JPH08253693A - Near-infrared ray absorbent, its production and use thereof - Google Patents

Abstract

PURPOSE: To obtain a phthalocyanine-based near-infrared ray absorbent, comprising a specific phthalocyanine-based compound, capable of simply obtaining at a low cost, excellent in light resistance and solubility and useful for recording layer of a light recording medium, near-infrared ray absorbing ink or a heat radiation absorbing filter, etc. CONSTITUTION: This absorbent comprises a compound of formula I [R<1> and R<2> are each a (substituted)alkyl, a (substituted)aryl or H; Y is a (substituted) alkyl, (substituted)aryl, etc.; Z is SH or a group of the formula NHR<3> (R<3> is R<1> ); X is OH, a halogen, a (substituted)alkoxy, etc.; M is a divalent metal, a trivalent substituted metal, trivalent oxy metal, etc.; Pc is a phthalocyanine skeleton; (m) is 0-4; (p) is 1-16; (q) and (r) are each 0-8; (p+2p+r)<=16]. The compound of formula 1 is obtained by reacting a compound of formula II [(n) is 4-16] with a compound of formula III in the presence of a base.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a phthalocyanine-based near-infrared absorber having a wide absorption in the near-infrared region, a method for producing the same, a near-infrared absorbing composition containing the same, and a heat ray absorbing filter.

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. Further, it is also possible to produce a heat ray absorption filter which absorbs near infrared rays by coating (plasticizing) plastic or glass as a resin composition in combination with a binder resin, or by kneading 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.
In addition, by cutting a specific wavelength region, it can be used as a film for selective use of light quality control of plant growth, infrared cut of a semiconductor light receiving element, and eyeglasses that protect human eyes from rays containing harmful infrared rays. .

Among the above, the heat ray absorption filter for the purpose of intercepting the heat ray particularly contributes to energy saving.
This is a field that is drawing attention.

[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. Further, the heat ray absorbing glass in which metal ions are dispersed in glass has many problems in terms of cost and the like. Compared with those inorganic type heat ray reflection filters, heat ray absorption filters using near-infrared absorbing dyes have wide application fields and large market needs because they are easy to manufacture and have no problem of radio interference. 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. Further, compounds of the aminium salt type described in JP-A-3-161644, or JP-B-54-25060 and JP-A-50-
The metal complex compounds described in 51549 and the like are insufficient in heat resistance and light resistance. In addition, Japanese Patent Laid-Open No. 3-115362,
The anthraquinone-based compound described in JP-A-62-903 also has heat resistance but is insufficient in light resistance.

As a near-infrared absorbing dye having high durability, JP-B-59-1311 and JP-A-60-20958.
3, Japanese Patent Publication No. 2-5155, Japanese Patent Laid-Open No. 61-152685,
The phthalocyanines described in JP-A-61-223056 and JP-A-3-62878 are complicated in the manufacturing process and have a short λ _max of at most 800 nm, and have a narrow absorption wavelength region. It was

In Japanese Examined Patent Publication No. 4-75916, a chlorinated copper phthalocyanine is reacted with 2-aminothiophenol to obtain a dye having a λ _max of 909 nm, which is measured in pyridine. However, there is no data measured by coating on glass, data on extinction coefficient, etc. That is, since the compound has a low solubility in an organic solvent or a resin, when it is dissolved in the resin, a clouding phenomenon occurs, and a transparent resin composition or a heat ray absorbing filter cannot be obtained. The claim has 1 to 4 carbon atoms
Although a compound having a substituent of is also disclosed, if the carbon number is 1 to 4, it is insufficient to suppress the clouding phenomenon,
Further, there is no description about the manufacturing method thereof.

Further, Japanese Patent Laid-Open No. 63-308073 discloses a method in which 2-aminothiophenol and 4-methylphenylthiol are allowed to coexist in order to increase the solubility of phthalocyanine, and λ _max is 890 nm.
And short.

