JPH08225752A - Near infrared ray-absorbing compound and its production - Google Patents

Abstract

PURPOSE: To obtain the subject compound having high light resistance by reacting phthalocyanine having eliminating group such as a halogen atom with an aminothiophenol derivative. CONSTITUTION: The objective compound is obtained by reacting (A) a phthalocyanine of formula I (X is independently a halogen, hydroxyl group, an alkoxy, an aryloxy or an alkylthio, etc., at least 4 pieces are halogen; n is an integer of 4-16; M is a divalent metal atom or 3-4 valent substituting metal or a metal oxide) with (B) at least one kind of 2-aminothiophenol derivative of formula II (R is H, an alkyl or an aryl, R is not simultaneously H in a reaction of plural formula II; Y is independently an alkyl, an aryl or an alkoxy, etc.; m is an integer of 0-4) in the presence of a base. For instance, a compound of formula III is obtained by using C.I. pigment green-7 as the component A and 2-(n-octylamino)thiophenol as the component B.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a simple method for producing a near-infrared absorbing compound having absorption in the near-infrared region and a near-infrared absorbing compound obtained by this method.

The near-infrared absorbing compound can be used in 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 possible to produce a near-infrared absorption filter by combining it with a binder resin to form a paint, coating it on plastic or glass, or kneading it with a resin.

Near-infrared absorption filters are used for buildings, cars,
As a window material for trains, ships, airplanes, etc., it can block heat rays from the outside and suppress the temperature rise inside the room and inside the vehicle.
Further, by cutting a specific wavelength region, it can be used as an agricultural film for selectively using light quality for controlling plant growth, cutting infrared rays of a semiconductor light receiving element, and eyeglasses for protecting human eyes from rays containing harmful infrared rays.

Among the above, the near-infrared absorption filter for the purpose of intercepting heat rays is a field of interest because it contributes to energy saving.

[0005]

2. Description of the Related Art PE is used as a window material for blocking heat rays.
A heat ray reflection filter is known in which metal oxides such as indium oxide and tin oxide and metals such as gold and silver are alternately laminated on a T film or glass, but with the drawback that the product cost is high due to the complicated manufacturing process. , It may cause radio interference. Compared with those inorganic type heat ray reflection filters, near infrared absorption filters using near infrared absorption dyes have a wide application field because they are easy to manufacture and do not have the problem of radio interference.
Market needs are also great. However, due to the problems of cost and durability (especially stability against light) of dyes, the current situation is that they have not spread.

As an organic dye that absorbs near infrared rays, a cyanine dye has been well known. However, since cyanine dyes have extremely low light fastness, there are many restrictions when using them. In addition, JP-A-3
The aminium salt type compounds described in JP-A-161644 or the metal complex compounds described in JP-B No. 54-25060 and JP-A No. 50-51549 are insufficient in heat resistance and light resistance. . Also, Japanese Patent Laid-Open No. 3-11
The anthraquinone-based compounds described in JP-A No. 5362 and JP-A No. 62-903 are also heat resistant but insufficient in light resistance.

As a near-infrared absorbing dye having high durability, JP-B-59-1311 and JP-A-60-209 are available.
583, Japanese Patent Publication No. 2-5155, JP-A-61
The phthalocyanines described in JP-A-152685, JP-A-61-223056, JP-A-3-62878 and the like have complicated production processes and have a λ _max of at most 800 n.
Since it was as short as m, it was insufficient for the purpose of absorbing heat rays.

In Japanese Patent Publication No. 4-75916, a dye having a λ _max of 909 nm is obtained by reacting chlorinated copper phthalocyanine with 2-aminothiophenol in the examples. Λ _max at this time is pyridine. Data measured by coating on glass,
Alternatively, there is no data on extinction coefficient. Since the compound has a low solubility in an organic solvent or a resin, when it is dissolved in the resin for producing a near infrared absorption filter, a clouding phenomenon occurs, and a transparent resin plate or film cannot be obtained. The claim also discloses a compound having a substituent having 1 to 4 carbon atoms, but a compound having 1 to 4 carbon atoms is not sufficient for suppressing the clouding phenomenon, and the manufacturing method thereof is not described.

