coated film.
  • the heat ray absorbing material further contains at least one of a near infrared absorbing dye and an inorganic compound having a maximum absorption wavelength of 800 nm or more.
  • the inorganic compound is preferably a metal oxide, specifically, an alkali metal doped tungsten oxide such as zinc oxide, titanium oxide, tin oxide, indium oxide, indium tin oxide, cesium doped tungsten oxide (CsWO 3 ), oxidized Examples include antimony, antimony-doped tin oxide (ATO), and zinc antimonate.
  • the inorganic compound can absorb a wavelength range of 900 nm or more, preferably 1100 nm or more, and more preferably 1200 nm or more, which cannot be absorbed by the phthalocyanine compound or the organic dye, while maintaining the visible light transmittance and the solar transmittance. Can be lowered.
  • alkali metal doped tungsten oxide indium tin oxide or antimony doped tin oxide.
  • alkali metal doped tungsten oxide examples include SG-IRC90SPM (manufactured by Sukkyung).
  • indium tin oxide examples include PI-3 (manufactured by Mitsubishi Materials).
  • antimony-doped tin oxide examples 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 ⁇ m.
  • the thickness is preferably 0.005 to 0.15 ⁇ m. This range is preferable because the transparency is not impaired.
  • the blending amount of the inorganic compound is not particularly limited, and cannot be determined unconditionally because the absorption wavelength range, visible light transmittance, and solar transmittance required depending on the application are different.
  • the compounding amount of the inorganic compound is preferably 1 to 1000 parts by mass and more preferably 10 to 500 parts by mass with respect to 100 parts by mass of the phthalocyanine compound of the present invention in the heat ray absorbing material.
  • the mixing ratio with the phthalocyanine compound of the present invention is not particularly limited.
  • the mixing ratio of the phthalocyanine compound of the present invention to the other absorbent is preferably 20 to 5000 parts by mass, more preferably 50 to 400 parts by mass with respect to 100 parts by mass of the phthalocyanine compound of the present invention.
  • 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 window films for buildings and vehicles, heat ray absorbing laminated glass, heat ray absorbing resin glazing, daylighting building materials and the like.
  • room temperature means 25 ⁇ 5 ° C.
  • Example 1 Phthalocyanine compound containing naphthalene structure> Synthesis Example 1-1: Synthesis of 4,5-bis (4-methoxycarbonylphenoxy) -3,6-bis (4-methoxyphenoxy) phthalonitrile Into a 500 ml eggplant flask, 20 g of tetrafluorophthalonitrile and 13 g of potassium fluoride And 20 g of acetone were added and mixed at 5 ° C. A mixed solution prepared with 31 g of methyl 4-hydroxybenzoate and 30 g of acetone was added dropwise over 3 hours, the reaction temperature was raised to 25 ° C., and the mixture was stirred overnight.
  • Synthesis Example 1-2 Synthesis of 3,4,5,6-tetrakis (4-methoxycarbonylphenoxy) phthalonitrile
  • 30 g of tetrafluorophthalonitrile, 91 g of potassium carbonate, 92 g of methyl 4-hydroxybenzoate and 180 g of acetonitrile was added and stirred at 70 ° C. for 7 hours.
  • the reaction solution was filtered, the solvent 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 107 g (yield: 98%) of 3,4,5,6-tetrakis (2-methoxycarbonylphenoxy) phthalonitrile.
  • Synthesis Example 1-6 3,6-bis (2-isopropylphenoxy) -4,5-bis (2,3,4,5,6-pentafluorophenoxy) phthalonitrile 2-methylphenol of Synthesis Example 1-5 3,6-bis (2-isopropylphenoxy) -4,5-bis (2,3,4,5,6-pentafluorophenoxy) phthalonitrile, except for changing to 2-isopropylphenol 5.5 g (yield: 76%) was obtained.
