JPH11152414A - Naphthalocyanine compound and its use - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a new compound having amino group on each naphthalene ring, exhibiting excellent near infrared absorptivity and compatibility with solvents and resins and useful as a near infrared absorption filter, an aqricultural film, a light guard, an optical recording medium, etc. SOLUTION: This compound is expressed by formula I [R1 and R2 are each a (substituted) alkyl; R3 and R4 are each H, a (substituted)alkyl or the like; M is a bivalent metal, an oxymetal or the like], e.g. a compound of formula II (one of X1 and X2 is NH2 and the other is H). The compound of the formula I can be produced e.g. by reacting a dicyanonaphthalene derivative of formula III (e.g. a compound of formula IV) with a metal or a metal compound (e.g. copper chloride) in a solvent such as n-amyl alcohol, preferably at a temp. of 130-220 deg.C and reacting the synthesized nitronaphthalocyanine compound in the presence of a reducing agent such as sodium hydrosulfide in a solvent. This new compound has excellent near infrared absorptivity in a long wavelength range of about 900 nm or longer.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a novel naphthalocyanine compound and a near-infrared absorbing material containing the compound. In detail, near infrared absorbing paints or inks, photothermal conversion materials, optical cards, optical recording media, organic photoconductors, near infrared absorbing filters, heat ray shielding films, agricultural films, etc. To a naphthalocyanine compound that can be developed into

[0002]

2. Description of the Related Art Since naphthalocyanine compounds have excellent near-infrared absorption ability, various applications to optical cards, near-infrared absorption filters, heat ray shielding films, organic photoconductors of laser printers, etc. have been studied, and wavelengths according to the applications have been studied. Studies have been conducted mainly on compounds having selectivity and compounds having an absorption maximum at 700 to 800 nm, but for applications such as blocking heat rays, and for applications that need to absorb near-infrared rays in a long wavelength region. Thus, there are few examples of suitable compounds.

For example, Japanese Patent Application Laid-Open Nos.
JP-A-60-184565 and JP-A-60-43605 disclose a naphthalocyanine compound substituted with an alkyl group, a chlorine atom, a sulfonic acid group, a sulfonamide group which may be substituted, or Disclosed are naphthalocyanine compounds substituted with an optionally substituted aminomethyl group. The naphthalocyanine compounds disclosed therein have an absorption maximum wavelength of at most about 800 nm and lack the ability to absorb near-infrared rays in a long wavelength region. Japanese Patent Application Laid-Open No. 4-81995 discloses a naphthalocyanine compound which is substituted with a halogen atom and is a specific central metal compound. Although the naphthalocyanine compound disclosed here has a maximum absorption wavelength of up to 900 nm, it has little solubility in a solvent and needs to use a specific technique such as vapor deposition.

Further, Japanese Patent Application Laid-Open Nos. Sho 60-209583 and
JP-A-270765 discloses a compound which is soluble in a solvent and has an absorption of 900 nm or more. However, this compound lacks absorption wavelength selectivity because the absorption is broad.

Further, in Japanese Patent Application Laid-Open No. 2-298885, a compound having an amino group is also included in the scope of claims, but as in the present invention, one amino acid is attached to each of the four naphthalene rings of naphthalocyanine. The compound having a group is not described in the text or Examples, and the wavelength absorption characteristics are not mentioned at all.

[0006]

An object of the present invention is to provide a polymer having excellent compatibility with a solvent or a resin and having a maximum absorption wavelength (λma).
x) is to provide a naphthalocyanine compound which selectively absorbs a wavelength in the near infrared region near 900 nm or more in the near infrared region, and a near infrared absorbing material using the compound.

[0007]

The present inventors have conducted intensive studies to solve the above-mentioned problems, and as a result, have found that a naphthalocyanine compound obtained by introducing a substituent containing an amino group into a naphthalocyanine compound having an alkoxy group. However, the present inventors have found that the compound has excellent properties as a near-infrared absorbing compound having high wavelength selectivity in a long wavelength region near 900 nm or more, and completed the present invention.

That is, the present invention relates to a novel naphthalocyanine compound represented by the following general formula (1). Further, the present invention relates to a near infrared absorbing resin composition and a near infrared absorbing material containing the naphthalocyanine compound.