Further, Japanese Patent Application Laid-Open No. 63-308073 discloses a method of reacting coexisting 2-aminothiophenol and 4-methylphenylthiol in order to increase the solubility of phthalocyanine. _max is 8
It is as short as 90 nm.

Further, in JP-A-63-270765, perchlorocopper phthalocyanine (trade name: phthalocyanine green) is reacted with 2-aminothiophenol, and then the nitrogen atom is alkylated with alkyl bromide,
A method for improving both solubility and absorption wavelength is disclosed.
However, as in the present invention, the nitrogen atom is first alkylated,
No method is described for reacting with a halogenated phthalocyanine after making 2-alkylaminothiophenol. That is, in the post-alkylation, the efficiency of the alkylation is poor, and the solubility of the product may not be sufficiently increased.

Further, a naphthalocyanine compound as disclosed in JP-A-60-23451 is known, but its manufacturing process is long, and it is an industrially expensive compound, which is not suitable for industrial use. Was enough.

[0012]

SUMMARY OF THE INVENTION An object of the present invention is to provide a highly soluble phthalocyanine-based near-infrared absorbing compound having high light resistance at low cost and easily.
Furthermore, λ _max effective as a heat ray absorption filter is 91
It is to provide a near-infrared absorbing dye having a wavelength of 0 nm or more.

[0013]

Means for Solving the Problems As a result of intensive studies to solve the above problems, the present inventors have found that a phthalocyanine having a leaving group such as a halogen atom is reacted with a 2-aminothiophenol derivative, They have found that the desired near-infrared absorbing compound can be easily produced, and have completed the present invention.

That is, in the present invention, the phthalocyanine represented by the general formula (1) and at least one 2-aminothiophenol derivative represented by the general formula (2) are reacted in the presence of a base. The present invention relates to a method for producing an infrared absorbing compound, a near infrared absorbing compound produced by this method, and a near infrared absorbing compound obtained by further reacting this near infrared absorbing compound with an alkyl halide. . Furthermore, it relates to a near-infrared absorbing resin composition containing such a near-infrared absorbing compound and a heat ray absorbing filter.

[0015]

Embedded image [In the formula (1), X is independently a halogen atom, a hydroxyl group,
Substituted or unsubstituted alkoxy group, substituted or unsubstituted aryloxy group, substituted or unsubstituted alkylthio group, substituted or unsubstituted arylthio group, substituted or unsubstituted alkylamino group, substituted or unsubstituted arylamino group Represents a substituted or unsubstituted alkylarylamino group, and adjacent Xs may form a 5-membered ring or a 6-membered ring through two hetero atoms, n represents an integer of 4 to 16, and M represents a divalent group. Represents a metal atom of or a trivalent or tetravalent substituted metal or oxymetal. However, at least four of X are halogen atoms. ]

[0016]

[Chemical 4] [In Formula (2), R represents a hydrogen atom, a substituted or unsubstituted alkyl group, or a substituted or unsubstituted aryl group, and Y is independently a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group. Represents a group, a substituted or unsubstituted alkoxy group, or a substituted or unsubstituted aryloxy group, and m represents an integer of 0 to 4. However, when several kinds of formula (2) are reacted, R in all formula (2) does not simultaneously become a hydrogen atom.]

[0017]

BEST MODE FOR CARRYING OUT THE INVENTION The present invention provides a highly soluble phthalocyanine-based near-infrared absorbing compound having high light resistance by a simple method.

In the phthalocyanine represented by the general formula (1) used in the present invention, the halogen atom represented by X includes fluorine, chlorine, bromine and iodine. The substituted or unsubstituted alkoxy group is not particularly limited, and examples thereof include a methoxy group, an ethoxy group, an n-propoxy group, an iso-propoxy group, an n-butoxy group,
iso-butoxy group, sec-butoxy group, n-pentoxy group, iso-pentoxy group, n-hexyloxy group, cyclohexyloxy group, n-heptyloxy group,
n-octyloxy group, 2-ethylhexyloxy group,
Examples thereof include n-nonyloxy group, methoxyethoxy group, ethoxyethoxy group, ethoxyethoxyethoxy group, hydroxyethoxyethoxy group, diethylaminoethoxy group and benzyloxy group.

