JP2000017184A - Compound absorbing near infrared light and its use - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain the subject compound capable of being simply produced at a low cost, exhibiting high light resistance and high solubility in aqueous solvents, and useful for near IR light-absorbing inks, near IR light absorbing materials, etc., by allowing a phthalocyanine compound to contain an ion pair group. SOLUTION: This near IR light-absorbing compound contains an ion pair group G comprising a cationic group for example, a group of formula I [R10 and R11 are each H, a (substituted) alkyl group or the like; D is a bonding group or a bond; (j) is 0-4]}: A+ and its counter-anionic group (for example, a halogen ion): B-, and is expressed by a structure of formula II EX is H, a halogen, OH or the like; R1-R9 are each H, a (substituted) alkyl, a (substituted) aryl(oxy) or the like; G1 and G2 are each H or a group G, provided that at least one of G1 and G2 is the group G; M is a divalent metal, a trivalent or tetravalent substituted metal or the like; (l), (m) and (n) are 1-8, 0-14, and 0-14, respectively, provided that (n)+2(1)+(m)=16].

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a near-infrared absorbing compound which is excellent in durability (especially, stability against light) and excellent in solubility in water and alcohols and is easily processed. The present invention also relates to a near-infrared absorbing resin composition containing the near-infrared absorbing compound and a near-infrared absorbing material containing the compound.

[0002]

2. Description of the Related Art A near-infrared absorbing compound can be used for a recording layer of an optical recording medium such as an optical disk, or can be used as a near-infrared absorbing ink which can be read by a near-infrared detector by forming an ink. It is also used as a photothermal conversion compound used in direct plate making with a semiconductor laser or in a printing recording system. In addition, a near-infrared absorbing material can be produced by combining with a binder resin to form a paint and coat it on plastic or glass, or by kneading with a resin.

[0003] Near-infrared absorbing materials are used as windows for buildings, cars, trains, ships, aircrafts, etc., to block external heat rays.
It is possible to suppress the temperature rise in the room and in the vehicle. In addition, by cutting a specific wavelength range, cutting of near infrared rays generated from displays etc., control of plant growth as a film for selective use of light quality, infrared cut of semiconductor light receiving element,
It can also be used for eyeglasses and the like that protect human eyes from rays containing harmful infrared rays.

[0004] In recent years, while demands for reducing the load on the human body and the surrounding environment have been raised, there is a strong demand for various materials that do not affect the environment. In particular, with respect to paints and the like, there is a strong interest from organic solvent types to water-based types, and materials that are soluble in water or alcohol corresponding to these are desired.

As the near-infrared absorbing compound, a cyanine compound, an aminium salt type compound, a dithiol metal complex compound, and an anthraquinone compound have been known. Particularly, as a near-infrared absorbing compound having high durability, Phthalocyanine compounds are known.

Most of the phthalocyanine compounds studied so far have high solubility in resins and organic solvent type inks, and therefore most of them are compounds showing solubility in organic solvents. Phthalocyanine compounds exhibiting high solubility in water and alcohols have a λmax of at most 600 to 800 n.
Compounds having absorption in the short wavelength region of m and absorption in the long wavelength region and being soluble in water, alcohol, and the like are hardly known.

As a phthalocyanine compound, for example, in Japanese Patent Publication No. 4-75916, a compound having a λmax of 909 nm is obtained by reacting a chlorinated copper phthalocyanine compound with 2-aminothiophenol in Examples. The solvent is soluble but not soluble in water or alcohol.

Japanese Patent Application Laid-Open No. Sho 63-308073 discloses a method for increasing the solubility of a phthalocyanine compound.
-Aminothiophenol and 4-methylphenylthiol in the coexistence of the reaction,
No. 70765 discloses that after reacting a perchloro copper phthalocyanine compound with 2-aminothiophenol,
A method for alkylating a nitrogen atom with alkyl bromide to improve solubility is disclosed. These are all compounds that have been studied to exhibit high solubility in organic solvents.

[0009]

SUMMARY OF THE INVENTION An object of the present invention is to provide a near-infrared absorbing compound which has a high light resistance and a high solubility in water or alcohol at low cost and easily. . Another object is to provide a resin composition and a near-infrared absorbing material containing the near-infrared absorbing compound.

[0010]

The present inventors Means for Solving the Problems] As a result of extensive studies to solve the above problems, a cationic group in the phthalocyanine compound A ⁺ and its counter anion B ^- at least one ion pair groups G consisting of The present inventors have found that the addition of the compound can provide a near-infrared absorbing compound represented by the general formula (1) having high solubility particularly in an aqueous solvent such as water or alcohol, and completed the present invention.

[0011] Namely, the present invention is a cationic group A ⁺ and its counter anion B ^- near infrared ray absorbing compound represented by the general formula (1), characterized in that at least one containing an ion pair groups G, The present invention relates to a resin composition containing the near-infrared absorbing compound and a near-infrared absorbing material.

[0012]

Embedded image

[Wherein X is independently a hydrogen atom, a halogen atom, a hydroxyl group, an optionally substituted alkoxy group,
Represents an aryloxy group which may be substituted, an alkylthio group which may be substituted, an arylthio group which may be substituted, an alkylamino group which may be substituted, and an arylamino group which may be substituted; Adjacent Xs may form a 5- or 6-membered ring through two heteroatoms, and R _{1 to} R ₉ are each independently a hydrogen atom, an optionally substituted alkyl group, or an optionally substituted Aryl group, optionally substituted alkoxy group, optionally substituted aryloxy group, optionally substituted alkylsulfonyl group, optionally substituted arylsulfonyl group, optionally substituted alkylcarbonyl A group, an optionally substituted arylcarbonyl group, G ₁ and G ₂ represent a hydrogen atom or the above-mentioned ion pair group G, May be the same or different, at least one is the ion pair group G, 1 represents an integer of 1 to 8, m represents an integer of 0 to 14, and n represents 0 to 14
And n + 2l + m = 16, and M represents a divalent metal atom or a trivalent or tetravalent substituted metal or oxymetal. ]

[0014]

BEST MODE FOR CARRYING OUT THE INVENTION The near-infrared absorbing compound of the present invention will be described.

In the near-infrared absorbing compound (1) of the present invention, the cationic group A ⁺ of the ion pair group G includes:
Preferred examples include a pyridinium ion (formula (a) or (b)) and an ammonium ion (formula (c)) shown below.

[0016]

Embedded image (In the formulas (a), (b) and (c), R ₁₀ , R _{13 to} R ₁₅ are each independently a hydrogen atom, an optionally substituted alkyl group,
Represents an aryl group which may be substituted, R _{13 to} R ₁₅ may form a ring, and R ₁₁ and R ₁₂ each independently represent a halogen atom, an alkyl group, an alkoxy group, or an alkylthio group; k represents an integer of 0 to 4. In addition, adjacent R ₁₁
Together, they may form a ring with R ₁₂ to each other. D, D ', D "
Represents a linking group, and may be linked via no linking groups D, D ′, and D ″.)