  • Synthesis Example 1-7 3,6-bis (2-methylphenoxy) -4,5-bis (4-fluorophenoxy) phthalonitrile 3,6-difluoro-4,5-obtained in Synthesis Example 1-4
  • Bis (4-fluorophenoxy) phthalonitrile (15 g), potassium carbonate (13 g), 2-methylphenol (9 g) and acetonitrile (45 g) were mixed and stirred at 70 ° C. for 3 hours. After cooling to 25 ° C., the reaction solution was filtered, the solvent 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 18 g (yield: 81%) of 3,6-bis (2-methylphenoxy) -4,5-bis (4-fluorophenoxy) phthalonitrile.
  • Synthesis Example 1-10 3,6-bis (2-naphthoxy) -4,5-bis (4-fluorophenoxy) phthalonitrile Into a 200 ml eggplant flask, 3,6-difluoro obtained in Synthesis Example 1-4 -4,5-bis (4-fluorophenoxy) phthalonitrile (20 g), potassium carbonate (9 g), 2-naphthol (16 g) and acetonitrile (90 g) were mixed and stirred at 60 ° C. for 3 hours. After cooling to 25 ° C., the reaction solution was filtered, the solvent 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 29 g (yield: 87%) of 3,6-bis (2-naphthoxy) -4,5-bis (4-fluorophenoxy) phthalonitrile.
  • Example 1-1 Synthesis of Phthalocyanine Compound (1-1) [ ⁇ 4- (COOCH 3 ) PhO ⁇ 6 ⁇ 4- (OCH 3 ) PhO ⁇ 6 NpVOPc]
  • Synthesis Example 1-1 5,5-bis (4-methoxycarbonylphenoxy) -3,6-bis (4-methoxyphenoxy) phthalonitrile obtained in 1), 2,3-dicyanonaphthalene 0.4 g, vanadium (III) chloride 0.5 g 7.5 g of benzonitrile and 0.4 g of 1-octanol were added, and the mixture was stirred at 185 ° C. for 21 hours in a nitrogen gas atmosphere. After cooling to 25 ° C., the reaction solution was dropped into methanol for crystallization. The precipitate was collected by filtration and dried under reduced pressure to obtain 4 g (yield: 79%) of the phthalocyanine compound (1-1).
  • Example 1-2 Synthesis of phthalocyanine compound (1-2) [ ⁇ 4- (COOCH 3 ) PhO ⁇ 6 ⁇ 4- (COOCH 3 ) PhO ⁇ 6 NpSnCl 2 Pc]
  • the above Synthesis Example 1 was added.
  • the reaction solution was dropped into methanol for crystallization.
  • the precipitate was collected by filtration and dried under reduced pressure to obtain 5 g (yield: 88%) of the phthalocyanine compound (1-2).
  • Example 1-3 Phthalocyanine compound (1-3) [ ⁇ 2,5- (Cl 2 ) PhO ⁇ 6 ⁇ 4- (COOCH 3 ) PhO ⁇ 3 ⁇ 2,6- (CH 3 ) 2 PhO ⁇ 3 NpSnCl 2 Pc]
  • the 3,4,5,6-tetrakis (4-methoxycarbonylphenoxy) phthalonitrile of Example 1-2 was converted to 3- (2,6-dimethylphenoxy obtained in Synthesis Example 1-3 above.
  • Example 1-4 Synthesis of Phthalocyanine Compound (1-4) [ ⁇ 4- (F) PhO ⁇ 6 ⁇ 2- (Ph) PhO ⁇ 6 NpVOPc] Obtained in Synthesis Example 1-4 in a 50 ml test tube.
  • 3,6-bis (2-phenylphenoxy) -4,5-bis (4-fluorophenoxy) phthalonitrile 2 g 0.2 g of 2,3-dicyanonaphthalene, 0.2 g of vanadium (III) chloride, benzonitrile 3 g and 1-octanol 0.2 g were added, and the mixture was stirred at 185 ° C. for 23 hours in a nitrogen gas atmosphere. After cooling to 25 ° C., the reaction solution was dropped into methanol for crystallization. The precipitate was collected by filtration and dried under reduced pressure to obtain 2 g (yield: 80%) of the phthalocyanine compound (1-4).
  • the obtained phthalocyanine compound (1-4) was analyzed using a liquid chromatography with a multi-wavelength detector (LC-DAD; LaChrom ⁇ Elite manufactured by Hitachi High-Technologies Corporation). The elution shown in FIG. Each component was separated over time and found to be a mixture of three components. The structure of each component was estimated from the peak retention time and ⁇ max. In FIG. 1, the detection wavelength was 300 to 900 nm.