The substituted or unsubstituted aryloxy group is not particularly limited, and examples thereof include a phenoxy group, a 2-methylphenoxy group, a 3-methylphenoxy group, a 4-methylphenoxy group and a naphthoxy group. To be

The substituted or unsubstituted alkylthio group is not particularly limited, and examples thereof include methylthio group, ethylthio group, n-propylthio group, 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 group, cyclohexylthio group, n-heptylthio group, 2-ethylhexylthio group, n-octylthio group, n-nonylthio group, methoxymethylthio group, methoxyethylthio group, ethoxyethylthio group, propoxyethylthio group, butoxyethylthio group. Group, γ-methoxypropylthio group, γ-ethoxypropylthio group, methoxyethoxyethylthio group, ethoxyethoxyethylthio group,
Alkoxyalkylthio group such as dimethoxymethylthio group, diethoxymethylthio group, dimethoxyethylthio group, diethoxyethylthio group, alkoxyalkoxyalkylthio group, alkoxyalkoxyalkoxyalkylthio group, chloromethylthio group, dimethylaminoethylcythio group, diethylaminoethylthio group Examples thereof include an alkylaminoalkylthio group such as a group, a dialkylaminoalkylthio group, and the like.

The substituted or unsubstituted arylthio group is not particularly limited, and examples thereof include a phenylthio group, a naphthylthio group, a 4-methylphenylthio group and a 4-methylphenylthio group.
Ethylphenylthio group, 4-propylphenylthio group,
4-t-butylphenylthio group, 4-methoxyphenylthio group, 4-ethoxyphenylthio group, 4-aminophenylthio group, 4-alkylaminophenylthio group, 4-
Dialkylaminophenylthio group, 4-phenylaminophenylthio group, 4-diphenylaminophenylthio group, 4-hydroxyphenylthio group, 4-chlorophenylthio group, 4-bromophenylthio group, 2-methylphenylthio group, 2 -Ethylphenylthio group, 2-propylphenylthio group, 2-t-butylphenylthio group, 2-
Methoxyphenylthio group, 2-ethoxyphenylthio group, 2-aminophenylthio group, 2-alkylaminophenylthio group, 2-dialkylaminophenylthio group,
2-phenylaminophenylthio group, 2-diphenylaminophenylthio group, 2-hydroxyphenylthio group,
Examples thereof include a 2-chlorophenylthio group and a 2-bromophenylthio group.

The substituted or unsubstituted alkylamino group is not particularly limited, and examples thereof include a methylamino group, an ethylamino group, an n-propylamino group and is.
Examples thereof include o-propylamino group, butylamino group, pentylamino group, dipentylamino group, hexylamino group, heptylamino group, octylamino group, nonylamino group and benzylamino group.

The substituted or unsubstituted arylamino group is not particularly limited, but examples thereof include a phenylamino group, an alkylphenylamino group, an alkoxyphenylamino group, a hydroxyphenylamino group and a naphthylamino group. Can be mentioned.

Examples of the substituent which may form a 5-membered ring or a 6-membered ring with adjacent Xs through two hetero atoms include the substituents represented by the following formulas.

[0025]

Embedded image

In order for the phthalocyanine of the general formula (1) to smoothly react with the 2-aminothiophenol derivative represented by the general formula (2), the substituent X needs to be excellent as a leaving group, At least four of X are halogen atoms, and more preferably all X are halogen atoms. As the method for obtaining the phthalocyanine, those having X as a chlorine atom, bromine atom and the like are industrially available, and those having X as an iodine atom are those industrially obtainable It can be obtained by treating with potassium, sodium iodide or the like according to a conventional method and substituting with an iodine atom.

The fluorinated phthalocyanine is prepared by converting fluorinated phthalonitrile into Dyes and Pigment.
It can be produced by the method described on page 91 (1992).

Examples of the divalent metal atom represented by M include Cu (II), Zn (II), Fe (II) and Co (I
I), Ni (II), Ru (II), Rh (II), Pd (I
I), Pt (II), Mn (II), Mg (II), Ti (I
I), Be (II), Ca (II), Ba (II), 1d (I
I), Hg (II), Pb (II), Sn (II) and the like.