The alkyl group which may be substituted for R ₁₀ and R _{13 to} R ₁₅ is not particularly limited, but may be, for example, a methyl group, an ethyl group, an n-propyl group, an iso- Propyl, n-butyl, iso-butyl, sec-butyl, tert-butyl, n-pentyl, iso-pentyl, n-hexyl, n-
Unsubstituted alkyl groups such as heptyl group, n-octyl group, n-nonyl group, n-decanyl group, aralkyl groups such as benzyl group, phenethyl group, methoxymethyl group, ethoxyethyl group, methoxyethylethoxyethyl group, propoxy Ethyl group, alkoxyalkyl group such as butoxyethyl group, hydroxymethyl group, hydroxyethyl group, hydroxyalkyl group such as hydroxypropyl group, methoxyethoxyethyl group, ethoxyethoxyethyl group, alkoxyalkoxyalkyl group such as propoxyethoxyethyl group, Examples thereof include a hydroxyalkoxyalkyl group such as a hydroxyethoxyethyl group and a hydroxypropoxypropyl group.

The aryl group which may be substituted is not particularly limited, but may be a phenyl group, 2-
Mercaptophenyl group, 3-mercaptophenyl group, 4
-Mercaptophenyl group, 2-methylphenyl group, 3-
Examples include a methylphenyl group, a 4-methylphenyl group, and a naphthyl group.

The halogen atoms of R ₁₁ and R ₁₂ are fluorine, chlorine, bromine and iodine atoms, and the alkyl groups are
Examples of a methyl, ethyl, propyl, butyl group and the like, examples of the alkoxy group include methoxy, ethoxy, propoxy and butoxy groups, and examples of the alkylthio group include a methylthio, ethylthio, propylthio and butylthio group.
Further, adjacent R ₁₁ or adjacent R ₁₂ may form a ring. For example, quinoline or isoquinoline in which a benzene ring is condensed with a pyridine ring may be formed.

As the linking groups D, D 'and D ", those having 1 to 1 carbon atoms such as methylene, ethylene, propylene and butylene are exemplified.
Examples thereof include alkylene of 0, and carbonylalkylene having 2 to 10 carbon atoms such as carbonylmethylene, carbonylethylene, and carbonylpropylene, but are not limited thereto.

Examples of the counter anion B ⁻ include a halogen atom such as a fluorine atom, a chlorine atom, a bromine atom and an iodine atom, paratoluenesulfonium, CH ₃ OSO ₃ ⁻ , CF ₃
SO ₃ ^- sulfonium ions, such as, carboxyl _{^{ions, ClO 4 -, PF 6 -}} , BF 4 -, SbF 6 - , and the like.

In X, the halogen atom includes fluorine, chlorine, bromine and iodine.

The alkoxy group which may be substituted is not particularly restricted but includes, for example, methoxy, ethoxy, n-propoxy, iso-propoxy, n-butoxy and iso-butoxy. , Sec-
Butoxy group, n-pentoxy group, iso-pentoxy group, n-hexyloxy group, cyclohexyloxy group,
n-heptyloxy group, n-octyloxy group, 2-ethylhexyloxy group, n-nonyloxy group, methoxyethoxy group, ethoxyethoxy group, ethoxyethoxyethoxy group, hydroxyethoxyethoxy group, diethylaminoethoxy group, aminoethoxy group, n -Butylaminoethoxy group, benzylaminoethoxy group, methylcarbonylaminoethoxy group, phenylcarbonylaminoethoxy group, benzyloxy group and the like.

The aryloxy group which may be substituted is not particularly restricted but includes, for example, phenoxy, 2-methylphenoxy, 3-methylphenoxy, 4-methylphenoxy, naphthoxy and the like. Is mentioned.

The alkylthio group which may be substituted is not particularly restricted but includes, for example, methylthio, ethylthio, n-propylthio, iso-
Propylthio group, n-butylthio group, iso-butylthio group, sec-butylthio group, t-butylthio group, n-
Pentylthio group, iso-pentylthio group, neo-pentylthio group, 1,2-dimethyl-propylthio group, n
-Hexylthio, cyclohexylthio, n-heptylthio, 2-ethylhexylthio, n-octylthio, n-nonylthio, methoxyethylthio, ethoxyethylthio, propoxyethylthio, butoxyethylthio, amino Ethylthio group, n-butylaminoethylthio group, benzylaminoethylthio group, methylcarbonylaminoethylthio group, phenylcarbonylaminoethylthio, methylsulfonylaminoethylthio group,
A phenylsulfonylaminoethylthio group, a dimethylaminoethylthio group, a diethylaminoethylthio group, and the like.

The arylthio group which may be substituted is not particularly restricted but includes, for example, a phenylthio group, a naphthylthio group, a 4-methylphenylthio group, a 4-ethylphenylthio group and a 4-propylphenylthio group. Group, 4-t-butylphenylthio group, 4-methoxyphenylthio group, 4-ethoxyphenylthio group, 4-aminophenylthio group, 4-alkylaminophenylthio group, 4-dialkylaminophenylthio group, 4- Phenylaminophenylthio, 4-diphenylaminophenylthio, 4-hydroxyphenylthio, 4-chlorophenylthio, 4-bromophenylthio, 2-methylphenylthio, 2-ethylphenylthio, 2- Propylphenylthio group, 2-t-butylphenylthio group, 2-methoxyphenyl Ruthio group, 2-ethoxyphenylthio group, 2-aminophenylthio group, 2-alkylaminophenylthio group, 2-dialkylaminophenylthio group, 2-phenylaminophenylthio group, 2-diphenylaminophenylthio group, 2 -Hydroxyphenylthio group, 4-dimethylaminophenylthio group, 4-methylaminophenylthio group, 4-methylcarbonylaminophenylthio group, 4-phenylcarbonylaminophenylthio group, 4-methylsulfonylaminophenylthio group,
4-phenylsulfonylaminophenylthio group and the like.

The alkylamino group which may be substituted is not particularly restricted but includes, for example, a methylamino group, an ethylamino group, an n-propylamino group,
iso-propylamino group, butylamino group, pentylamino group, dipentylamino group, hexylamino group, heptylamino group, octylamino group, nonylamino group,
Examples include a benzylamino group, a phenylethylamino group, a phenylpropylamino group, and the like.

Examples of the optionally substituted arylamino group include, but are not particularly limited to, for example,
Phenylamino group, 4-methylphenylamino group, 4-
Examples include a methoxyphenylamino group, a hydroxyphenylamino group, a naphthylamino group and the like.

Further, adjacent Xs may form a 5- or 6-membered ring via two heteroatoms. Examples of the substituent include a substituent represented by the following formula.