[0009]

Embedded image (Wherein, R ₁ and R ₂ each independently represent an optionally substituted alkyl group, and R ₃ and R ₄ each independently represent a hydrogen atom,
It represents an optionally substituted alkyl group or an optionally substituted aryl group, and M represents a divalent metal atom, a trivalent or tetravalent substituted metal, or an oxymetal. )

[0010]

BEST MODE FOR CARRYING OUT THE INVENTION The naphthalocyanine compound represented by the general formula (1) of the present invention is a novel compound,
A near-infrared absorbing compound having high wavelength selectivity in the long wavelength region near 900 nm or more.

In the general formula (1), R ₁ and R ₂ are each independently an optionally substituted alkyl group, and R ₃ and R ₄ are
Each independently represents a hydrogen atom, an optionally substituted alkyl group, or an optionally substituted aryl group, and M represents a divalent metal atom, a trivalent or tetravalent substituted metal, or an oxymetal.

In R ₁ and R ₂ , the alkyl group which may be substituted includes methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl,
sec-butyl group, n-pentyl group, isopentyl group,
Neopentyl group, n-hexyl group, isohexyl group, s
ec-hexyl group, n-heptyl group, isoheptyl group,
linear or branched alkyl group such as sec-heptyl group, n-octyl group, 2-ethylhexyl group, halogenoalkyl group such as chloroethyl group, trifluoromethyl group, methoxymethyl group, methoxyethyl group, ethoxyethyl group, propoxy group Ethyl group, alkoxyalkyl group such as butoxyethyl group, hydroxyethyl group, hydroxyalkyl group such as hydroxypropyl group, hydroxyethoxyethyl group, hydroxypolyether group such as hydroxyethoxyethoxyethyl group, methoxyethoxyethyl group,
Examples thereof include alkoxypolyether groups such as an ethoxyethoxyethyl group, a propoxyethoxyethyl group, and a butoxyethoxyethyl group.

R ₃ and R _{4 each} represent a hydrogen atom, an optionally substituted alkyl group or an optionally substituted aryl group, and the optionally substituted alkyl group includes
Methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group,
n-pentyl group, isopentyl group, neopentyl group, n
-Hexyl group, isohexyl group, sec-hexyl group,
n-heptyl group, isoheptyl group, sec-heptyl group, n-octyl group, linear or branched alkyl group such as 2-ethylhexyl group, halogenoalkyl group such as chloroethyl group, methoxymethyl group, methoxyethyl group, ethoxyethyl And an aryl group which may be substituted, such as a phenyl group, a naphthyl group, a 4-methylphenyl group, a 4-ethylphenyl group, and the like.
-Propylphenyl group, 4-t-butylphenyl group, 4
-Methoxyphenyl group, 4-ethoxyphenyl group, 4
-Chlorophenyl group, 4-bromophenyl group, 2-methylphenyl group, 2-ethylphenyl group, 2-propylphenyl group, 2-t-butylphenyl group, 2-methoxyphenyl group, 2-ethoxyphenyl group, 2- Examples thereof include a hydroxyphenyl group, a 2-chlorophenyl group, and a 2-bromophenyl group.

Particularly preferred are compounds in which R ₁ and R ₂ are straight-chain or branched unsubstituted alkyl groups, and R ₃ and R ₄ are hydrogen atoms, straight-chain or branched unsubstituted alkyl groups.

As the divalent metal represented by M, Cu
(II), Zn (II), Fe (II), Co (II), Ni
(II), Ru (II), Rh (II), Pd (II), Pt
(II), Mn (II), Mg (II), Ti (II), Be
(II), Ca (II), Ba (II), Cd (II), Hg
(II), Pb (II), Sn (II) and the like.

As the monosubstituted trivalent metal, Al—Cl,
Al-Br, Al-F, Al-I, Ga-Cl, Ga-
F, Ga-I, Ga-Br, In-Cl, In-Br,
In-I, In-F, Tl-Cl, Tl-Br, Tl-
I, Tl-F, Al- C 6 H 5, Al-C 6 H 4 (C
_{H 3), In-C 6} H 5, In-C 6 H 4 (CH 3), In-
C ₆ H ₅ , Mn (OH), Mn (OC ₆ H ₅ ), Mn [OS
i (CH ₃ ) ₃ ], Fe—Cl, Ru—Cl and the like.