Examples of mono-substituted trivalent metals 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
l-I, Tl-F, Al-C ₆H_Five, Al-C₆H_Four(CH
₃), In-C₆H_Five, In-C₆H_Four(CH₃), In-C
₆H_Five, Mn (OH), Mn (OC₆H_Five), Mn [OSi
(CH₃)₃], Fe—Cl, Ru—Cl and the like.
It

An example of a disubstituted tetravalent metal is CrCl.
₂, SiCl₂, SiBr₂, SiF₂, SiI₂, ZrC
l₂, GeCl₂, GeBr₂, GeI₂, GeF₂, Sn
Cl₂, SnBr₂, SnF₂, TiCl₂, TiBr₂,
TiF₂, Si (OH)₂, Ge (OH)₂, Zr (O
H)₂, Mn (OH)₂, Sn (OH)₂, TiR₂, Cr
R₂, SiR₂, SnR₂, GeR₂[R is 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 alkyl
Group, phenyl group, naphthyl group, trialkylsilyl group,
Table showing dialkylalkoxysilyl groups and their derivatives
], Sn (SR ")₂, Ge (SR ")₂(R "is Al
Kill group, phenyl group, naphthyl group, and its derivatives
Representation] and the like.

Examples of oxymetals are VO, MnO,
TiO etc. are mentioned.

Cu and AlC are particularly preferable as M.
1, TiO or VO. More preferably, it is Cu.

In the phthalocyanine represented by the general formula (1), a particularly preferable compound is C.I. I. Pigment Green 7 (trade name: Phthalocyanine Green),
C. I. Pigment Green 36, C.I. I. Pigment Green 37, or C.I. I. Pigment Green 38, which is a commercially available compound as a halogenated phthalocyanine.

2 represented by the general formula (2) used in the present invention
Examples of the substituent represented by R and Y in the aminothiophenol are shown below.

Examples of the substituted or unsubstituted alkyl group represented by R are 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-
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, Two
-Phenylethyl group, 3-dimethylaminopropyl group,
2-dimethylaminoethyl group, 2-diisopropylaminoethyl group, 2-diethylaminoethyl group, 2,2,2
-Trifluoro-1- (trifluoromethyl) ethyl group, 2- (1-piperidino) ethyl group, 3- (1-piperidino) propyl group, 3- (4-morpholino) propyl group, 3- (4-morpholino) ) Ethyl group, 2- (1-
Examples thereof include a pyrrolidino) ethyl group, a 2-pyridylmethyl group and a furfuryl group.

As the substituted or unsubstituted aryl group,
Examples thereof include a phenyl group, a 2-methylphenyl group, a 3-methylphenyl group, a 4-methylphenyl group and a naphthyl group.

Of these, an alkyl group having 5 to 20 carbon atoms is particularly preferable. In order for the product to have high solubility in organic solvents, resins, etc., and to prevent the clouding phenomenon in the near infrared absorption filter resin, at least one substituent having 5 or more carbon atoms must be substituted. . However, if the carbon number exceeds 20, the product may not be obtained as a solid and may be unsuitable as a filter dye.

The substituted or unsubstituted alkyl group represented by Y is a methyl group, an ethyl group, an n-propyl group, i
so-propyl group, n-butyl group, iso-butyl group,
Examples thereof include sec-butyl group and t-butyl group.

As the substituted or unsubstituted aryl group,
Examples thereof include a phenyl group, a 2-methylphenyl group, a 3-methylphenyl group, a 4-methylphenyl group and a naphthyl group.

Examples of the substituted or unsubstituted alkoxy group are methoxy group, ethoxy group, n-propoxy group, is
Examples thereof include o-propoxy group, n-butoxy group, iso-butoxy group, sec-butoxy group and the like.

Examples of the substituted or unsubstituted aryloxy group include a phenoxy group, a 2-methylphenoxy group, a 3-methylphenoxy group, a 4-methylphenoxy group and a naphthoxy group.