[0030]

Embedded image

In R _{1 to} R ₉ , the alkyl group which may be substituted is not particularly limited.
Methyl group, ethyl group, n-propyl group, iso-propyl group, n-butyl group, iso-butyl group, sec-butyl group, n-pentyl group, iso-pentyl group, 1,2-
Dimethyl-propyl group, n-hexyl group, 1,3-dimethyl-butyl group, 1,2-dimethylbutyl group, n-heptyl group, 1,4-dimethylpentyl group, 1-ethyl-3
-Methylbutyl group, n-octyl group, 2-ethylhexyl group, n-nonyl group, n-decyl group, n-undecyl group, n-dodecyl group, n-tridecyl group, n-tetradecyl group, n-pentadecyl group, n A hexadecyl group, n
-Heptadecyl group, n-octadecyl group, n-nonadecyl group, n-eicosyl group, benzyl group, sec-phenylethyl group, 2-methylbenzyl group, 3-methylbenzyl group, 4-methylbenzyl group, 2-phenylethyl Group,
3-dimethylaminopropyl group, 2-dimethylaminoethyl group, 2-diisopropylaminoethyl group, 2-diethylaminoethyl group, 2,2,2-trifluoro-1-
(Trifluoromethyl) ethyl group, 2- (1-piperidinyl) ethyl group, 3- (1-piperidinyl) propyl group, 3- (4-morpholinyl) propyl group, 3- (4
-Morpholinyl) ethyl group, 2- (1-pyrrolidinyl) ethyl group, 2-pyridylmethyl group, furfuryl group and the like.

The aryl group which may be substituted is not particularly limited, but may be a phenyl group, 2-
Mercaptophenyl group, 3-mercaptophenyl group, 4
-Mercaptophenyl group, 2-methylphenyl group, 3-
Examples include a methylphenyl group, a 4-methylphenyl group, and a naphthyl group.

The alkoxy group which may be substituted is not particularly limited, but includes a methoxy group, an ethoxy group, an n-propoxy group, an iso-propoxy group,
-Butoxy group, iso-butoxy group, sec-butoxy group, n-pentoxy group, iso-pentoxy group, benzyloxy group and the like.

The aryloxy group which may be substituted is not particularly limited, but may be a phenoxy group, 2-methylphenoxy group, 3-methylphenoxy group, 4-methylphenoxy group, naphthoxy group or the like. And a substituted aryloxy group.

Examples of the alkylsulfonyl group which may be substituted include, but are not particularly limited to, a methylsulfonyl group, an ethylsulfonyl group and a trifluoromethylsulfonyl group.

The arylsulfonyl group which may be substituted is not particularly restricted but includes a phenylsulfonyl group and a 4-methylphenylsulfonyl group.

The alkylcarbonyl group which may be substituted is not particularly limited, but may be acetyl, propionyl, butyryl, iso-butyryl, valeryl, iso-valeryl, trimethylacetyl, Hexanoyl group, t-butylacetyl group, heptanoyl group, octanoyl group, 2-ethylhexanoyl group, nonanoyl group, decanoyl group, undecanoyl group,
Lauroyl group, tridecanoyl group, tetradecanoyl group, pentadecanoyl group, hexadecanoyl group, heptadecanoyl group, octadecanoyl group, oleoyl group, cyclopentanecarbonyl group, cyclohexanecarbonyl group, 6-chlorohexanoyl group, 6 -Bromohexanoyl group, trifluoroacetyl group, pentafluoropropionyl group, perfluorooctanoyl group, 2,2,4,
4,5,5,7,7,7-nonafluoro-3,6-dioxaheptanoyl group, methoxyacetyl group, 3,6-dioxaheptanoyl group and the like.

The arylcarbonyl group which may be substituted is not particularly limited, but may be a benzoyl group, an o-chlorobenzoyl group, an m-chlorobenzoyl group, a p-chlorobenzoyl group, an o-fluorobenzoyl group. , M-fluorobenzoyl group, p-fluorobenzoyl group, o-acetylbenzoyl group, m-acetylbenzoyl group, p-acetylbenzoyl group, o-methoxybenzoyl group, m-methoxybenzoyl group, p-methoxybenzoyl group, o -Methylbenzoyl group, m-methylbenzoyl group, p-methylbenzoyl group, pentafluorobenzoyl group, 4- (trifluoromethyl) benzoyl group and the like.

In M, examples of the divalent metal include C
u (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.

Examples of the monosubstituted trivalent metal include Al—C
1, Al-Br, Al-F, Al-I, Ga-Cl, G
a-F, Ga-I, Ga-Br, In-Cl, In-B
r, In-I, In-F, Tl-Cl, Tl-Br, T
1-1, Tl-F, Al-C ₆H_Five, Al-C₆H_Four(CH
_Three), In-C₆H_Five, In-C₆H_Four(CH_Three), Mn (O
H), Mn (OC₆H_Five), Mn [OSi (CH_Three)_Three],
Fe-Cl, Ru-Cl and the like can be mentioned.

Examples of disubstituted tetravalent metals include 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 , Ti (R) ₂ ,
Cr (R) ₂ , Si (R) ₂ , Sn (R) ₂ , Ge (R) ₂
[R represents an alkyl group, a phenyl group, a naphthyl group, and derivatives thereof], Si (OR ′) ₂ , Sn (O
R ') ₂ , Ge (OR') ₂ , Ti (OR ') ₂ , Cr
(OR ′) ₂ [R ′ represents an alkyl group, a phenyl group, a naphthyl group, a trialkylsilyl group, 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 derivatives thereof] and the like.

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

Further preferred compounds of the formula (1) include:
The cationic group A ⁺ is a pyridinium ion represented by the formula (a) or (b) or an ammonium ion represented by the formula (c), and the linking groups D, D ′, and D in the respective formulas. "is an alkylene group, a carbonyl alkylene group, R _10, R ₁₃ ~R ₁₅ is a hydrogen atom, a optionally substituted alkyl group, j and k are 0, X is each independently a hydrogen atom Or a halogen atom;
_{1 to} R ₉ are each independently a hydrogen atom or an optionally substituted alkyl group, an optionally substituted alkylsulfonyl group, an optionally substituted arylsulfonyl group,
An alkylcarbonyl group which may be substituted or an arylcarbonyl group which may be substituted;
+ M is 6 to 16, and M is Cu, AlCl, TiO or VO. As the number of l and / or m increases, the absorption wavelength becomes longer and the near infrared region can be widely covered.

Preparation of the highly durable near-infrared absorbing compound of the present invention
The production method is, for example, a cationic group A ⁺Is the above equation (a)
In the case of a pyridinium group represented by the following general formula (2),
Phthalocyanine compound represented by the following general formula (3) and / or
Or 2-aminothiophenol derivative represented by (4)
After reacting the body or at least one of its analogs
A pyridine ring is introduced via a linking group D
By quaternizing the nitrogen atom of

[0045]

Embedded image Wherein Y is independently a hydrogen atom, a halogen atom, a nitro group, a hydroxyl group, an optionally substituted alkoxy group, an optionally substituted aryloxy group, an optionally substituted alkylthio group, Represents an optionally substituted arylthio group, an optionally substituted alkylamino group, or an optionally substituted arylamino group, which may be the same or different, r represents an integer of 4 to 16, and M represents 2
Represents a valent metal atom or a trivalent or tetravalent substituted metal or oxymetal. ]

[0046]

Embedded image [Wherein, R _{1 to} R ₉ are the same as described above]

Among the phthalocyanine compounds represented by the general formula (2), particularly preferred compounds are C.I. I. Pigment Green 7 (trade name: Phthalocyanine Green), C.I. I. Pigment Green 36, C.I. I. Pigment Green 37 or C.I. I. Pigment Green 38, which is a commercially available halogenated phthalocyanine compound.