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 to improve the solubility and absorption. A method of improving both wavelengths is disclosed. That is, the dye has a maximum absorption wavelength near 900 nm,
700-180 because the absorption waveform is relatively broad
Although it can absorb the near-infrared region of 0 nm relatively broadly, it is still insufficient as compared with the inorganic near-infrared absorbing glass.
Further, in the method of performing alkylation later, the efficiency of alkylation is poor, and the solubility of the product may not be sufficiently increased.

[0011]

An object of the present invention is to have a high light resistance, a high dissolution type, and a near infrared region (7
It is to provide a phthalocyanine-based near-infrared absorbing compound having a wide absorption in the range of 0 to 1800 nm) easily at low cost. Furthermore, it is to provide a near infrared absorbing compound which is effective as a near infrared absorbing resin composition or a heat ray absorbing filter.

[0012]

Means for Solving the Problems As a result of intensive studies for solving the above problems, the present inventors have found that a certain kind of phthalocyanine near-infrared absorber has excellent performance, and completed the present invention. Came to do.

That is, the present invention is a phthalocyanine-based near-infrared absorber having a broad absorption in the near-infrared region represented by the general formula (1).

[0014]

Embedded image [In the formula, R ¹ and R ² represent a hydrogen atom, a substituted or unsubstituted alkyl group, or a substituted or unsubstituted arule group, and Y is independently a substituted or unsubstituted alkyl group,
A substituted or unsubstituted aryl group, a substituted or unsubstituted alkoxy group, or a substituted or unsubstituted aryloxy group, m represents an integer of 0 to 4, Pc represents a phthalocyanine nucleus, and Z represents -SH. Group or a —NHR ³ group (R ³ represents a hydrogen atom, a substituted or unsubstituted alkyl group, or a substituted or unsubstituted aryl group), and Xs are each independently a halogen atom, a hydroxyl group, a substituted or unsubstituted group. An alkoxy group, a substituted or unsubstituted aryloxy group, a substituted or unsubstituted alkylthio group, a substituted or unsubstituted arylthio group, a substituted or unsubstituted alkylamino group, a substituted or unsubstituted arylamino group, a substituted or unsubstituted It represents a substituted alkylarylamino group, and adjacent Xs may form a 5-membered ring or a 6-membered ring through two hetero atoms, and Represents a divalent metal atom or a trivalent or tetravalent substituted metal or oxymetal, and p is 1
Is an integer of 0 to 16, q is an integer of 0 to 8, r is an integer of 0 to 8, and p + 2q + r ≦ 16. ]

The present invention is also obtained by reacting a phthalocyanine represented by the general formula (2) with at least one 2-aminothiophenol derivative represented by the general formula (3) in the presence of a base. The present invention relates to a method for producing a phthalocyanine-based near-infrared absorber having the broad absorption in the near-infrared region and represented by the general formula (1).

[0016]

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

[0017]

[Chemical 7] [Wherein, R ¹ and R ² represent a hydrogen atom, a substituted or unsubstituted alkyl group, or a substituted or unsubstituted aryl group, and Y's each independently represent a substituted or unsubstituted alkyl group,
Substituted or unsubstituted aryl group, a substituted or unsubstituted alkoxy group, or a substituted or unsubstituted aryloxy group, Z is -SH group or -NHR ³ group (R ³ is a hydrogen atom, a substituted or unsubstituted Alkyl group of, or
Represents a substituted or unsubstituted aryl group), and m is 0.
~ Represents an integer of 4]

Further, the present invention relates to a near-infrared absorbing resin composition containing the near-infrared absorbing agent represented by the general formula (1) and a heat ray absorbing filter.

[0019]

BEST MODE FOR CARRYING OUT THE INVENTION The present invention is described in detail below.

The near infrared absorber of the present invention has the general formula (1):
It is a phthalocyanine-based near-infrared absorber having a wide absorption in the near-infrared region represented by.