The disubstituted tetravalent metal includes CrCl ₂ ,
SiCl ₂ , SiBr ₂ , SiF ₂ , SiI ₂ , ZrC
l ₂ , GeCl ₂ , GeBr ₂ , GeI ₂ , GeF ₂ , Sn
Cl ₂ , SnBr ₂ , SnF ₂ , TiCl ₂ , TiBr ₂ ,
TiF ₂ , Si (OH) ₂ , Ge (OH) ₂ , Zr (O
H) ₂ , Mn (OH) ₂ , Sn (OH) ₂ , TiR ₂ , Cr
R ₂ , SiR ₂ , SnR ₂ , GeR ₂ [R represents an alkyl group, a phenyl group, a naphthyl group, and derivatives thereof], S
i (OR ') ₂ , Sn (OR') ₂ , Ge (OR ') ₂ ,
Ti (OR ′) ₂ , Cr (OR ′) ₂ [R ′ is an alkyl group, a phenyl group, a naphthyl group, a trialkylsilyl group,
Represents a dialkylalkoxysilyl group and a derivative thereof], Sn (SR ″) ₂ , Ge (SR ″) ₂ (R ″ represents an alkyl group, a phenyl group, a naphthyl group, and a derivative thereof).

Examples of oxymetals include VO, MnO,
TiO and the like are exemplified.

Particularly preferred M is Co, Ni, Cu, Z
n, Pd, AlCl, InCl, TiO, and VO.

The aminonaphthalocyanine compound of the present invention represented by the general formula (1) can be prepared by reacting a dicyanonaphthalene derivative represented by the following formula (2) with a metal or a metal compound in a solvent. Can be produced by reducing the nitro group. Further, it can be produced by alkylating and arylating this amino group.

[0021]

Embedded image (Wherein R _{1 and} R ₂ have the same meaning as in the general formula (1))

The starting compound (2) is preferably a dicyanonaphthalene derivative in which the nitro group is substituted at the 5-position in view of availability and ease of synthesis.

As a specific method for synthesizing the compound (2),
Synthetic Organic Chemistry, Vol. 16 (Vol. 16), Using Dicyanonaphthoquinone
No. 10 (1958), page 50, nitration, followed by synthesis of a dicyano compound by the method described in The Chemical Society of Japan, No. 12 (1981), page 1916, and the resulting diol is easily obtained by alkylation. .

As the metal or metal compound, Al,
Si, Ti, V, Mn, Fe, Co, Ni, Cu, Z
n, Ge, Ru, Rh, Pd, In, Sn, Pt, P
b, Mg, Ca, Ba, Be, Cd, Hg and their halides, carboxylate, sulfate, nitrate, carbonyl compound, oxide, complex and the like. In particular, metal halides or carboxylate salts are preferably used,
Examples of these are copper chloride, copper bromide, copper iodide, nickel chloride, nickel bromide, nickel acetate, cobalt chloride, cobalt bromide, cobalt acetate, iron chloride, zinc chloride, zinc bromide, zinc iodide, Zinc acetate, vanadium chloride, vanadium oxytrichloride, palladium chloride, palladium acetate, aluminum chloride, manganese chloride, manganese acetate, manganese acetylacetone, manganese chloride, lead chloride, lead acetate, indium chloride, titanium chloride, tin chloride, etc. .

The amount of the metal or metal compound to be used is 0.2 to 0.2 with respect to the dicyanonaphthalene derivative of the general formula (2).
It is 0.6 mole, preferably 0.25 to 0.4 mole.

The solvent used for the reaction has a boiling point of 100
An organic solvent having a temperature of at least 130 ° C, preferably at least 130 ° C, is used. Examples include n-amyl alcohol, n-hexanol, cyclohexanol, 2-methyl-1-pentanol, 1-heptanol, 2-heptanol, 1-octanol, 2-ethylhexanol, benzyl alcohol, ethylene glycol, propylene glycol, Alcohol solvents such as ethoxyethanol, propoxyethanol, butoxyethanol, dimethylaminoethanol and diethylaminoethanol, trichlorobenzene, chloronaphthalene, sulfolane, nitrobenzene, quinoline, N, N-dimethylformamide, N-methyl-2
-Pyrrolidone, N, N-dimethylimidazolidinone,
High-boiling solvents such as N, N-dimethylacetamide and urea are exemplified.

The amount of the solvent to be used is 1 to 100 times by weight, preferably 5 to 20 times by weight, relative to the dicyanonaphthalene derivative.

In the reaction, ammonium molybdate or DBU (1,8-diazabicyclo [5,4,0] undecene) may be added as a catalyst. The addition amount is 0.1 to 1 mol of the dicyano naphthalene derivative.
It is 10 mol, preferably 0.5 to 2 mol.

The reaction temperature is 100 to 300 ° C., preferably 130 to 220 ° C.