The phthalocyanine compound represented by the general formula (2) and the 2-phthalocyanine compound represented by the general formulas (3) and / or (4)
The reaction with the aminothiophenol derivative or its analog can be carried out in the presence of a base such as sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium hydride, potassium t-butoxide and the like. Alternatively, those obtained by isolating formulas (3) and / or (4) as sodium salt, potassium salt, and zinc salt can also be used.

Solvents used in the reaction include dimethylformamide (DMF), dimethylsulfoxide (DMS)
O), N, N'-dimethylimidazolidinone (DM
I), polar solvents such as sulfolane, ketone solvents such as acetone and methyl ethyl ketone, and aromatic hydrocarbon solvents such as toluene, xylene, monochlorobenzene and dichlorobenzene.

The reaction is usually carried out by adding a phthalocyanine compound represented by the general formula (2) and a base (4 to 100 times equivalent to the phthalocyanine compound) to a solvent (1 to 1000 times by weight to the phthalocyanine compound). The 2-aminothiophenol derivative represented by the general formula (3) and / or (4) or an analog thereof (4 to 4 with respect to the phthalocyanine compound) is dissolved or suspended and stirred.
(30 equivalents) and react at 50-220 ° C.
The addition of the 2-aminothiophenol derivative or an analog thereof may be performed before the temperature rise, during the temperature rise, or after the temperature rise. Further, they may be added at once, or may be added in portions. Further, the phthalocyanine compound may be added after the base is added using the 2-aminothiophenol derivative itself as a solvent. One or two or more kinds of 2-aminothiophenol derivatives may be used. A nucleophilic reagent other than 2-aminothiophenol derivatives such as thiols and alcohols or analogs thereof can also be added at the same time. The reaction is
The reaction may be carried out under normal pressure or under pressure, and a quaternary ammonium salt, crown ether or the like may be added as a reaction accelerator.

The degree of progress of the reaction is, for example, determined by
Can be determined by measuring. By the above reaction, a phthalocyanine compound reacted with a 2-aminothiophenol derivative represented by the following general formula (5) is obtained.

[0052]

Embedded image [Wherein, X, R _{1 to} R ₉ , l, m, and n have the same meaning as described above. ]

After the completion of the reaction, the general formula (a) can be introduced, for example, by adding an amidating reagent or an alkylating agent to the reaction mixture and reacting the 2-aminothiophenol derivative with the phthalocyanine compound (5). , Or after isolating the phthalocyanine compound (5) once reacted with the intermediate 2-aminothiophenol derivative, and adding the above reagent to carry out the reaction.

For example, as an amidating reagent used in the reaction, an acid having a pyridine ring substituted by (R ₁₁ ) _j , wherein the nitrogen atom of the pyridine ring can be quaternized, or an acid halide thereof (for example, Nicotinic acid chloride, isonicotinic acid chloride, methyl nicotinic acid chloride, methoxynicotinic acid chloride, chloronicotinic acid chloride, and the like, but not limited thereto.) (To the phthalocyanine compound (5)). 1
After the reaction is completed, the phthalocyanine compound (6) is obtained by discharging the mixture into water or an alcohol solution such as methanol, ethanol, propanol, butanol and pentanol.

[0055]

Embedded image [Wherein, X, R _{1 to} R ₉ , D, R ₁₁ , j, l, m, and n have the same meaning as described above. ]

The reaction with the amidation reagent is carried out according to a conventional method in a pyridine solvent or in the presence of a tertiary amine such as triethylamine in a solvent such as toluene, xylene or methylene chloride. The reagent (1 to 100 equivalents based on the phthalocyanine compound (5)) can be reacted at 0 to 150 ° C. for 1 to 20 hours. At this time, a reaction accelerator such as dimethylaminopyridine may be added.

Further, as a method for producing the near-infrared absorbing compound (1) of the present invention, a cationic group A ⁺ and its counter anion B ⁻ can be obtained by utilizing a conventional quaternization reaction of a nitrogen atom. For example, halogenoalkyl represented by R ₁₀ X ′ (R ₁₀ is the same as above and X ′ represents a halogen atom), dialkyl sulfates such as dimethyl sulfate, diethyl sulfate and the like, R ₁₀ -OTs (R ₁₀ is And Ts represents a tosyl group) to form a cationic group A ⁺ and its counter anion B ⁻ .

The quaternization reaction using the cationic group A ⁺ and its counter anion B ⁻ is carried out according to a conventional method, for example, in a solvent with the phthalocyanine compound (6) and the above-mentioned quaternization additive (phthalocyanine compound ( 6) to 1 to 100 times equivalent) at 0 to 150 ° C. for 1 to 20 hours.

Solvents used in the reaction include dimethylformamide (DMF), dimethylsulfoxide (DMS)
O), N, N'-dimethylimidazolidinone (DM
I), polar solvents such as sulfolane, ketone solvents such as acetone and methyl ethyl ketone, and aromatic hydrocarbon solvents such as toluene, xylene, monochlorobenzene and dichlorobenzene.

Furthermore, the obtained near-infrared absorbing compound of the present invention can be purified by column chromatography or the like, if necessary.

On the other hand, the method of introducing the general formula (b) or (c) is described in, for example, the above-mentioned phthalocyanine compound (5) obtained by reacting a 2-aminothiophenol derivative by adding an amidating reagent or an alkylating agent to a reaction mixture. ), Or after isolating the phthalocyanine compound (5) once reacted with the intermediate 2-aminothiophenol derivative, and then adding the reagent to carry out the reaction. .

For example, as an amidating reagent or an alkylating agent used in the reaction, a carboxylic acid or a carboxylic acid halide thereof (for example, chloroacetyl chloride,
Examples include, but are not limited to, chloroethylcarbonyl chloride, chloropropylcarbonyl chloride, chlorobutylcarbonyl chloride, and the like. ) Or a compound of the formula W-Alk-W (W
Represents a halogen atom, OTs (Ts = tosyl group), Alk
Represents an alkylene group having 1 to 10 carbon atoms, for example, dichloroethane, dibromopropane, dibromobutane, chloroethyl tosylate, ethylene glycol ditosylate, propanediol ditosylate, pentanediol ditosylate, and the like, It is not limited to these. ) Is added (1 to 100 times equivalent to phthalocyanine compound (5)) and reacted. After completion of the reaction, water or methanol, ethanol, propanol, butanol, pentanol or the like is usually added. By discharging into alcohol solvent,
A phthalocyanine compound (7) is obtained.

[0063]

Embedded image [In the formula, X, R _{1 to} R ₉ have the same meaning as described above, E represents the D ′ or D ″, and Q represents a halogen atom or an OTs group.]