[0021] In the general formula ^{(1), R 1, R} 2, an alkyl group substituted or unsubstituted represented by R ³ in the Z is, C ₁ ~
A C ₂₀ substituted or unsubstituted alkyl group, examples of which include a methyl group, an ethyl group, an n-propyl group, and iso.
-Propyl group, n-butyl group, iso-butyl group, se
c-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 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-
Examples thereof include a phenylethyl group, a 2-methylbenzyl group, a 3-methylbenzyl group, a 4-methylbenzyl group and a 2-phenylethyl group.

Further, the substituted or unsubstituted aryl group is
It is a C ₆ -C ₂₀ substituted or unsubstituted aryl group, and examples thereof include a phenyl group, a 2-mercaptophenyl group, a 3-mercaptophenyl group, a 4-mercaptophenyl group, a 2-methylphenyl group, and a 3-methylphenyl group. Methylphenyl group,
Examples include 4-methylphenyl group and naphthyl group.

Of the substituents represented by R ¹ and R ² , more preferable ones are methyl group, ethyl group, n-propyl group and is.
o-propyl group, n-butyl group, iso-butyl group, s
ec-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-
It is an ethylhexyl group, an n-nonyl group, an n-decyl group, or a phenyl group.

Examples of the substituent represented by Z include SH group and NHR ³ . Particularly preferred is NHR ³ , and more preferred R ³ is phenyl group, 2-mercaptophenyl group, 3-mercaptophenyl group, 4-mercapto
A C _{6 to} C ₂₀ substituted or unsubstituted aryl group such as a mercaptophenyl group, a 2-methylphenyl group, a 3-methylphenyl group, a 4-methylphenyl group, and a naphthyl group.

The substituted or unsubstituted alkyl group represented by Y is a C ₁ -C ₂₀ substituted or unsubstituted alkyl group, and examples thereof include a methyl group, an ethyl group, an n-propyl group and iso. -Propyl group, n-butyl group, iso-butyl group, sec-butyl group, t-butyl group and the like. The substituted or unsubstituted aryl group is a C _{6 to} C ₂₀ substituted or unsubstituted aryl group, and examples thereof include:
Examples thereof include a phenyl group, a 2-methylphenyl group, a 3-methylphenyl group, a 4-methylphenyl group and a naphthyl group. The substituted or unsubstituted alkoxy group is a C _{1 to} C ₂₀ substituted or unsubstituted alkoxy group, and examples thereof include a methoxy group, an ethoxy group, an n-propoxy group, and is.
Examples thereof include o-propoxy group, n-butoxy group, iso-butoxy group, sec-butoxy group and the like. The substituted or unsubstituted aryloxy group is a C _{6 to} C ₂₀ substituted or unsubstituted aryloxy group, and examples thereof include a phenoxy group, a 2-methylphenoxy group, a 3-methylphenoxy group, and a 4-methylphenoxy group. Group, naphthoxy group and the like.

Examples of the halogen atom represented by X include fluorine, chlorine, bromine and iodine. The substituted or unsubstituted alkoxy group represented by X is not particularly limited, and examples thereof include a methoxy group, an ethoxy group, and n.
-Propoxy group, iso-propoxy group, n-butoxy group, iso-butoxy group, sec-butoxy group, n-pentoxy group, iso-pentoxy group, n-hexyloxy group, cyclohexyloxy group, n-heptyloxy group, Examples thereof include n-octyloxy group, 2-ethylhexyloxy group, n-nonyloxy group, methoxyethoxy group, ethoxyethoxy group, ethoxyethoxyethoxy group, hydroxyethoxyethoxy group, diethylaminoethoxy group and benzyloxy group.

The substituted or unsubstituted aryloxy group represented by X is not particularly limited, and examples thereof include a phenoxy group, a 2-methylphenoxy group, a 3-methylphenoxy group, a 4-methylphenoxy group, A naphthoxy group etc. are mentioned.