Further, as a method for obtaining the compound of the present invention by reducing the nitronaphthalocyanine compound, a usual reduction technique can be used. For example, the nitronaphthalocyanine compound obtained above is dissolved in a solvent. And in the presence of a reducing agent.

Examples of the solvent used in the reaction include, for example,
Alcohol solvents such as methanol, ethanol, 2-propanol, butanol, n-amyl alcohol, benzyl alcohol, ethylene glycol, ethoxyethanol, and dimethylaminoethanol; ethers such as tetrahydrofuran (THF), dioxane, diethylene glycol dimethyl ether, diethyl ether and dibutyl ether Solvent N, N-dimethylformamide, N-methyl-2-pyrrolidone, N, N-dimethylimidazolidinone, N, N-dimethylacetamide, sulfolane,
Examples include polar solvents such as water and acetic acid, but are not limited thereto.

The amount of the solvent used is 1 to 100 times, preferably 5 to 20 times the weight of the nitronaphthalocyanine compound.

Examples of the reducing agent include metal hydrides such as lithium aluminum hydride, sodium borohydride and diisobutylaluminum hydride, metals such as sodium, zinc and tin, sodium hydrosulfide, triphenylphosphite and thiosulfate. Sodium and the like.

The amount of the reducing agent to be used is 0.08 to 800 times, preferably 8 to 80 times the mol of the nitronaphthalocyanine compound.

Further, hydrogen reduction can be carried out in the presence of a catalyst such as Raney nickel, palladium carbon or the like.

At this time, the amount of the catalyst used is 0.004 to 40 times, preferably 0.04 to 4 times the weight of the nitronaphthalocyanine compound. Reaction temperature is -80
C. to 200C, preferably 20C to 100C.

As a post-treatment after completion of the reaction, the aminonaphthalocyanine compound of the present invention can be obtained by distilling off the solvent after the reaction or discharging the reaction solution into a poor solvent for the naphthalocyanine compound and filtering the precipitate. Obtainable.

Further, when alkylation or arylation of the amino group is carried out, ordinary alkylation or arylation techniques can be used. For example, the aminonaphthalocyanine compound obtained above is dissolved in a solvent. It is obtained by reacting with a halide or a sulfonic ester in the presence of a base.

As the solvent used in the reaction, N, N-
Dimethylformamide, N-methyl-2-pyrrolidone,
Examples of the amount of the solvent used include polar solvents such as N, N-dimethylimidazolidinone, N, N-dimethylacetamide, and sulfolane; and ether solvents such as tetrahydrofuran (THF), dioxane, diethylene glycol dimethyl ether, diethyl ether, and dibutyl ether. Is 1 to 100 times, preferably 5 to 20 times the weight of the naphthalocyanine compound.

Examples of the halide to be used include methyl iodide, ethyl bromide, propyl chloride, butyl bromide, isobutyl chloride, bromobenzene, and benzene iodide. Examples of the sulfonic acid ester include methyl paratoluenesulfonate and paratoluene. Examples thereof include ethyl sulfonate, butyl paratoluenesulfonate, phenyl paratoluenesulfonate, and phenyl trifluorosulfonate.

The amount used is 0.4 to 40 moles, preferably 2 to 8 moles, per mole of the aminonaphthalocyanine compound.
Is a mole.

As the base to be used, sodium hydroxide,
Potassium hydroxide, potassium carbonate, inorganic bases such as sodium carbonate, triethylamine, tributylamine, pyridine, amines such as DBU and the like, the amount of use is 0.4 to 40 moles per mole of the aminonaphthalocyanine compound, Preferably it is 2 to 8 mol. Reaction temperature is 20-2
00 ° C, preferably 80 to 150 ° C.

Further, as another method, an alkylating agent such as diazomethane and dimethyl sulfate may be used.

The near infrared absorbing resin composition and near infrared absorbing material of the present invention will be described. The naphthalocyanine compound of the present invention is a compound that can selectively absorb light in a long wavelength region around 900 nm or more, and a near infrared absorbing resin composition and a near infrared absorbing material containing the naphthalocyanine compound. About
It is a material that can selectively absorb light in a long wavelength region, and is a material that has not existed in the past.

The near-infrared absorbing resin composition of the present invention is obtained by incorporating the naphthalocyanine compound of the present invention into a resin. As a method of containing, a method of heating and mixing with a resin, dissolving in a solvent to form a coating with a resin,
Alternatively, there is a method of forming an ink. At that time, additives such as an ultraviolet absorber and an antioxidant can be added as needed.