The reaction with an amidating reagent or an alkylating agent represented by the formula W-Alk-W is performed by using dimethylformamide (DMF), dimethylsulfoxide (DMSO),
In polar solvents such as N, N'-dimethylimidazolidinone (DMI) and sulfolane, ketone solvents such as acetone and methyl ethyl ketone, aromatic hydrocarbon solvents such as toluene, xylene, monochlorobenzene and dichlorobenzene, and solvents such as methylene chloride With the phthalocyanine compound (5) and the above-mentioned amidating reagent or an alkylating agent represented by the formula W-Alk-W (1 to 1 with respect to the phthalocyanine compound (5))
(100 equivalents) with 0 to 150 ° C. for 1 to 20 hours to obtain the phthalocyanine compound (7). On this occasion,
A reaction accelerator such as dimethylaminopyridine may be added.

Further, the near-infrared absorbing compound of the present invention
As a method for producing (1), a conventional method of quaternizing a nitrogen atom is used.
By utilizing the reaction, the cationic group A⁺And its ani
On B^-Is obtained as For example, phthalocyanine compounds
Object (7) and (R₁₂)_kSubstituted pyridines
(R₁₂, K is the same as above), R₁₃~ R_FifteenReplaced by
Mins (R ₁₃~ R_FifteenIs the same as above)
Can be quaternized.

The quaternization reaction using the cationic group A ⁺ and its counter anion B ⁻ is carried out according to a conventional method, for example, in a solvent with the phthalocyanine compound (7) and the above-mentioned quaternization additive (phthalocyanine compound ( 7) is reacted at 0 to 150 ° C. for 1 to 20 hours.

Solvents used in the reaction include dimethylformamide (DMF), dimethylsulfoxide (DMS)
O), N, N'-dimethylimidazolidinone (DM
I), polar solvents such as sulfolane, ketone solvents such as acetone and methyl ethyl ketone, and aromatic hydrocarbon solvents such as toluene, xylene, monochlorobenzene and dichlorobenzene.

Further, the obtained near-infrared absorbing compound of the present invention can be purified by column chromatography or the like, if necessary.

The near-infrared absorbing compound of the present invention is a compound having absorption at a long wavelength, high light fastness, and particularly a high solubility type in water, alcohols and the like. Further, in the production method, an inexpensive pigment can be used as a starting material, and the reaction is simple. Furthermore,
The product obtained by the method of the present invention is not a single compound,
Because it is obtained as a mixture of several types, the absorption wavelength becomes relatively broad, and because it absorbs a wide range of near-infrared rays,
It is easy to apply to near-infrared absorbing water-based paints, near-infrared absorbing materials, etc., and is an excellent compound for near-infrared absorbing materials.

The method for producing a near-infrared absorbing material using the above-mentioned near-infrared absorbing compound is not particularly limited. For example, the following three methods can be used. (1) A method in which a paint containing a near-infrared absorbing compound is prepared and coated on a transparent resin plate, a transparent film, or a transparent glass plate. (2) A method of kneading a resin with a near-infrared absorbing compound and heat molding to produce a resin plate or film. (3) A method of producing a laminated resin plate, a laminated resin film, a laminated glass, and the like by incorporating a near-infrared absorbing compound into an adhesive.

First, after forming a paint, coating (1)
In the method, a method for preparing a water-based paint in which the near-infrared absorbing compound of the present invention is dissolved or dispersed in a water-based emulsion, a method for dissolving in a binder resin and an organic solvent to form a paint, or a method for forming a binder. There is a method in which a near-infrared absorbing dye is chemically bonded to a structural unit of a resin to form an aqueous emulsion paint or a solvent-based paint.

Usually, a water-based emulsion is prepared by dissolving a near-infrared absorbing compound in an aqueous emulsion such as an acrylic resin-based emulsion, a urethane resin-based emulsion, or an aqueous polyester resin-based emulsion, or by dispersing a finely pulverized (50 to 500 nm) emulsion. An emulsion paint is obtained. A water-based emulsion paint can be obtained by a conventional emulsion production method by chemically bonding a near-infrared absorbing dye to an acrylic resin or a urethane-based resin constituting the emulsion.

The water-based emulsion paint can be used as a modified product by blending with another water-soluble resin or by reacting with another component. further,
It can also be used as a hybrid obtained by polymerizing at least one monomer such as acrylic acid, acrylic acid ester, methacrylic acid, methacrylic acid ester, acrylamide, methacrylamide, styrene, acrylonitrile, and vinyl acetate in the resin.

Further, as other water-based paints, water-based acrylic resin paints, water-based urethane resin paints, and the like described in “Latest technology of water-based coating (CMC)”, “Technical trend of water-based paints (Nippon Paint Shimbun)” Examples include aqueous polyester resin paints, but are not limited thereto.

In addition, aliphatic ester resins, acrylic resins, melamine resins, urethane resins, aromatic ester resins, polycarbonate resins, aliphatic polyolefin resins, aromatic polyolefin resins, polyvinyl resins,
Polyvinyl alcohol resin, polyvinyl modified resin (P
VB, EVA, etc.) or their copolymer resins can be used as the binder. As the solvent, a solvent such as an alcohol-based, ketone-based, ester-based, aliphatic hydrocarbon-based, aromatic hydrocarbon-based, ether-based, halogen-based, or a mixture thereof can be used. In such a case, a water-soluble organic solvent that is mixed without being separated from water is preferable, and alcohols such as methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, and 2-butanol, etc., ethylene glycol, diethylene glycol, and triethylene glycol , Polyethylene glycol, propylene glycol, polypropylene glycol, 1,3-propanediol, glycerin,
Polyhydric alcohols such as thioglycol, polyhydric alcohol ethers such as ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, diethylene glycol monobutyl ether, dipropylene glycol monoethyl ether, and triethylene glycol monomethyl ether; ketones such as acetone and methyl ethyl ketone Amides such as N, N-dimethylformamide, N, N-diethylformamide, N, N-dimethylacetamide, 2-pyrrolidone, N-methyl-2-pyrrolidone, N-vinyl-2-pyrrolidone, 1,3 -Dimethyl-
Examples include nitrogen-containing compounds such as 2-imidazolidinone, and ethers such as tetrahydrofuran and dioxane. These water-soluble organic solvents may be used alone or in combination of two or more.

In the preparation of a paint, the concentration of the near-infrared absorbing compound varies depending on the thickness of the coating, the desired absorption intensity, the desired near-infrared transmittance, the desired visible transmittance, and the like. 001 to 100%. The resin concentration is usually 1 to 50% based on the whole paint.
It is.