The substituted or unsubstituted alkylthio group represented by X is not particularly limited, and examples thereof include methylthio group, ethylthio group, n-propylthio group, iso-propylthio group, n-butylthio group, and is.
o-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,
Alkoxyalkylthio groups such as γ-methoxypropylthio group, γ-ethoxypropylthio group, methoxyethoxyethylthio group, ethoxyethoxyethylthio group, dimethoxymethylthio group, diethoxymethylthio group, dimethoxyethylthio group, diethoxyethylthio group Examples thereof include an alkylaminoalkylthio group such as an alkoxyalkoxyalkylthio group, an alkoxyalkoxyalkoxyalkylthio group, a chloromethylthio group, a dimethylaminoethylcythio group, and a diethylaminoethylthio group, and a dialkylaminoalkylthio group.

The substituted or unsubstituted arylthio group represented by X is not particularly limited, but for example,
Phenylthio group, naphthylthio group, 4-methylphenylthio group, 4-ethylphenylthio group, 4-propylphenylthio group, 4-t-butylphenylthio group, 4-methoxyphenylthio group, 4-ethoxyphenylthio group, Four
-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 Group, 2-phenylaminophenylthio group, 2-diphenylaminophenylthio group, 2-hydroxyphenylthio group, 2-chlorophenylthio group, 2-bromophenylthio group and the like.

The substituted or unsubstituted alkylamino group represented by X is not particularly limited, and examples thereof include a methylamino group, an ethylamino group, an n-propylamino group, an iso-propylamino group and a butyl group. Amino group,
Examples thereof include a pentylamino group, a dipentylamino group, a hexylamino group, a heptylamino group, an octylamino group, a nonylamino group and a benzylamino group.

The substituted or unsubstituted arylamino group represented by X is not particularly limited, and examples thereof include a phenylamino group, an alkylphenylamino group,
Examples thereof include an alkoxyphenylamino group, a hydroxyphenylamino group and a naphthylamino group.

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.

[0033]

Embedded image

An example of a divalent metal represented by M is 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 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), Mn (O
H), Mn (OC₆H_Five), Mn [OSi (CH₃)₃],
Fe-Cl, Ru-Cl, etc. are mentioned.

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.

P is an integer of 1 to 16, particularly preferably 4 to 12. q is an integer of 0 to 8 and particularly preferably 1 to 4. r is an integer of 0 to 8 and particularly preferably 0 to 4. Although p + 2q + r ≦ 16, the larger p and q, the wider the absorption. It is particularly preferable that q increases.

The method for producing the phthalocyanine-based near infrared ray absorbent of the present invention can be easily produced by reacting a phthalocyanine having a leaving group such as a halogen atom with a 2-aminothiophenol derivative. That is, the method for producing a phthalocyanine-based near-infrared absorber of the present invention comprises a phthalocyanine represented by the general formula (2) and at least one 2-aminothiophenol derivative represented by the general formula (3), A method for producing a near-infrared absorber, which comprises reacting in the presence of a base.

[0041]

[Chemical 9]

[0042]

[Chemical 10] (In the above formula, R ¹ , R ² , X, Y, Z, M, m and n have the same meanings as described above.)

In general, by introducing an amino group into the benzene ring of phthalocyanine, the absorption of phthalocyanine can be made longer in wavelength and broadened. However, the compound having an amino group has poor reactivity and does not easily react with the phthalocyanine represented by the general formula (2). In the present invention, a compound having both a thiol and an amino group is used, and a thiol having a good reactivity and a general formula (2)
Is a method of introducing an amino group by causing an intramolecular cyclization reaction after reacting with the phthalocyanine of. In the intramolecular cyclization reaction, a stable 6-membered ring structure is formed via a sulfur atom and a nitrogen atom, so that a dye resistant to light can be formed.

In the phthalocyanine represented by the general formula (2) used in the present invention, the substituent represented by X is the same as X in the general formula (1). n is an integer of 4 to 16, and particularly preferably 8 to 16. However, X must be excellent as a leaving group in order to smoothly cause the nucleophilic substitution reaction, and at least four of X are halogen atoms.