Examples of the resin to be used include polyethylene, polystyrene, polyacrylic acid, polyacrylate, polyvinyl acetate, polyacrylonitrile, polyvinyl chloride, polyvinyl fluoride such as polyvinyl fluoride, and addition polymers of vinyl compounds, and polymethacrylic acid. , Polymethacrylate, polyvinylidene chloride, polyvinylidene fluoride, polyvinylidene cyanide, vinylidene fluoride / trifluoroethylene copolymer, vinylidene fluoride / tetrafluoroethylene copolymer, vinylidene cyanide / vinyl acetate copolymer, etc. A vinyl compound or a copolymer of a fluorine-based compound, a compound containing fluorine such as polytrifluoroethylene, polytetrafluoroethylene, and polyhexafluoropropylene; a polyamide such as nylon 6, nylon 66; a polyimide; Polyurethane, polypeptides, polyesters such as polyethylene terephthalate, polycarbonate, polyoxymethylene, polyethylene oxide,
Examples include polyethers such as polypropylene oxide, epoxy resins, polyvinyl alcohol, polyvinyl butyral, and the like, but are not limited to these resins.

Since the near-infrared absorbing resin composition of the present invention has low absorption in the visible region and high wavelength selectivity, it is excellent in light-to-heat conversion materials, optical recording media, near-infrared absorbing filters, agricultural films, heat ray shielding films, Near infrared absorbing paint,
It can be used as a near-infrared absorbing material such as a printing ink for preventing forgery and a light receiving element.

The method for producing a near-infrared absorbing material such as a film, a sheet and a plate using the naphthalocyanine compound is not particularly limited. For example, the following three methods can be used.

That is, (1) a method in which a naphthalocyanine compound is kneaded with a resin and heat molding is performed to produce a resin plate or film, and (2) a paint containing the naphthalocyanine compound is produced, and a transparent resin plate and a transparent film are prepared. Or a method of coating on a transparent glass plate, (3) a naphthalocyanine compound is contained in an adhesive, a laminated resin plate,
A method for producing a laminated resin film, laminated glass, etc.,
It is.

First, in the method (1) in which a naphthalocyanine compound is kneaded with a resin and heat-molded, as the resin material, polyethylene, polystyrene, polyacrylic acid,
Polyacrylic acid esters, polyvinyl acetate, polyacrylonitrile, polyvinyl chloride, polyvinyl compounds such as polyvinyl fluoride and addition polymers of vinyl compounds, polymethacrylic acid, polymethacrylic acid esters, polyvinylidene chloride, polyvinylidene fluoride, polyvinylidene cyanide ,
Vinylidene fluoride / trifluoroethylene copolymer, vinylidene fluoride / tetrafluoroethylene copolymer, vinylidene cyanide / vinyl acetate copolymer and other vinyl compound or fluorine compound copolymer, polytrifluoroethylene, poly Compounds containing fluorine such as tetrafluoroethylene and polyhexafluoropropylene, nylon 6,
Polyamide such as nylon 66, polyimide, polyurethane, polypeptide, polyester such as polyethylene terephthalate, polycarbonate, polyoxymethylene,
Examples thereof include polyethers such as polyethylene oxide and polypropylene oxide, epoxy resins, polyvinyl alcohol, and polyvinyl butyral, but are not limited to these resins.

Although the processing temperature, film forming conditions, and the like are slightly different depending on the base resin used, a naphthalocyanine compound is usually added to powder or pellets of the base resin, and heated and dissolved at 150 to 350 ° C. After molding, make a resin plate, or make it into a film with an extruder, or make a raw material with an extruder,
It is obtained by a method of stretching uniaxially or biaxially 2 to 5 times at 30 to 120 ° C. to form a film having a thickness of 10 to 200 μm. In addition, dyes, pigments or other near-infrared absorbing compounds for controlling color tone may be added in addition to additives used for ordinary resin molding such as an ultraviolet absorber and a plasticizer at the time of kneading. The amount of the naphthalocyanine compound to be added varies depending on the thickness of the resin to be produced, the desired absorption intensity, the desired near-infrared transmittance, the desired solar transmittance, the desired visible transmittance, and the like, but is usually 1 ppm to 10%.