Additives such as an ultraviolet absorber, a light stabilizer and an antioxidant which are usually used in paints may be added to the paints. The paint prepared by the above method is coated on a transparent resin film, a transparent resin, a transparent glass, or the like with a bar coater, a blade coater, a spin coater, a reverse coater, a die coater, or a spray to produce a near-infrared absorbing material. . 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 (2) of kneading a resin with a near-infrared absorbing compound and heat molding, the resin material is preferably as transparent as possible when formed into a resin plate or a resin film. Polystyrene, polyacrylic acid, polyacrylate,
Polyvinyl acetate, polyacrylonitrile, polyvinyl chloride, addition polymer of vinyl resin such as polyvinyl fluoride and vinyl compound, polymethacrylic acid, polymethacrylic acid ester, polyvinylidene chloride, polyvinylidene fluoride,
Vinylidene cyanide, vinylidene fluoride / trifluoroethylene copolymer, vinylidene fluoride / tetrafluoroethylene copolymer, vinylidene cyanide / vinyl acetate copolymer, or other vinyl compound or fluorine compound copolymer, polytriene Fluorine-containing resins such as fluoroethylene, polytetrafluoroethylene, and polyhexafluoropropylene; polyamides such as nylon 6 and nylon 66;
Polyimide, polyurethane, polypeptide, polyester such as polyethylene terephthalate, polycarbonate, polyoxymethylene, polyethylene oxide, polyether such as polypropylene oxide, epoxy resin,
Examples thereof include 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 near-infrared absorbing compound is usually added to powder or pellets of the base resin, and the mixture is heated to 150 to 350 ° C. and dissolved. After forming, or extruded, thickness 0.1 ~ 100mm
Or a film is formed by an extruder, or a raw material is prepared by an extruder and stretched uniaxially or biaxially at 30 to 120 ° C. by 2 to 5 times to 10 Obtained by a method of forming a film having a thickness of 200 μm. The near-infrared absorbing material of the present invention can also be produced by casting a near-infrared absorbing compound of a resin monomer such as an acrylic resin or a prepolymer of the resin monomer in the presence of a polymerization initiator. When kneading, additives such as an ultraviolet absorber and a plasticizer used for ordinary resin molding may be added. The amount of the near-infrared absorbing compound to be added varies depending on the thickness of the product to be produced, the desired absorption intensity, the desired near-infrared transmittance, the desired visible transmittance, and the like.
%.

In the method of (3) in which a near-infrared absorbing compound is contained in an adhesive to produce a laminated resin plate, a laminated resin film, a laminated glass, and the like, the adhesive may be a common silicone, urethane, or the like. Polyvinyl butyral adhesive (PVB), ethylene-vinyl acetate adhesive (EV) for acrylic resin or laminated glass
Known transparent adhesives for laminated glass such as A) can be used. Resin plates, resin plate and resin film, resin plate and glass, resin films, resin film and glass, using an adhesive containing 0.1-50% of a near-infrared absorbing compound.
Glass is bonded to each other to produce a near infrared absorbing material. There is also a method of thermocompression bonding.

[0081]

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 I. Pigment Green 7 (10.0 g), 2-
(N-octylamino) thiophenol (19.0 g,
9 equivalents), 2-aminothiophenol (5.6 g, 5
Double equivalent), potassium carbonate (39.2 g, 32 equivalents)
At 120 ° C. in dimethylformamide (200 ml).
For 10 hours. After cooling to room temperature, the reaction mixture was discharged into methanol (500 ml). The precipitate was collected by suction filtration, washed with methanol, washed with water, and dried to isolate a phthalocyanine compound (25.6 g).
The phthalocyanine compound (10 g) was added to pyridine (100
g) In a solvent, after adding nicotinic acid chloride (12 g),
The reaction was performed at 90 ° C. for 3 hours. The reaction mixture was discharged into methanol (200g). The precipitate is collected by suction filtration, washed with water and methanol, dried, and dried according to the following formula (A).
Of a phthalocyanine compound (9.6 g) was obtained.

[0083]

Embedded image

Further, the phthalocyanine compound of the formula (A) (7.5 g) was reacted in an o-dichlorobenzene (75 ml) solvent at 50 ° C. for 2 hours after adding dimethyl sulfate (3.6 g). After cooling to room temperature, the reaction mixture was discharged into acetone (100 g). The precipitate was collected by suction filtration, washed with acetone and dried to obtain a near-infrared absorbing mixture (10.4 g) containing a compound of the following formula (B).

[0085]

Embedded image

The mixture was well soluble in solvents such as water, methanol and ethylene glycol, and had a λmax of 886 nm (in a methanol solvent).

Example 2 The phthalocyanine compound of the formula (A) obtained in Example 1 (5
g) was added to methyl iodide (2.2 g) in a solvent of o-dichlorobenzene (100 g) and reacted at 80 ° C. for 2 hours. After cooling the reaction mixture to room temperature, acetone (200
g). The precipitate was collected by suction filtration, washed with acetone, and dried to obtain a near-infrared absorbing mixture (5.5 g) containing the compound of the following formula (C).

[0088]

Embedded image

The mixture was well soluble in solvents such as water, methanol and ethylene glycol, and had a λmax of 894 nm (in a methanol solvent).

Example 3 The phthalocyanine compound (5) of the formula (A) obtained in Example 1
g) in o-dichlorobenzene (100 g) solvent was added with methyl tosylate (4.7 g) and reacted at 80 ° C. for 2 hours. After the reaction mixture was cooled to room temperature, acetone (2
00g). The precipitate was collected by suction filtration, washed with acetone, and dried to obtain a near-infrared absorbing mixture (7.0 g) containing a compound of the following formula (D).

[0091]

Embedded image

The mixture was well soluble in solvents such as water, methanol and ethylene glycol, and had a λmax of 890 nm (in a methanol solvent).

Embodiment 4 C.I. I. Pigment Green 7 (10.0 g), 2-
(N-octylamino) thiophenol (19.0 g,
9 equivalents), 2-aminothiophenol (5.6 g, 5
Double equivalent), potassium carbonate (39.2 g, 32 equivalents)
At 120 ° C. in dimethylformamide (200 ml).
For 10 hours. After cooling to room temperature, the reaction mixture was discharged into methanol (500 ml). The precipitate was collected by suction filtration, washed with methanol, washed with water, and dried to isolate a phthalocyanine compound (25.6 g).
The phthalocyanine compound (10 g) was added to pyridine (100
g) After adding chloroacetyl chloride (12 g) in a solvent, the mixture was reacted at 90 ° C. for 3 hours. The reaction mixture was discharged into methanol (200g). The precipitate was collected by suction filtration, washed with water and methanol, and then dried to obtain a phthalocyanine compound of the following formula (E) (9.6 g).

[0094]

Embedded image

Further, the phthalocyanine compound of the formula (E) (7.5 g) was added with pyridine (3.6 g) in a solvent of o-dichlorobenzene (75 ml) and reacted at 50 ° C. for 2 hours. After the reaction mixture was cooled to room temperature, acetone (1
00g). The precipitate was collected by suction filtration, washed with acetone and dried to obtain a near-infrared absorbing mixture (10.4 g) containing the compound of the following formula (F).

[0096]

Embedded image

The mixture was well soluble in solvents such as water, methanol and ethylene glycol, and had a λmax of 886 nm (in a methanol solvent).

Example 5 The phthalocyanine compound of the formula (E) obtained in Example 4 (5
g) was added to triethanolamine (4.7 g) in a solvent of o-dichlorobenzene (100 g) and reacted at 80 ° C. for 2 hours. After cooling to room temperature, the reaction mixture was discharged into acetone (200 g). The precipitate was collected by suction filtration, washed with acetone, and dried to obtain a near-infrared absorbing mixture (7.0 g) containing a compound of the following formula (G).