As the method for obtaining the phthalocyanine, those having X as chlorine atom, bromine atom and the like are industrially available. Those in which X is an iodine atom can be obtained by treating these industrially available ones with potassium iodide, sodium iodide and the like according to a conventional method and substituting the iodine atom. In addition, as the fluorinated phthalocyanine, commercially available fluorinated phthalonitrile can be obtained by using Dyes and Pigment.
It can be produced by the method described on page 91 (1992). Further, a substituent in which X is other than a halogen atom is reacted with a halogenated phthalocyanine and various mercaptans, alcohols, amines or the like to substitute a part thereof, or JP-A-3-6.
It can also be prepared using 2,3-dicyano-5,6-dichloroquinone (DDQ) as a starting material as described in 2878.

In the phthalocyanine represented by the general formula (2), a particularly preferable compound is 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 compound that is industrially easily available as a halogenated phthalocyanine.

Similarly, M is the same as M in the general formula (1), particularly preferably Cu, AlCl, TiO, or VO, and more preferably Cu.

2 represented by the general formula (3) used in the present invention
Y, m, R ¹ in the aminothiophenol derivative,
R ² and Z are the same as in the general formula (1), and more preferred are compounds represented by the general formula (4).

[0049]

[Chemical 11] [In the formula, R ¹ and R ² represent a hydrogen atom, a substituted or unsubstituted alkyl group, or a substituted or unsubstituted aryl group. ]

Further, this compound may form a salt with a metal such as zinc, mercury, cadmium, iron (II) or nickel. In particular, the zinc salt stabilizes the compound of the general formula (4), easily releases zinc when reacting by adding a base, and reacts with the compound of the general formula (2).

The 2-aminothiophenol derivative used in the present invention is generally described in Synthesis, p. 288 (1985), Chem. Ber. , 101 volumes, 1
579 (1968), or Can. J.
Chem. , 52, pp. 1054 (1974) and the like. For example, it can be easily produced by reacting 2-aminothiophenol with a corresponding aldehyde or ketone and then reducing the same.

The reaction between the phthalocyanine represented by the general formula (2) and the 2-aminothiophenol derivative represented by the general formula (3) is carried out under the usual nucleophilic substitution reaction conditions, that is,
Sodium hydroxide, potassium hydroxide, sodium carbonate,
It is 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, in which case dimethylformamide (D
MF), dimethyl sulfoxide (DMSO), 1,3-
Dimethyl-2-imidazolidinone (DMI), polar solvents such as sulfolane, ketone solvents such as acetone and methyl ethyl ketone, toluene, xylene, monochlorobenzene,
An aromatic hydrocarbon solvent such as dichlorobenzene may be used.

The method for producing the near-infrared absorber of the present invention is usually a phthalocyanine represented by the general formula (2) and a base (4 to 100 times equivalent to the phthalocyanine, preferably 5).
~ 50 times equivalent) to the solvent (based on phthalocyanine) 1
Dissolved or suspended in 1 to 1000 times by weight) and with stirring, a 2-aminothiophenol derivative represented by the general formula (3) (equivalent to 1 to 30 times equivalent to phthalocyanine, preferably 2 to 10 times). 50 to 22
React at 0 ° 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.

If desired, a plurality of 2-aminothiophenol derivatives described in the present application may be combined and reacted, or a substituted or unsubstituted phenol, a substituted or unsubstituted thiophenol, or a 2-aminothiophenol, A compound having a reactive substituent such as 2-alkylaminothiophenol can also be added and reacted at the same time.

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.

In the reaction of the present invention, the case where the mercapto group of the general formula (3) reacts with the general formula (2) at one point and the general formula (1) which is a mixture of the mercapto group and the amino group at two points is mainly used. Obtained as the product, but with the addition of Z 3
You may react in points.