These 2-aminothiophenol derivatives used in the present invention are usually produced by Synthesis, 2
It can be easily produced by the method described on page 88 (1985).

That is, 2-aminothiophenol and aldehydes are reacted to give the corresponding 2,3-dihydro-
It is obtained by treating with 1,3-benzothiozole and then treating with a reducing agent such as sodium borohydride or lithium aluminum hydride. It should be noted that there are other manufacturing methods and there is no particular limitation.

The reaction between the phthalocyanine represented by the general formula (1) and the 2-aminothiophenol derivative represented by the general formula (2) is carried out under the usual nucleophilic substitution reaction conditions, that is,
Sodium hydroxide, potassium hydroxide, sodium carbonate,
It can be carried out in the presence of a base such as potassium carbonate or sodium hydride.

This reaction may be carried out in the presence of a solvent, and the solvent used in this case is dimethylformamide (D
MF), dimethyl sulfoxide (DMSO), N, N '
Examples include polar solvents such as dimethylimidazolidinone (DMI) and sulfolane, ketone solvents such as acetone and methyl ethyl ketone, and aromatic hydrocarbon solvents such as toluene, xylene, monochlorobenzene and dichlorobenzene.

In the method for producing a near infrared ray absorbing compound of the present invention, usually, a phthalocyanine represented by the general formula (1) and a base (4 to 100 times equivalent to phthalocyanine) are added to a solvent (to phthalocyanine: 1). ˜1000 times by weight), or while stirring, the 2-aminothiophenol derivative represented by the general formula (2) (4 to 30 times equivalent to phthalocyanine) is added with stirring, and 5
React at 0-220 ° C. The addition of the 2-aminothiophenol derivative may be performed before the temperature rise, during the temperature rise, or after the temperature rise. Further, they may be added all at once or may be added in portions. Further, the 2-aminothiophenol derivative itself may be used as a solvent, and the phthalocyanine may be added after adding the base.

In the reaction, as a catalyst, metallic copper, copper chloride,
It is also possible to add a copper catalyst such as copper bromide, copper iodide or copper oxide. The reaction may be carried out under normal pressure or under pressure.

The degree of progress of the reaction is, for example, λ of the reaction solution.
It can be judged by measuring _max .

After the completion of the reaction, the reaction mixture is discharged into cooled water or an alcohol solution such as methanol, ethanol, propanol, butanol or pentanol to precipitate the target compound. The precipitated target substance is separated by suction filtration, washed with water and alcohol to remove salt, residual base, unreacted 2-aminothiophenol derivative and the like, and dried to absorb near infrared rays of the present invention. The compound is isolated.

The obtained near-infrared absorbing compound of the present invention is
Since it dissolves well in an organic solvent such as toluene, xylene and ethyl acetate, it can be purified by column chromatography if necessary.

The near infrared absorbing compound produced by the method of the present invention further comprises methyl halide, ethyl halide, 1
-Halopropane, 2-halopropane, 1-halobutane,
2-halobutane, 1-halo-2-methylbutane, 1-halo-3-methylbutane, 1-halopentane, 1-halohexane, 1-halo-2-ethyl-hexane, 1-haloheptane, 1-halooctane, 1-halononane, An alkyl halide such as 1-halodecane or benzyl halide,
By reacting under the same conditions as above, λ
It is possible to use a near-infrared absorbing compound whose _max has a long wavelength. As a halogen atom, a chlorine atom, a bromine atom,
Alternatively, iodine atom is used.

In this case, the near-infrared absorbing compound isolated by the above method and the above-mentioned base (for the near-infrared absorbing compound,
1 to 100 times by weight) is dissolved or suspended in a solvent (1 to 1000 times by weight with respect to the near-infrared absorbing compound) and stirred, and alkyl halide (with respect to the near infrared absorbing compound is 100 times by weight) to add 50
The reaction is carried out at ~ 220 ° C.

It is also possible to add the alkyl halide directly to the reaction mixture obtained by reacting the phthalocyanine and the 2-aminothiophenol derivative without isolating the near-infrared absorbing compound and further heat to continue the reaction. it can. After the reaction, it can be treated in the same manner as the above method.