[0099]

Embedded image

The mixture was well soluble in solvents such as water, methanol and ethylene glycol, and had a λmax of 890 nm (in a methanol solvent).

Embodiment 6 C.I. I. Pigment Green 38 (10.0 g), 2
Aminothiophenol (40.0 g, 319 mmol
l), 2- [3- (1-piperidyl) propyl] aminothiophenol (35.5 g, 141.8 mmol), potassium carbonate (39.2 g, 284 mmol) were added to N,
In N'-dimethylimidazolidinone (200 ml), 1
The reaction was performed at 20 ° C. for 3 hours. After cooling the reaction mixture to room temperature, it was discharged into methanol (500 ml). The precipitate is collected by suction filtration, washed with methanol, washed with water, and dried, and then dried with a phthalocyanine compound of the following formula (H) (23.2).
g) was obtained.

[0102]

Embedded image

Further, a phthalocyanine compound of the formula (H) (7.5 g) was added to dimethylsulfuric acid (3.6 g) in a solvent of o-dichlorobenzene (75 ml) and reacted at 50 ° C. for 2 hours. After cooling to room temperature, the reaction mixture was discharged into acetone (100 g). The precipitate was collected by suction filtration, washed with acetone, and dried to obtain a near-infrared absorbing mixture (10.4 g) containing the compound of the following formula (I).

[0104]

Embedded image

The mixture was well soluble in solvents such as water, methanol and ethylene glycol, and had a λmax of 890 nm (in a methanol solvent).

Example 7 A phthalocyanine compound (7.7) represented by the following formula (J)
g, 8.88 mmol), 2-aminothiophenol (16.7 g, 133 mmol, 15 equivalents), potassium carbonate (39.2 g, 284 mmol, 32 equivalents)
At 120 ° C. in dimethylformamide (200 ml).
And reacted for 5 hours. After cooling the reaction mixture to room temperature, it was discharged into methanol (500 ml). The precipitate was collected by suction filtration, washed with methanol, washed with water, and dried to isolate a phthalocyanine compound (15.6 g). The phthalocyanine compound (10 g) was treated with 4-dimethylaminopyridine (1.0 g, 8.19 mmol) in pyridine (10 g).
0 g) After adding chloroacetyl chloride (12 g) in a solvent, the mixture was reacted at 90 ° C. for 3 hours. The reaction mixture was discharged into methanol (200g). The precipitate was collected by suction filtration, washed with water and methanol, and then dried to obtain a phthalocyanine compound of the following formula (K) (9.6 g).

[0107]

Embedded image

[0108]

Embedded image

Further, the phthalocyanine compound of the formula (K) (7.5 g) was added with pyridine (3.6 g) in a solvent of o-dichlorobenzene (75 ml) and reacted at 50 ° C. for 2 hours. After the reaction mixture was cooled to room temperature, acetone (1
00g). The precipitate was collected by suction filtration, washed with acetone, and dried to obtain a near-infrared absorbing mixture (10.4 g) containing a compound of the following formula (L).

[0110]

Embedded image

The mixture was well soluble in solvents such as water, methanol and ethylene glycol, and had a λmax of 950 nm (in a methanol solvent).

Example 8 A near-infrared absorbing mixture (0.05 g) of the formula (B) synthesized in Example 1 was applied to an emulsion paint “ALMATEX E
470 "(trade name, manufactured by Mitsui Toatsu Chemicals, Inc.). To this, 0.3 g of an ultraviolet absorber "Tinuvin 1130" (trade name, manufactured by Ciba Geigy) and 0.1 g of a light stabilizer "Sanol LS765" (trade name, manufactured by Sankyo) were dissolved in 1 g of butyl cellosolve. The solution was added to produce a near infrared absorbing paint. The coating was coated on glass with a bar coater to provide an excellent near-infrared absorbing material that well absorbs light of 700 to 1100 nm. JIS
According to -R-3106, Tv (visible light transmittance) and Te (solar transmittance) were measured with a spectrophotometer UV-3100 manufactured by Shimadzu Corporation, and found to be 51% and 39%, respectively.
Met. In addition, a 1000-hour carbon arc lamp (6
(3 ° C.), a light fastness test was carried out, but no decrease in absorption due to decomposition of the dye was observed, and the light fastness was good.

Example 9 A near-infrared absorbing mixture (0.05 g) of the formula (B) synthesized in Example 1 was applied to an acrylic emulsion paint "E-4".
622 "(trade name, manufactured by Daido Kasei Co., Ltd.). To this, 0.3 g of an ultraviolet absorber "Tinuvin 1130" (trade name, manufactured by Ciba Geigy) and 0.1 g of a light stabilizer "Sanol LS765" (trade name, manufactured by Sankyo) were dissolved in 1 g of butyl cellosolve. The solution was added to produce a near infrared absorbing paint. The coating was coated on glass with a bar coater to provide an excellent near-infrared absorbing material that well absorbs light of 700 to 1100 nm. Also,
When Tv and Te were measured, they were 50% and 37%, respectively.
%Met. Further, as a result of the light resistance test, the light resistance was good.

Example 10 The near-infrared absorbing mixture (0.05 g) of the formula (B) synthesized in Example 1 was mixed with an aqueous urethane resin "Olester UD1".
01N "(trade name, manufactured by Mitsui Toatsu Chemicals, Inc.). To this, 0.3 g of an ultraviolet absorber "Tinuvin 1130" (trade name, manufactured by Ciba Geigy) and 0.1 g of a light stabilizer "Sanol LS765" (trade name, manufactured by Sankyo) were dissolved in 1 g of butyl cellosolve. The solution was added to produce a near infrared absorbing paint. The coating was coated on glass with a bar coater to provide an excellent near-infrared absorbing material that well absorbs light of 700 to 1100 nm. Also,
When Tv and Te were measured, they were 55% and 42%, respectively.
%Met. Further, as a result of the light resistance test, the light resistance was good.

Example 11 In the same manner as in Example 9, except that the near-infrared absorbing mixture (0.05 g) of the formula (C) synthesized in Example 2 was used instead of the formula (B), Was prepared. The paint is coated on the glass with a bar coater.
It became an excellent near-infrared absorbing material that well absorbs light of 00 to 1100 nm. When Tv and Te were measured, they were 55% and 44%, respectively. Further, as a result of the light resistance test, the light resistance was good.

Example 12 In the same manner as in Example 9, except that the near infrared absorbing mixture (0.05 g) of the formula (D) synthesized in Example 3 was used instead of the formula (B), a near infrared absorbing coating was used. Was prepared. The paint is coated on the glass with a bar coater.
It became an excellent near-infrared absorbing material that well absorbs light of 00 to 1100 nm. When Tv and Te were measured, they were 50% and 39%, respectively. Further, as a result of the light resistance test, the light resistance was good.