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

After completion of the reaction, the reaction mixture was cooled with water,
Alternatively, the target compound is precipitated by discharging into an alcohol solution of methanol, ethanol, propanol, butanol, pentanol, or the like. 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. Separate the agent. The near-infrared absorber of the present invention obtained,
Since it dissolves well in an organic solvent such as chloroform, toluene, xylene, and ethyl acetate, it can be purified by column chromatography if necessary.

The near-infrared absorber 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, 1 -Unreacted mercapto group or amino group can be alkylated by reacting with an alkyl halide such as -halodecane or benzyl halide under the same conditions as above. As a halogen atom, a chlorine atom, a bromine atom,
Alternatively, iodine atom is used.

In this case, the near-infrared absorbing agent isolated by the above method and a base (1 to 100 times by weight of the near infrared absorbing agent) are used as a solvent (1 to 1000 times by weight of the near infrared absorbing agent). Alky halide (1-10 with respect to the near-infrared absorber) while being dissolved or suspended in
(0 times by weight) is added and the reaction is carried out at 50 to 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 absorber and further heat to continue the reaction. it can.

After the reaction, the same treatment as described above can be carried out.

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.

Further, by mixing the near-infrared absorbing agent with a photopolymerization catalyst and 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 producing a resin plate using the above-mentioned kneaded resin mixture, or extruding the kneaded resin mixture, stretching it and forming a film.

Furthermore, the above ink or paint is coated on glass, a transparent resin film such as polyester, polymethacrylate, polyvinyl chloride, or polycarbonate, or a transparent resin plate, or in a glass adhesive such as polyvinyl butyral. It is also possible to prepare a laminated glass by kneading and mixing a near-infrared absorber and use it as 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, it has absorption in a long wavelength, has high light resistance, and a compound highly soluble in a resin, a solvent or the like is simple. It is a method that can be obtained. Furthermore, 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, it has a broad absorption wavelength and absorbs a wide range of near-infrared region, so that it can be used as a near-infrared absorption filter. It is a compound that is easy to apply and excellent for absorbing heat rays.

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

Example 1 C. I. Pigment Green 7 (Phthalocyanine Green) (10.0 g, 8.87 mmol), the following formula (6)

[0071]

[Chemical 12] The zinc complex of a 2-aminothiophenol derivative represented by (16.3 g, 44.35 mmol, 5 times equivalent) and potassium carbonate (39.2 g, 283.63 mmol, 32 times equivalent) were added to 1,3-dimethyl- The reaction was carried out in 2-imidazolidinone (DMI) (200 ml) at 170 ° C. for 2 hours. The reaction mixture was cooled to room temperature and then methanol (5
(00 ml). The precipitate is collected by suction filtration, washed with methanol, washed with water, and dried to obtain the following formula (7).
A near-infrared absorber (14.5 g) containing was obtained.

[0072]

[Chemical 13]

The absorption spectrum of the mixture in chloroform is shown in FIG. As is clear from the figure, the absorption peak of the mixture is broader than the absorption peak of ordinary phthalocyanine, and absorbs near-infrared rays at 700 to 1800 nm well. Particularly, the difference in absorption is remarkable in the region of 1000 nm or more (see Comparative Example).

Example 2 In Example 1, instead of the zinc complex of the 2-aminothiophenol derivative of the formula (6), the following formula (8) was used.

[0075]

Embedded image 2-aminothiophenol derivative represented by (8.8
g, 26.61 mmol, 3-fold equivalent) and 2- (n-
Octylamino) thiophenol (12.6 g, 53.
The reaction was performed in the same manner as in Example 1 except that (22 mmol, 6 times equivalent) was used. The reaction mixture was post-treated in the same manner as in Example 1 to give a near-infrared absorber (1
3.7 g) was obtained.