  • ⁇ LC-DAD measurement conditions Eluent: THF 70% -water 30%, column: Inertsil ODS-4 (5 ⁇ m, 4.6 ⁇ 250 mm), temperature: 40 ° C., flow rate: 1 ml / min.
  • Peak 1 Retention time: about 9 minutes, ⁇ max: about 805 nm A phthalocyanine compound into which two benzoisoindole rings have been introduced.
  • Peak 2 retention time: about 13 minutes, ⁇ max: about 815 nm A phthalocyanine compound into which one benzoisoindole ring has been introduced, that is, a phthalocyanine compound (1-4).
  • Peak 3 Retention time: about 20 minutes, ⁇ max: about 790 nm
  • a phthalocyanine compound having no benzoisoindole ring that is, a phthalocyanine compound having no naphthalene ring represented by the above formula (I).
  • FIG. 2 shows the absorption spectrum of each compound shown in FIG. In order from the bottom, it is attributed to the absorption spectra of the above peak 1, peak 2, and peak 3. Therefore, as apparent from FIG. 2, it is shown that the maximum absorption wavelength ⁇ max of the phthalocyanine compound (1-4) of the present invention is about 770 nm. In addition, the phthalocyanine compound (1-4) is also shown to have a high transmittance in the range of 500 to 600 nm. Further, FIG. 2 shows that the maximum absorption wavelength ⁇ max of the phthalocyanine compound not containing the naphthalene ring is about 790 nm.
  • Example 1-5 Synthesis of phthalocyanine compound (1-5) [ ⁇ 2,3,4,5,6- (F 5 ) PhO ⁇ 6 ⁇ 2- (Me) PhO ⁇ 6 NpSnCl 2 Pc] 50 ml test Into the tube, 5.6 g of 3,6-bis (2-methylphenoxy) -4,5-bis (2,3,4,5,6-pentafluorophenoxy) phthalonitrile obtained in Synthesis Example 1-5 above. 2,3-dicyanonaphthalene 0.5 g, tin (II) chloride 0.8 g, and benzonitrile 8.5 g were added, and the mixture was stirred at 185 ° C. for 18 hours in a nitrogen gas atmosphere. After cooling to 25 ° C., the reaction solution was dropped into methanol for crystallization. The precipitate was collected by filtration and dried under reduced pressure to obtain 5 g (yield: 77%) of a phthalocyanine compound (1-5).
  • Example 1-6 Synthesis of phthalocyanine compound (1-6) [ ⁇ 2,3,4,5,6- (F 5 ) PhO ⁇ 6 ⁇ 2- ( i Pr) PhO ⁇ 6 NpSnCl 2 Pc] 1-5 3,6-bis (2-methylphenoxy) -4,5-bis (2,3,4,5,6-pentafluorophenoxy) phthalonitrile was obtained in Synthesis Example 1-6.
  • Example 1-7 Synthesis of phthalocyanine compound (1-7) [ ⁇ 4- (F) PhO ⁇ 6 ⁇ 2- (Me) PhO ⁇ 6 NpVOPc] 4,5-bis (4- Methoxycarbonylphenoxy) -3,6-bis (4-methoxyphenoxy) phthalonitrile was converted to 3,6-bis (2-methylphenoxy) -4,5-bis (4-fluoro) obtained in Synthesis Example 1-7. Synthesis was performed in the same manner except that the phenoxy) phthalonitrile was changed to obtain 4 g (yield: 54%) of the phthalocyanine compound (1-7).
  • Example 1-8 Synthesis of phthalocyanine compound (1-8) [ ⁇ 2,4- (F 2 ) PhO ⁇ 6 ⁇ 2- (Ph) PhO ⁇ 6 NpVOPc] 4,5-bis of Example 1-1 (4-Methoxycarbonylphenoxy) -3,6-bis (4-methoxyphenoxy) phthalonitrile was converted to 3,6-bis (2-phenylphenoxy) -4,5-bis ( The synthesis was carried out in the same manner except that it was changed to 2,4-difluorophenoxy) phthalonitrile, to obtain 2 g of phthalocyanine compound (1-8) (yield: 39%).