The near-infrared absorber of the present invention is polyethylene, polypropylene, polyvinyl chloride, polystyrene,
Melamine, polyurethane, polyether, polycarbonate, polyester, polyacrylate, polymethacrylate, polyvinyl butyral, a resin such as ethylene-vinyl acetate copolymer, heating, kneading, or a mixture of the compound and those resins, Chloroform, toluene, xylene, acetone, methyl ethyl ketone (ME
K), ethyl acetate, butyl acetate, dibutyl ether, dimethylformamide (DMF) and the like can be dissolved into an organic solvent to obtain a near infrared absorbing resin composition, which can be used as a near infrared absorbing ink or paint.

By mixing the near-infrared absorbing agent together with a photopolymerization catalyst with a photoreactive monomer or oligomer, a photocurable near-infrared absorbing resin composition can be prepared. Similarly, a near-infrared absorbing ink or paint is prepared. Available as

A heat ray absorbing filter can also be produced by using the above kneaded resin mixture to prepare a resin plate, or extruding the kneaded resin mixture, stretching it and forming a film.

Furthermore, the above-mentioned ink or paint is coated on glass, a transparent resin film or a transparent resin plate such as polyester, polymethacrylate, polyvinyl chloride, or polycarbonate, or in a glass adhesive such as polyvinyl butyral. It is also possible to prepare a laminated glass by kneading a near-infrared absorbing compound and use the laminated glass for a heat ray absorbing laminated glass.

In the method for producing a near-infrared absorber of the present invention, an inexpensive pigment can be used as a starting material, has absorption in a long wavelength, has high light resistance, and is highly soluble in resins, solvents, etc. It is a method that can be obtained.

Further, since the product obtained by the method of the present invention is not a single compound but is obtained as a mixture of several kinds, the absorption wavelength becomes broad and it absorbs a wide range of near infrared rays. The compound is easy to apply to and is an excellent compound for absorbing heat rays.

[0060]

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

Reference Example After dissolving 2-aminothiophenol (40.0 g, 319 mmol) in 300 ml of ethanol, capryl aldehyde (41.0 g, 320 mmol) was added dropwise and reacted at room temperature for 4 hours. Then, sodium borohydride (21.0 g, 555 mmol) was charged in portions under ice cooling, and the mixture was reacted overnight at room temperature. After the reaction, ethanol was distilled off, the residue was put into ice water, and the reaction product was extracted with toluene. After separating the toluene phase, it was washed with water and saturated saline.

After dehydration with anhydrous sodium sulfate, toluene was distilled off to obtain 2- (n-octylamino) thiophenol (70.4 g, 297 mmol).

Example 1 C. I. Pigment Green 7 (trade name: Phthalocyanine Green) (10.0 g, 8.87 mmol),
2- (n-octylamino) thiophenol (33.7 g, 141.96 mmol, 16 times equivalent) obtained in Reference Example, potassium carbonate (39.2 g, 283.63 mmo)
1, 32 times equivalent) was added to dimethylformamide (200 m
The reaction was carried out in 1) at 120 ° C. for 5 hours. The reaction mixture was cooled to room temperature and then discharged into methanol (500 ml). The precipitate was collected by suction filtration, washed with methanol, washed with water, and dried to obtain a near-infrared absorbing compound (26.5 g) containing a compound of the following formula (3).

The compound was well soluble in an aromatic solvent such as toluene and benzene (dissolved in toluene at 5% or more), and λ _max was 940 nm (toluene solvent).

[0065]

[Chemical 6]

Furthermore, the compound was added to Unitika polyethylene terephthalate pellets 1203 in a weight ratio of 0.02:
After mixing at a ratio of 1, melted at 260 to 280 ° C., a film having a thickness of 100 μm was produced by an extruder, and then the film was biaxially stretched to produce a near infrared absorption filter having a thickness of 25 μm. The filter is 700-1100 nm
Well absorbed the light. According to JIS-R-3106
Shimadzu Corporation spectrophotometer UV-3100 T
_{When V} (visible light transmittance) and T _E (solar radiation transmittance) were measured, they were 70% and 65%, respectively.