Example 13 In the same manner as in Example 9, except that the near infrared absorbing mixture (0.05 g) of the formula (F) synthesized in Example 4 was used instead of the formula (B), the near infrared absorbing coating was used. Was prepared. The paint is coated on the glass with a bar coater.
It became an excellent near-infrared absorbing material that well absorbs light of 00 to 1100 nm. When Tv and Te were measured, they were 49% and 37%, respectively. Further, as a result of the light resistance test, the light resistance was good.

Example 14 In the same manner as in Example 9 except that the near-infrared absorbing mixture (0.05 g) of the formula (G) synthesized in Example 5 was used instead of the formula (B), Was prepared. The paint is coated on the glass with a bar coater.
It became an excellent near-infrared absorbing material that well absorbs light of 00 to 1100 nm. When Tv and Te were measured, they were 52% and 41%, respectively. Further, as a result of the light resistance test, the light resistance was good.

Example 15 In the same manner as in Example 9 except that the near-infrared absorbing mixture (0.05 g) of the formula (I) synthesized in Example 6 was used instead of the formula (B), Was prepared. The paint is coated on the glass with a bar coater.
It became an excellent near-infrared absorbing material that well absorbs light of 00 to 1100 nm. When Tv and Te were measured, they were 53% and 45%, respectively. Further, as a result of the light resistance test, the light resistance was good.

Example 16 In the same manner as in Example 9, except that the near infrared absorbing mixture (0.05 g) of the formula (L) synthesized in Example 7 was used instead of the formula (B), the near infrared absorbing paint was used. Was prepared. The paint is coated on the glass with a bar coater.
It became an excellent near-infrared absorbing material that well absorbs light of 00 to 1100 nm. When Tv and Te were measured, they were 50% and 39%, respectively. Further, as a result of the light resistance test, the light resistance was good.

Example 17 The near-infrared absorbing compound of the formula (B) synthesized in Example 1 was used as a polyethylene terephthalate pellet 120 manufactured by Unitika.
3 and a weight ratio of 0.03: 1.
After melt-kneading at 0 ° C., a film having a thickness of 0.1 mm was prepared using an extruder, and then this film was biaxially stretched to prepare a near-infrared absorbing film having a thickness of 25 μm. The film was an excellent near-infrared absorbing material that well absorbs light of 700 to 1100 nm. Also, T
When v and Te were measured, they were 56% and 45%, respectively.
Met. Further, as a result of the light resistance test, the light resistance was good.

Example 18 5 parts of the near-infrared absorbing compound of the formula (B) synthesized in Example 1 and 100,000 parts of polymethyl methacrylate were added to 28
The mixture was melt-kneaded at 0 ° C., and a near-infrared absorbing plate having a thickness of 2.5 mm and a width of 1 m was produced using an extruder. The plate was an excellent near-infrared absorbing material that well absorbs light of 700 to 1100 nm. When Tv and Te were measured, they were 55% and 44%, respectively. Further, as a result of the light resistance test, the light resistance was good.

Examples 19 to 22 Each of the near-infrared absorbing compounds shown in the table was synthesized by the same synthesis method as described in the above examples. As a result, all the near-infrared absorbing compounds were dissolved in water, alcohols such as methanol, or glycols such as diethylene glycol. Those showing solubility were indicated by “○”. Further, a near-infrared absorbing material was produced by the method described in Example 10, and Tv and Te were measured. The produced near-infrared absorbing material sufficiently absorbed light in the near-infrared region. No deterioration was observed in the light resistance test, and the light resistance was good.

[0124]

[Table 1]

[0125]

[Table 2]

[0126]

According to the present invention, a phthalocyanine-based near-infrared absorbing compound having high light resistance and having high solubility in water and alcohols can be provided by a simple production method. Is extremely valuable in practice.

 ──────────────────────────────────────────────────続 き Continued on the front page (72) Inventor Kazuhiro Seino 1190 Kasama-cho, Sakae-ku, Yokohama-shi, Kanagawa Prefecture Within Mitsui Chemicals Co., Ltd. (72) Inventor Ryu 1190 Kasama-cho, Sakae-ku, Yokohama-shi, Kanagawa Prefecture Mitsui Chemicals F Term (reference) 4H056 FA05 JA10 JB04 JE04

Claims (6)

[Claims] 1. A cationic group A ⁺ and its counter anion B ⁻
A near-infrared absorbing compound represented by the general formula (1), comprising at least one ion pair group G consisting of: Embedded image Wherein X is independently a hydrogen atom, a halogen atom, a hydroxyl group, an optionally substituted alkoxy group, an optionally substituted aryloxy group, an optionally substituted alkylthio group, or an optionally substituted X represents a good arylthio group, an optionally substituted alkylamino group, or an optionally substituted arylamino group, and adjacent Xs may form a 5- or 6-membered ring through two heteroatoms; _{1 to} R ₉ are each independently a hydrogen atom, an alkyl group which may be substituted, an aryl group which may be substituted, an alkoxy group which may be substituted, an aryloxy group which may be substituted, Optionally substituted alkylsulfonyl group, optionally substituted arylsulfonyl group, optionally substituted alkylcarbonyl group, optionally substituted It represents an arylcarbonyl group, G _1,
G ₂ represents a hydrogen atom or the above-mentioned ion pair group G, which may be the same or different; at least one is the above-mentioned ion pair group G; l represents an integer of 1 to 8; N represents an integer of 0 to 14, n + 2l + m = 16, and M represents a divalent metal atom or a trivalent or tetravalent substituted metal or oxymetal. ] 2. The cationic group A ⁺ is a pyridinium group represented by the following formula (a) or (b) or an ammonium group represented by the following formula (c), the counter anion B ⁻ is a halogenium ion, The near-infrared absorbing compound according to claim 1, which is one selected from the group consisting of a sulfonium ion and a carboxyl ion. Embedded image (In the formulas (a), (b) and (c), R ₁₀ , R _{13 to} R ₁₅ are each independently a hydrogen atom, an optionally substituted alkyl group,
Represents an aryl group which may be substituted, R _{13 to} R ₁₅ may form a ring, and R ₁₁ and R ₁₂ each independently represent a halogen atom, an alkyl group, an alkoxy group, or an alkylthio group; k represents an integer of 0 to 4. In addition, adjacent R ₁₁
Together, they may form a ring with R ₁₂ to each other. D, D ', D "
Represents a linking group, and may be linked via no linking groups D, D ′, and D ″.) 3. The linking group D, D ′, D ″ is an alkylene group,
The near-infrared absorbing compound according to claim 2, which is a carbonylalkylene group. 4. In the general formula (1), X is each independently a hydrogen atom or a halogen atom, and R _{1 to} R ₉ are each independently a hydrogen atom or an optionally substituted alkyl group, A good alkylsulfonyl group, an optionally substituted arylsulfonyl group, an optionally substituted alkylcarbonyl group or an optionally substituted arylcarbonyl group, wherein 2l + m is 6 to 1
6. The near-infrared absorbing compound according to claim 1, wherein M is Cu, AlCl, TiO or VO. 5. A near-infrared absorbing resin composition containing the near-infrared absorbing compound according to any one of claims 1 to 4. 6. A near-infrared absorbing material containing the near-infrared absorbing compound according to any one of claims 1 to 4.