  • Example 1-9 Synthesis of phthalocyanine compound (1-9) [ ⁇ 2- (Me) PhO ⁇ 6 ⁇ 2- (Me) PhO ⁇ 6 NpVOPc] 4,5-bis (4- Other than changing methoxycarbonylphenoxy) -3,6-bis (4-methoxyphenoxy) phthalonitrile to 3,4,5,6-tetrakis (2-methylphenoxy) phthalonitrile obtained in Synthesis Example 1-9 above was synthesized in the same manner to obtain 3.7 g (yield: 64%) of the phthalocyanine compound (1-9).
  • Example 1-10 Synthesis of phthalocyanine compound (1-10) [ ⁇ 4- (F) PhO ⁇ 6 ⁇ 2-NpO ⁇ 6 NpVOPc] 3,6-bis (4-methoxyphenoxy) of Example 1-1 3,6-bis (2-naphthoxy) -4,5-bis (4-fluorophenoxy) phthalonitrile obtained by synthesizing -4,5-bis (4-methoxycarbonylphenoxy) phthalonitrile in Synthesis Example 1-10 above The same synthesis except for the above was performed to obtain 4.4 g (yield: 77%) of the phthalocyanine compound (1-10).
  • Comparative Example 1-1 Synthesis of Comparative Phthalocyanine Compound (1-1) [ ⁇ 4- (COOCH 3 ) PhO ⁇ 8 ⁇ 4- (OCH 3 ) PhO ⁇ 8 VOPc]
  • Synthesis Example 1 15 g of 4,5-bis (4-methoxycarbonylphenoxy) -3,6-bis (4-methoxyphenoxy) phthalonitrile obtained in 1 above, 1.1 g of vanadium (III) chloride, 22.5 g of benzonitrile and 1- 0.9 g of octanol was added and 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 dried under reduced pressure to obtain 13.8 g (yield: 89.9%) of a comparative phthalocyanine compound (1).
  • 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.
  • the mixture containing the phthalocyanine compounds (1-1) to (1-10) of the present invention has a comparative phthalocyanine compound (1) when the visible light transmittance (Tv) is equal. It can be seen that the solar radiation transmittance (Te) at any visible light transmittance (Tv) is significantly lower than that of -1). 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 1-11 With respect to the phthalocyanine compound (1-1) obtained in Example 1-1, a heat ray absorbing material (1-1) comprising a phthalocyanine compound-containing film on a PET film was produced as follows.
  • Phthalocyanine compound (1-1) 100 mg, 17 wt% CsWO 3 dispersion (Sukkyung, SG-IRC90SPM; average dispersed particle size: 39.2 nm) (heat ray absorbing inorganic compound) 6 g, acrylic monomer (manufactured by Kyoei Chemical Co., Ltd., 2 g of light acrylate DPE-6A), 125 mg of photopolymerization initiator (manufactured by BASF, Irgacure 369) and 2 g of methyl ethyl ketone were sufficiently stirred and mixed to obtain a resin composition (1-1).
  • Phthalocyanine compound (1-1) 100 mg, 17 wt% CsWO 3 dispersion (Sukkyung, SG-IRC90SPM; average dispersed particle size: 39.2 nm) (heat ray absorbing inorganic compound) 6 g, acrylic monomer (manufactured by Kyoei Chemical Co., Ltd.,
  • the resin composition (1-1) obtained above was applied onto a PET film (thickness: 0.1 mm) using a spin coater and dried at 80 ° C. for 2 minutes, and then an irradiation dose of 500 mJ / cm. 2 was irradiated with ultraviolet rays for 1 second to prepare a film (heat ray absorbing material (1-1)) coated with the resin composition (1-1) having a thickness of 0.101 mm.
  • Example 1-12 With respect to the phthalocyanine compound (1-1) obtained in Example 1-1, a heat ray absorbing material (1-2) obtained by providing a phthalocyanine compound-containing film on a PET film was produced as follows.