300 hours carbon arc lamp (63 ° C)
A light fastness test was conducted, but no decrease in absorption due to decomposition of the dye was observed and the light fastness was good.

Example 2 Near-infrared absorbing compound (1.0 g) prepared in Example 1,
Potassium carbonate (3.9 g, 28.22 mmol) and methyl iodide (2.0 g, 14.09 mmol) were reacted in dimethylformamide (20 ml) at 120 ° C. for 3 hours. The reaction mixture was cooled to room temperature and then methanol (1
00g). The precipitate is collected by suction filtration, washed with methanol, washed with water, and dried to obtain the following formula (4).
A near-infrared absorbing compound (1.1 g) containing the above compound was obtained.

The compound is well soluble in an aromatic solvent such as toluene and benzene (dissolved in toluene at 5% or more), and has a λ _max
Was 950 nm (toluene solvent).

[0070]

[Chemical 7]

Example 3 C. I. Pigment Green 7 (trade name: Phthalocyanine Green) (10.0 g, 8.87 mmol),
2- (n-octylamino) thiophenol (19.0 g, 79.83 mmol, 9 times equivalent) obtained in Reference Example, 2-aminothiophenol (5.55 g, 44.
35 mmol, 5 times equivalent, potassium carbonate (39.2)
g, 283.63 mmol, 32 times equivalent) were reacted in dimethylformamide (200 ml) at 120 ° C. for 10 hours. The reaction mixture was cooled to room temperature and then discharged into methanol (500 ml). The precipitate is collected by suction filtration, washed with methanol, washed with water, and then dried to obtain a near-infrared absorbing compound (25.
6 g) was obtained.

The compound is well soluble in an aromatic solvent such as toluene and benzene (dissolved in toluene at 5% or more), and λ _max
Was 965 nm (toluene solvent).

[0073]

Embedded image

Example 4 C. I. Pigment Green 7 (trade name: Phthalocyanine Green) (10.0 g, 8.87 mmol),
2- (n-octylamino) thiophenol obtained in Reference Example (21.1 g, 88.88 mmol, 10 times equivalent), 2-methylaminothiophenol (3.7 g, 2
6.61 mmol, 3 times equivalent, potassium carbonate (39.
2 g, 283.63 mmol, 32 times equivalent) were reacted in dimethylformamide (200 ml) at 120 ° C. for 10 hours. The reaction mixture was cooled to room temperature and then discharged into methanol (500 ml). The precipitate is collected by suction filtration, washed with methanol, washed with water, and then dried to obtain a near-infrared absorbing compound (23.
1 g) was obtained.

The compound is well soluble in an aromatic solvent such as toluene and benzene (dissolved in toluene at 5% or more), and has a λ _max
Was 938 nm (toluene solvent).

[0076]

[Chemical 9]

Example 5 C. I. Pigment Green 36 (10.0 g), 2
-Aminothiophenol (40.0 g, 319 mmo
l) and benzaldehyde (33.96 g, 320 mmo
2- (benzylamino) thiophenol (30.6 g), potassium carbonate (39.2 g), cuprous chloride (0.5 g), which had been synthesized by the same method as in Reference Example using 1).
1 in N'-dimethylimidazolidinone (200 ml)
The reaction was carried out at 50 ° C for 10 hours. The reaction mixture was cooled to room temperature and then discharged into methanol (500 ml). The precipitate was collected by suction filtration, washed with methanol, washed with water, and dried to obtain a near infrared absorbing compound (24.0 g) containing a compound of the following formula (7).

The compound is well soluble in an aromatic solvent such as toluene and benzene (dissolved in toluene 5% or more), and has a λ _max
Was 950 nm (toluene solvent).

[0079]

[Chemical 10]

Example 6 C. I. Pigment Green 38 (10.0 g), 2
-Aminothiophenol (40.0 g, 319 mmo
l) and piperidinopropionaldehyde (45.2 g,
320 mmol) was used to synthesize 2- [3- (1-piperidyl) propyl] aminothiophenol (35.5 g, 141.78 mmol) and potassium carbonate (39.2 g, 283.63 mmol) in the same manner as in Reference Example. To
N, N'-Dimethylimidazolidinone (200 ml)
The reaction was carried out at 120 ° C. for 3 hours. The reaction mixture was cooled to room temperature and then discharged into water (500 ml). The precipitate was collected by suction filtration, washed with methanol, washed with water, and dried to obtain a near-infrared absorbing compound (23.0 g) containing the compound of the following formula (8).