In the method (2) of coating after coating, a method of dissolving the naphthalocyanine compound of the present invention in a binder resin and an organic solvent to form a coating, and pulverizing the naphthalocyanine compound to several μm or less. A method of preparing a water-based paint dispersed in an acrylic emulsion, or based on an amino group in a naphthalocyanine compound, by reacting with an isocyanate, an ester, or a double bond to form a urethane resin, an acrylic resin, a polyester resin or a polyolefin resin. For example, there is a method of dissolving a resin bonded to an organic solvent in an organic solvent to form a coating, or a method of forming an aqueous emulsion coating.

In the above method, usually, an aliphatic ester resin, an acrylic resin, a melamine resin, a urethane resin, an aromatic ester resin, a polycarbonate resin, an aliphatic polyolefin resin, an aromatic polyolefin resin,
A polyvinyl resin, a polyvinyl alcohol resin, a modified polyvinyl resin (PVB, EVA, or the like) or a copolymer resin thereof is used as a binder. As the solvent, a halogen-based, alcohol-based, ketone-based, ester-based, aliphatic hydrocarbon-based, aromatic hydrocarbon-based, ether-based solvent, or a mixture thereof is used.

The concentration of the naphthalocyanine compound depends on the thickness of the coating, the desired absorption intensity, the desired near-infrared transmittance,
Depending on the desired solar transmittance, the desired visible transmittance, etc., it is usually 0.1 to 100 with respect to the weight of the binder resin.
%. Further, the binder resin concentration is usually 1 to 50% with respect to the whole paint.

Similarly, the acrylic emulsion-based water-based paint can be obtained by dispersing a finely pulverized naphthalocyanine compound (1 μm or less, preferably 50 to 500 nm) in an uncolored acrylic emulsion paint. Dyes, pigments, or other near-infrared absorbing compounds for controlling the color tone may be added to the paint, in addition to additives such as an ultraviolet absorber and an antioxidant, which are used in ordinary paints.

The paint prepared by the above method is applied on a transparent resin film, a transparent resin, a transparent glass or the like with a bar coater,
A near-infrared absorbing filter is prepared by coating with a blade coater, spin coater, reverse coater, die coater, spray or the like. It is also possible to provide a protective layer to protect the coating surface, or to bond the coating surface to a transparent resin plate, a transparent resin film, or the like. A cast film is also included in the method.

In the method (3) for producing a laminated resin plate, a laminated resin film, a laminated glass, etc. by incorporating the naphthalocyanine compound of the present invention into an adhesive, a general silicone-based or urethane is used as the adhesive. A known adhesive for laminated glass, such as a polyvinyl butyral adhesive (PVB) or an ethylene-vinyl acetate adhesive (EVA) for a resin or an acrylic resin or a laminated glass can be used. Adhesion of naphthalocyanine compound with 0.1 to 50% is used to bond resin plates, resin plate and resin film, resin plate and glass, resin film, resin film and glass, and glass, and absorb near infrared rays Prepare the material. There is also a method of thermocompression bonding.

The near-infrared absorbing filter manufactured as described above is actually made more practical by providing an ultraviolet cut layer, a hard coat layer, an anti-reflection layer, or an adhesive layer on one or both sides thereof. Filter. If necessary, a near-infrared reflective layer laminated by alternately sputtering metal oxides such as indium oxide, tin oxide and zinc oxide and metals such as gold and silver, or a copper salt or zinc oxide as a main component The near-infrared absorbing paint of the present invention is prepared by atomizing a metal mixture, a tungsten compound, YbPO ₄ , ITO (tin-doped indium oxide), ATO (tin-doped antimony oxide) or the like into an average particle size of 100 μm or less. Can be combined with filters.

Since the near-infrared absorbing material of the present invention has low absorption in the visible region and high wavelength selectivity, it is excellent in light-to-heat conversion materials, optical recording media, near-infrared absorbing filters, agricultural films, heat ray blocking films, light receiving elements. Etc. can be used.

[0060]

EXAMPLES Hereinafter, the present invention will be described in more detail with reference to Examples, but the present invention is not limited thereto.

Example 1 Synthesis of naphthalocyanine compound (A) 4.0 g of the following compound (a), 0.323 of copper (I) chloride
g, DBU 1.63 mL, n-amyl alcohol 20 m
After mixing L, the mixture was stirred under reflux for 6 hours. After cooling, the mixture was discharged into 100 mL of methanol, and the precipitate was separated by filtration to obtain 2.83 g of a nitronaphthalocyanine compound. Furthermore, 2.5 g of the obtained compound and 50 mL of N, N-dimethylformamide (hereinafter abbreviated as DMF) were mixed, and the mixture was heated to 70 ° C. To this, 5 g of a 20% NaSH aqueous solution was dropped, and the mixture was stirred for 1 hour. After cooling, the solution was discharged into 500 mL of water, neutralized with dilute sulfuric acid, and crystallized. The precipitate is filtered off,
2.40 g of the target compound (A) was obtained.