  • Phthalocyanine compound (1-1) 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 ⁇ m) 10 g, dipentaerystol hexaacrylate (Kyoei Chemical Co., Ltd., Light Acrylate DPE-6A) 2 g and photopolymerization initiator (BASF Co., Ltd., Irgacure 369) 125 mg were sufficiently stirred and mixed to obtain a resin composition (1-2).
  • ATO antimony-doped tin oxide
  • Example 1-11 A resin composition (Example 1-11) was prepared in the same manner as in Example 1-11 except that the resin composition (1-1) was changed to the resin composition (1-2) obtained above. A film coated with 1-2) (heat-absorbing material (1-2)) was produced.
  • the solar transmittance (Te) can be significantly reduced by combining the phthalocyanine compound (1-1) of the present invention with other heat ray absorbing inorganic compounds. This is considered to be because the other heat ray-absorbing inorganic compounds are not sufficiently absorbed in the near-infrared region, and are thus supplemented by the phthalocyanine compound (1-1) of the present invention.
  • Example 2 Phthalocyanine compound not containing naphthalene structure> Synthesis Example 2-1: 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.
  • Synthesis Example 2-2 Synthesis of 3,6-bis (2-phenylphenoxy) -4,5-bis (2-methyloxycarbonylphenoxy) phthalonitrile
  • 70 g of tetrafluorophthalonitrile and 116 g of potassium carbonate Then, 108 g of methyl salicylate and 140 g of acetonitrile were added and stirred at 70 ° C. for 7 days.
  • Synthesis Example 2-3 Synthesis of 3,6-bis (2-phenylphenoxy) -4,5-bis (2-fluorophenoxy) phthalonitrile
  • 22 g of tetrafluorophthalonitrile, 15 g of potassium fluoride and 44 g of acetone was added and mixed at 0 ° C.
  • a mixed liquid prepared with 25 g of 2-fluorophenol and 25 g of acetone was added dropwise at a liquid temperature of 0 ° C. and stirred for 2 hours.
  • Synthesis Example 2-4 Synthesis of 3,6-bis (2-phenylphenoxy) -4,5-bis (4-fluorophenoxy) phthalonitrile
  • 22 g of tetrafluorophthalonitrile, 15 g of potassium fluoride and 44 g of acetone was added 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.
  • Comparative Synthesis Example 2-2 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 And stirred at 70 ° C. for 4 hours.
  • Example 2-1 Synthesis of Phthalocyanine Compound (2-1) [(2- (Ph) PhO) 8 (2- (Ph) PhO) 8 VOPc] Obtained in Synthesis Example 2-1 in a 50 ml test tube.
  • the resulting 3,4,5,6-tetrakis (2-phenylphenoxy) phthalonitrile (5 g), vanadium (III) chloride (0.4 g), benzonitrile (8 g) and 1-octanol (0.3 g) were placed at 185 ° C. in a nitrogen gas atmosphere. Stir for 8 hours. 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 (yield: 41 mol%) of a phthalocyanine compound (2-1).
  • Example 2-2 Synthesis of phthalocyanine compound (2-2) [(2- (COOCH 3 ) PhO) 8 (2- (Ph) PhO) 8 VOPc]
  • a 50 ml test tube the above synthesis example 2-2
  • Example 2-4 Synthesis of phthalocyanine compound (2-4) [(4- (F) PhO) 8 (2- (Ph) PhO) 8 VOPc] Obtained in Synthesis Example 2-4 in a 50 ml test tube 3 g of 3,6-bis (2-phenylphenoxy) -4,5-bis (4-fluorophenoxy) phthalonitrile obtained, 0.3 g of vanadium (III) chloride, 5 g of benzonitrile and 0.2 g of 1-octanol were added. The mixture was stirred at 185 ° C. for 6 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 (yield: 62 mol%) of a phthalocyanine compound (2-4).