The λ _max of the compound was 940 nm (toluene solvent).

[0082]

[Chemical 11]

Examples 7 to 15 Maximum absorption wavelengths of near-infrared absorbing compounds obtained by reacting the starting phthalocyanine according to Example 1 with 16 times equivalent of aminothiophenol derivative synthesized by the same method as in Reference Example. Is shown in Table 1. All compounds were well dissolved in aromatic solvents such as toluene and benzene (dissolved in toluene at 5% or more).

[0084]

[Table 1]

[0085]

INDUSTRIAL APPLICABILITY The present invention provides a method for easily producing a highly soluble phthalocyanine-based near-infrared absorbing compound having high light resistance, which is extremely valuable in practical use.

Claims (11)

[Claims] 1. A near infrared absorbing compound obtained by reacting a phthalocyanine represented by the general formula (1) with at least one 2-aminothiophenol derivative represented by the general formula (2) in the presence of a base. Manufacturing method. Embedded image [In the formula (1), X is independently a halogen atom, a hydroxyl group,
Substituted or unsubstituted alkoxy group, substituted or unsubstituted aryloxy group, substituted or unsubstituted alkylthio group, substituted or unsubstituted arylthio group, substituted or unsubstituted alkylamino group, substituted or unsubstituted arylamino group Represents a substituted or unsubstituted alkylarylamino group, and adjacent Xs may form a 5-membered ring or a 6-membered ring through two hetero atoms, n represents an integer of 4 to 16, and M represents a divalent group. Represents a metal atom of or a trivalent or tetravalent substituted metal or oxymetal. However, at least four of X are halogen atoms. ] [Chemical 2] [In Formula (2), R represents a hydrogen atom, a substituted or unsubstituted alkyl group, or a substituted or unsubstituted aryl group, and Y is independently a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group. Represents a group, a substituted or unsubstituted alkoxy group, or a substituted or unsubstituted aryloxy group, and m represents an integer of 0 to 4. However, when several kinds of formula (2) are reacted, R in all formula (2) does not simultaneously become a hydrogen atom.] 2. The method for producing a near infrared absorbing compound according to claim 1, wherein the central metal M of the phthalocyanine represented by the general formula (1) is Cu, AlCl, TiO or VO. 3. The phthalocyanine represented by the general formula (1), wherein all the substituents X are halogen.
A method for producing the described near-infrared absorbing compound. 4. The phthalocyanine represented by the general formula (1) is C.I. I. Pigment Green 7, C.I. I. Pigment Green 36, C.I. I. Pigment Green 3
7, or C.I. I. Pigment Green 38, The method for producing a near-infrared absorbing compound according to claim 1. 5. A 4-aminothiophenol derivative of the general formula (2) is added to the phthalocyanine of the general formula (1) in an amount of 4 times.
The method for producing a near-infrared absorbing compound according to any one of claims 1 to 4, wherein the reaction is performed in a double equivalent or more. 6. At least one of the 2-aminothiophenol derivatives has a carbon number of 5 to 5 in the general formula (2).
20 substituted or unsubstituted alkyl groups or 6 carbon atoms
2. The substituted or unsubstituted aryl group of -20.
6. The method for producing a near-infrared absorbing compound according to any one of 5 to 5. 7. A near-infrared absorbing compound produced by the production method according to claim 1. 8. The near infrared absorbing compound according to claim 7,
Further, a near infrared absorbing compound obtained by reacting with an alkyl halide. 9. The near-infrared absorbing compound according to claim 7, which has a maximum absorption wavelength λ _max at 910 nm or more. 10. A near infrared absorbing resin composition containing the phthalocyanine-based near infrared absorbing compound according to claim 7. 11. A heat ray absorption filter containing the phthalocyanine-based near-infrared absorbing compound according to claim 7.