[0062]

Embedded image

[0063]

Embedded image (X ₁ and X ₂ each independently represent an NH ₂ group, and the other is a hydrogen atom.)

The maximum absorption wavelength (λmax) of the naphthalocyanine compound in the toluene solution was 912 nm, and the half width was 58 nm. In addition, the compound had high solvent solubility and exhibited a solubility of 10% or more in toluene.

Further, 1.3 g of the compound (A) and 10 kg of polymethyl methacrylate (PMMA) (trade name: “Delpet 80N”, manufactured by Asahi Kasei Kogyo Co., Ltd.) were mixed.
The mixture was melted at 260 to 280 ° C., and a near-infrared absorbing filter having a thickness of 3 mm was prepared with an extruder. The filter is 9
Near-infrared rays near 10 nm were selectively and efficiently absorbed (FIG. 1).

Comparative Example 1 Using a compound represented by the following structural formula described in JP-A-8-225752, the spectrum in a toluene solution was measured in the same manner as in Example 1, and the maximum absorption wavelength (λm
ax) was 940 nm, and the half width was 136 nm. Further, when a near-infrared absorbing filter of 3 mm was produced in the same manner as in Example 1, the wavelength selectivity was inferior to the filter described in Example 1 (FIG. 2).

[0067]

Embedded image

Example 2 Synthesis of naphthalocyanine compound (B) 3.0 g of the compound (A), 0.18 g of potassium carbonate,
After mixing 1.02 g of ethyl bromide and 20 mL of DMF,
Stirred at 100 ° C. for 6 hours. After cooling, the mixture was discharged into 100 mL of water, and the precipitate was separated by filtration to obtain 2.7 g of the target compound (B).

[0069]

Embedded image (One of X ₃ and X ₄ independently represents an NHEt group, and the other represents a hydrogen atom.)

The maximum absorption wavelength (λmax) of the compound in a toluene solution is 928 nm, and the half width is 64.
nm. This compound also had high solvent solubility and exhibited a solubility of 10% or more in toluene.

Further, a near-infrared absorbing filter having a thickness of 3 mm was prepared using the compound in the same manner as in Example 1. The filter selectively and efficiently absorbed near-infrared light near 930 nm.

Example 3 Naphthalocyanine compound (A) synthesized in Example 1
7 g, "Tinuvin 329" (trade name; benzotriazole-based ultraviolet absorber manufactured by Ciba-Geigy) 100
g, "Seasolve 501" (trade name; Cipro Kasei Co., Ltd.)
UV absorber) 100 g, and polycarbonate (trade name: "Panlite K-1300Z", manufactured by Teijin Limited)
10 kg was melt-kneaded at 260 to 280 ° C, and a near-infrared absorbing filter having a thickness of 2 mm was produced using an extruder. Further, in order to enhance the durability of the polycarbonate resin plate, the filter and a 50 μm-thick acrylic film containing an ultraviolet absorber were thermally laminated.
The acrylic film is a benzotriazole-based ultraviolet absorber (trade name: "Tinuvin P", manufactured by Ciba Geigy Co., Ltd.)
100 g, and a cyanoacetic acid ultraviolet absorber (trade name;
"Ubinar 3039", manufactured by BASF Corporation) 100
g with polymethyl methacrylate (PMMA) (trade name;
"Delpet 80N", manufactured by Asahi Kasei Kogyo Co., Ltd.) 10 kg
Was melted at 260 to 280 ° C., and an extruder was used to prepare a 200 μm-thick raw film, which was then biaxially stretched.

The filter selectively and efficiently absorbed light near 910 nm.

Example 4 Naphthalocyanine compound (B) 1 synthesized in Example 2
g, 10 g of an ultraviolet absorber (trade name: "Tinuvin 327", manufactured by Ciba Geigy Co., Ltd.) in 300 ml of ethyl cellosolve.
1 g, and 200 g of an acrylic paint (trade name: "Almatex 1043" manufactured by Mitsui Toatsu Chemicals, Inc.) was added to prepare a near infrared absorbing paint. When the thickness of the paint is 10 μm
Was coated on the glass by flow coating.