  • Comparative Example 2-1 Synthesis of Comparative Phthalocyanine Compound (2-1) [(4- (COOCH 3 ) PhO) 8 (4- (MeO) PhO) 8 VOPc]
  • the above Comparative Synthesis Example 2- 15 g of 4,5-bis (4-methoxycarbonylphenoxy) -3,6-bis (4-methoxyphenoxy) phthalonitrile obtained in 1 above, 1.1 g of vanadium (III) chloride, 22.5 g of benzonitrile and 1- 0.9 g of octanol was added and 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 dried under reduced pressure to obtain 13.8 g (yield: 89.9 mol%) of a comparative phthalocyanine compound (2-1).
  • Comparative Example 2-2 Synthesis of Comparative Phthalocyanine Compound (2-2) [(3- (Ph) PhO) 8 (3- (Ph) PhO) 8 VOPc]
  • the above Comparative Synthesis Example 2-2 5 g of 3,4,5,6-tetrakis (3-phenylphenoxy) phthalonitrile obtained in 1), 0.4 g of vanadium (III) chloride, 8 g of benzonitrile and 0.3 g of 1-octanol were added, and 185 was added in a nitrogen gas atmosphere. 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 dried under reduced pressure to obtain 4 g (yield: 85 mol%) of a comparative phthalocyanine compound (2-2).
  • Comparative Example 2-3 Synthesis of Comparative Phthalocyanine Compound (2-3) [(F) 8 (2- (Ph) PhO) 8 VOPc] 3 obtained in Comparative Synthesis Example 2-3 in a 50 ml test tube , 6-Difluoro-4,5-bis (2-phenylphenoxy) phthalonitrile (3 g), vanadium (III) chloride (0.4 g), benzonitrile (5 g) and 1-octanol (0.3 g) were mixed at 185 ° C. in a nitrogen gas atmosphere. The reaction was allowed for 5 hours. 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 3 g (yield: 85 mol%) of a comparative phthalocyanine compound (2-3).
  • Comparative Example 2-4 Synthesis of Comparative Phthalocyanine Compound (2-4) [(F) 4 (2- (Ph) PhO) 4 (2- (Ph) PhO) 8 VOPc]
  • the above comparative synthesis was added to a 50 ml test tube.
  • the mixture was stirred at 185 ° C. for 5 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 3 g (yield: 83 mol%) of a comparative phthalocyanine compound (2-4).
  • ⁇ Measurement of maximum absorption wavelength ( ⁇ max)> The maximum absorption wavelength ( ⁇ max) (nm) was determined by measuring the transmittance of each phthalocyanine compound in chloroform at 300 to 2500 nm using a spectrophotometer (manufactured by Shimadzu Corporation: UV-3100), and between 600 and 900 nm. It is a wavelength (nm) which shows the minimum transmittance
  • the phthalocyanine compounds (2-1) to (2-4) of the present invention are compared with the comparative phthalocyanine compounds (2-1) to (2-4).
  • the solar radiation transmittance (Te) at any visible light transmittance (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 2-5 With respect to the phthalocyanine compound (2-1) obtained in Example 2-1, a laminated glass (heat ray absorbing material) was produced as follows.
  • the resin composition (2-1) obtained above was press molded at 180 ° C. to produce an interlayer film for laminated glass.
  • 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.
  • the visible light transmittance (Tv) (%) and solar radiation transmittance (Te) (%) were calculated for the obtained laminated glass. The results are shown in Table 5 below together with the maximum absorption wavelength ( ⁇ max) (nm).
  • the glass using the phthalocyanine compound (2-1) of the present invention has low solar transmittance (Te) while ensuring sufficient transparency.
  • Example 2-6 For the phthalocyanine compound (2-1) obtained in Example 2-1 above, a heat ray absorbing material (2-1) comprising a phthalocyanine compound-containing intermediate layer between two PET films was prepared as follows. Produced.
  • Example 2-6 except that the phthalocyanine compound (2-1) was not used, a film laminate having a thickness of 0.36 mm (comparative heat ray absorbent (2- 1)) was produced.
  • Example 2-7 With respect to the phthalocyanine compound (2-1) obtained in Example 1, a heat ray absorbing material (2-2) comprising a PET film provided with a phthalocyanine compound-containing film was produced as follows.
  • Example 2-8 With respect to the phthalocyanine compound (2-1) obtained in Example 2-1 above, a heat ray absorbing material (2-3) obtained by providing a phthalocyanine compound-containing film on a PET film was produced as follows.