[0076]

[Chemical 15]

The absorption spectrum of the mixture in chloroform is shown in FIG. As is clear from the figure, the absorption peak of the mixture is broader than the absorption peak of ordinary phthalocyanine, and absorbs near-infrared rays at 700 to 1800 nm well. Particularly, the difference in absorption is remarkable in the region of 1000 nm or more (see Comparative Example).

Example 3 In Example 1, instead of the zinc complex of the 2-aminothiophenol derivative of the formula (6), the following formula (10) was used.

[0079]

Embedded image 2-aminothiophenol derivative represented by (27.6
g, 79.83 mmol, 9 times equivalent)
The reaction was carried out in the same manner as in Example 1. The reaction mixture was prepared as in Example 1.
Post-treatment was carried out in the same manner as above to obtain a near-infrared absorber (19.2 g) containing the following formula (11).

[0080]

[Chemical 17]

The absorption spectrum of the mixture in chloroform is shown in FIG. As is clear from the figure, the absorption peak of the compound is broader than the absorption peak of ordinary phthalocyanine, and absorbs near-infrared rays of 700 to 1800 nm well. Particularly, the difference in absorption is remarkable in the region of 1000 nm or more (see Comparative Example).

Example 4 The amount of the 2-aminothiophenol derivative of the formula (6) used in Example 1 was tripled (48.9 g, 13).
(3.05 mmol, 15 times equivalent) was subjected to the same reaction as in Example 1 to obtain a near infrared absorber (25.3 g) containing the following formula (12). The absorption peak of the near-infrared absorbing agent is broader than that of a usual phthalocyanine, and well absorbs near-infrared rays of 700 to 1800 nm.

[0083]

Embedded image

Example 5 In Example 1, except that the zinc complex of the 2-aminothiophenol derivative of the formula (6) was replaced with (8) used in Example 2 (44.0 g, 133.05 mmo).
1, 15 times equivalent) was subjected to the same reaction as in Example 1 to obtain a near-infrared absorber (35.3 g) containing the following formula (13). The absorption peak of the compound is broader than that of ordinary phthalocyanine, and is 700 to 180.
It absorbs near-infrared rays of 0 nm well.

[0085]

[Chemical 19]

Example 6 The near infrared absorbent produced in Example 1 was mixed with polyethylene terephthalate pellets 1203 manufactured by Unitika at a weight ratio of 0.03: 1, and the mixture was melted at 260 to 280 ° C., and was then extruded. After producing a film having a thickness of 100 μm, this film was biaxially stretched to produce a heat ray absorbing film having a thickness of 25 μm. The transmittance spectrum of the film is shown in (FIG. 4). As is clear from the figure, the absorption peak of the film is broader than the absorption peak of a film similarly produced using a normal phthalocyanine, and absorbs near infrared rays at 700 to 1800 nm well. Particularly, the difference in absorption is remarkable in the region of 1000 nm or more (see Comparative Example 3).

Further, the film was subjected to a light fastness test at 63 ° C. for 300 hours using a carbon arc lamp, and the light fastness was good without any decrease in absorption due to decomposition of the dye.

Example 7 Near-infrared absorber (0.4 g) produced in Example 2 and polymethylmethacrylate (PMMA) pellets [Asahi Kasei Co., Ltd., trade name "Delpet 80N"] (5 g) were added to toluene. / Methyl ethyl ketone (MEK) = 1/1 was dissolved in a mixed solution (30 g) to prepare a near infrared absorbing coating. This coating material was coated on a PET film [manufactured by Toray Industries, Inc., trade name "Lumira"] using a coil bar and then dried at room temperature for 1 hour to remove the solvent and prepare a heat ray absorbing film. The transmittance spectrum of the film is shown in (FIG. 5). As is clear from the figure, the absorption peak of the film is broader than the absorption peak of a film similarly produced using a normal phthalocyanine, and absorbs near infrared rays at 700 to 1800 nm well. Particularly, the difference in absorption is remarkable in the region of 1000 nm or more (see Comparative Example 5).