The glass selectively and efficiently absorbed light near 930 nm.

Example 5 Synthesis of naphthalocyanine compound (C) Anhydrous nickel chloride (II) instead of copper chloride of Example 1
In the same manner as in Example 1 except that 0.42 g was used, 1.84 g of the target compound (C) was obtained.

[0077]

Embedded image (X ₁ and X ₂ each independently represent an NH ₂ group, and the other is a hydrogen atom.)

The maximum absorption wavelength (λmax) of the compound in a toluene solution is 906 nm, and the half width is 56
nm. This compound also had high solvent solubility and exhibited a solubility of 10% or more in toluene.

When the aminonaphthalocyanine compound (C) was used to coat glass in the same manner as in Example 4, the glass selectively and efficiently absorbed light near 900 nm.

Example 6 Synthesis of Naphthalocyanine Compound (D) 2.5 g of the following compound (b), 0.162 of copper (I) chloride
g, 0.815 mL of DBU, and 10 mL of diethylene glycol dimethyl ether, followed by stirring at 150 ° C. for 10 hours. After cooling, the mixture was discharged into 50 mL of methanol, and the precipitate was separated by filtration.
g was obtained. After mixing 1.0 g of the obtained compound and 20 mL of N, N-dimethylformamide (hereinafter abbreviated as DMF), the mixture was heated to 70 ° C. To this, 2 g of a 20% NaSH aqueous solution was dropped, and the mixture was stirred for 1 hour. Cool and add 200
The solution was discharged into mL and neutralized with dilute sulfuric acid for crystallization. The precipitate was separated by filtration to obtain 0.96 g of the target compound (D).

[0081]

Embedded image

[0082]

Embedded image (X ₁ and X ₂ each independently represent an NH ₂ group, and the other is a hydrogen atom.)

The maximum absorption wavelength (λmax) of the aminonaphthalocyanine compound in a toluene solution is 908 n
m and the half width was 56 nm. In addition, the compound had high solvent solubility and exhibited a solubility of 10% or more in toluene.

Examples 7 to 23 By the same method as the aminonaphthalocyanine compound (A) synthesized in Example 1, naphthalocyanine compounds shown in Table 1 were obtained.

The results are shown in Table 1. In all,
Light in the near-infrared region near 900 nm or more was highly selectively and efficiently absorbed. .

The substitution position of the amino group in the table is represented by β when the position is 1 or 4, 10 or 13, 19 or 22, 28 or 31 as shown in the following formula (E). , 2 or 3, 11 or 12, 20, 20 or 21, 29 or 30 is expressed as γ position.

[0087]

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[0088]

[Table 1]

[0089]

Industrial Applicability The naphthalocyanine compound of the present invention is a compound having excellent compatibility with a solvent and a resin, and excellent near-infrared absorption ability in a long wavelength region around 900 nm or more. It becomes an excellent material as a near-infrared absorbing material, and can be suitably used for applications such as near-infrared absorbing filters, agricultural films, optical cards, and optical recording media.

[Brief description of the drawings]

FIG. 1 is a graph showing a light absorption curve of a filter obtained in Example 1.

FIG. 2 is a graph showing a light absorption curve of a filter obtained in Comparative Example 1.

 ──────────────────────────────────────────────────続 き Continued on the front page (72) Inventor Ryu Ooi 1190 Kasama-cho, Sakae-ku, Yokohama-shi, Kanagawa Prefecture Inside Mitsui Chemicals, Inc.

Claims (5)

[Claims] 1. A naphthalocyanine compound represented by the following general formula (1). Embedded image (Wherein, R ₁ and R ₂ each independently represent an optionally substituted alkyl group, and R ₃ and R ₄ each independently represent a hydrogen atom,
It represents an optionally substituted alkyl group or an optionally substituted aryl group, and M represents a divalent metal atom, a trivalent or tetravalent substituted metal, or an oxymetal. ) 2. R ₁ and R ₂ are an unsubstituted alkyl group,
_3. The naphthalocyanine compound according to claim 1, wherein R ₃ and R ₄ are a hydrogen atom or an alkyl group. 3. M is Co, Ni, Cu, Zn, Pd,
3. The naphthalocyanine compound according to claim 1, which is AlCl, InCl, TiO, or VO. 4. A near-infrared absorbing resin composition comprising the naphthalocyanine compound according to claim 1. 5. A near-infrared absorbing material comprising the naphthalocyanine compound according to claim 1.