  • Example 2-7 A resin composition (Example 2-7) was prepared in the same manner as in Example 2-7, except that the resin composition (2-3) was changed to the resin composition (2-4) obtained above. A film coated with 2-4) (heat-absorbing material (2-3)) was produced.
  • Comparative Example 2-6 A film coated with an acrylic resin having a thickness of 0.101 mm according to the same method as in Example 2-8, except that the phthalocyanine compound (2-1) was not used in Example 2-8 (Comparison) A heat ray absorbing material (2-2)) was produced.
  • the phthalocyanine compound (2-1) of the present invention was added to another near infrared absorbing dye (Example 2-6) or a heat ray absorbing inorganic compound (Examples 2-7, 2-8). ), The visible light transmittance (Tv) is slightly lowered, but the solar radiation transmittance (Te) can be significantly reduced. This is because other near-infrared absorbing dyes (Example 2-6) or heat ray absorbing inorganic compounds (Examples 2-7 and 2-8) do not sufficiently absorb near-infrared wavelengths. It is thought to be supplemented with the phthalocyanine compound (2-1).
  • Example 2-9 For the phthalocyanine compound (2-1) obtained in Example 2-1 above, heat ray absorbing materials (2-4) to (2-6) containing the phthalocyanine compound were produced as follows.
  • phthalocyanine compound (2-1) was added at 35, 50, and 100 mass ppm with respect to the polycarbonate resin (manufactured by Teijin Kasei Co., Ltd., Panlite L1225WX), respectively, and the mixture was thoroughly stirred and mixed with a mixer. -5) to (2-7) were obtained.
  • the heat ray absorbing material using the phthalocyanine compound (2-1) of the present invention can control the solar transmittance (Te) by changing the concentration of the phthalocyanine compound.
  • 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.
  • the heat ray absorbing material using the phthalocyanine compound of the present invention is a heat ray absorbing glass such as a heat ray absorbing laminated glass, a heat ray shielding film, a heat ray shielding resin glass and a heat ray reflecting glass that can be used for vehicles and buildings. It can be used suitably.

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Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS61246091A (ja) * 1985-04-24 1986-11-01 Tdk Corp 光記録媒体
JPH01108265A (ja) * 1987-10-20 1989-04-25 Mitsui Toatsu Chem Inc 近赤外線吸収剤およびそれを用いた光記録媒体
JPH02240167A (ja) * 1989-03-15 1990-09-25 Yamamoto Chem Inc アザアヌレン化合物
JPH02276676A (ja) * 1989-04-19 1990-11-13 Mitsui Toatsu Chem Inc 光記録媒体
JPH0470631A (ja) * 1990-07-06 1992-03-05 Toyo Ink Mfg Co Ltd 有機非線形光学材料
WO1998016588A1 (fr) * 1996-10-14 1998-04-23 Nippon Shokubai Co., Ltd. Composes de phtalocyanine, procede de preparation desdits composes et support d'enregistrement optique les comprenant
JP2011094127A (ja) * 2009-09-29 2011-05-12 Nippon Shokubai Co Ltd 熱線吸収材

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS61246091A (ja) * 1985-04-24 1986-11-01 Tdk Corp 光記録媒体
JPH01108265A (ja) * 1987-10-20 1989-04-25 Mitsui Toatsu Chem Inc 近赤外線吸収剤およびそれを用いた光記録媒体
JPH02240167A (ja) * 1989-03-15 1990-09-25 Yamamoto Chem Inc アザアヌレン化合物
JPH02276676A (ja) * 1989-04-19 1990-11-13 Mitsui Toatsu Chem Inc 光記録媒体
JPH0470631A (ja) * 1990-07-06 1992-03-05 Toyo Ink Mfg Co Ltd 有機非線形光学材料
WO1998016588A1 (fr) * 1996-10-14 1998-04-23 Nippon Shokubai Co., Ltd. Composes de phtalocyanine, procede de preparation desdits composes et support d'enregistrement optique les comprenant
JP2011094127A (ja) * 2009-09-29 2011-05-12 Nippon Shokubai Co Ltd 熱線吸収材

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