Further, the film was subjected to a light fastness test at 63 ° C. for 300 hours using a carbon arc lamp, and no deterioration in absorption due to decomposition of the dye was observed and the light fastness was good.

Example 8 Near-infrared absorber (5 g) produced in Example 1, polyvinyl butyral adhesive [Sekisui Chemical Co., Ltd., trade name "ESREC Film"] (2000 g), ultraviolet absorber [Ciba Geigy ( Ltd., trade name "Tinubin P"] (10
g) was mixed and melted at 200 to 240 ° C., and a film having a thickness of 300 μm was produced by an extruder. Subsequently, the film was sandwiched by 3 mm-thick float glass and treated in an autoclave at 130 ° C. and 12 kg / cm ² for 20 minutes to prepare a laminated glass. The laminated glass is 70
It well absorbed near infrared rays of 0 to 1800 nm.

Further, the laminated glass was subjected to a light fastness test at 63 ° C. for 300 hours using a carbon arc lamp, and no deterioration in absorption due to decomposition of the dye was observed and the light fastness was good.

Example 9 Acrylate-based monomer [Kyoeisha Oil and Fat Chemical Co., Ltd.
Product name "Light acrylate BP-4EA"] (5
g) near-infrared absorber (0.2) produced in Example 1
g), a photopolymerization catalyst [manufactured by Nippon Kayaku Co., Ltd., trade name “Kayacure DEXT”] (0.2 g) was dissolved to prepare a photocurable resin composition. After coating this coating material on a transparent PET film [Toray Industries, Inc., trade name “Lumirror”] and a white PET film [Toray Co., Ltd., trade name “Lumirror” white type] using a coil bar,
A high-pressure mercury lamp (using "Rapid Cure" irradiator manufactured by Ushio Co., Ltd.) was irradiated with light of 400 mJ / cm ² to cure. When the transmittance spectrum or reflectance spectrum of each film was measured, it was 700 to 1800 n.
The near infrared rays of m were well absorbed.

Further, the film was subjected to a light fastness test at 63 ° C. for 300 hours using a carbon arc lamp, and the light fastness was good without any decrease in absorption due to decomposition of the dye.

Example 10 The near infrared absorber (1.0 g) obtained in Example 1, potassium carbonate (3.9 g, 28.22 mmol) and 1-iodinated hexane (3.0 g, 14.09 mmol) were added. , DMF
The reaction was carried out in (20 ml) at 120 ° C. for 3 hours. The reaction mixture was cooled to room temperature and then discharged into methanol (100 g). The precipitate was collected by suction filtration, washed with methanol, washed with water, and dried to obtain a near infrared absorption mixture (1.1
g) was obtained.

The absorption spectrum of the mixture was broad and well absorbed near-infrared rays of 700 to 1800 nm.

Example 11 C.I. I. Pigment Green 38 (10.0 g), a 2-aminothiophenol derivative (10.1 g, 44.35 mmol) represented by the following formula (14), cuprous chloride (0.5 g), potassium carbonate (39.2 g). , 283.6
3 mmol) in DMF (200 ml) at 120 ° C.
Then, it was reacted 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 absorber (1.1 g) containing the following formula (15).

[0097]

Embedded image

[0098]

[Chemical 21]

The absorption spectrum of the mixture was broad and well absorbed near-infrared rays of 700 to 1800 nm.

Examples 12 to 20 Table 1 shows the results of the reaction of phthalocyanine and aminothiophenol derivative according to Example 4. The absorption of each of the isolated near infrared absorbers is broad,
The near infrared rays of 700 to 1800 nm were well absorbed.

[0101]

[Table 1]

Comparative Example 1 C.I. I. Pigment Green 7 (trade name: Phthalocyanine Green) (10.0 g, 8.87 mmol), 2-
(N-octylamino) thiophenol (21.1 g,
88.70 mmol, 10 times equivalent, potassium carbonate (3
9.2 g, 283.63 mmol, 32 eq.), D
Reaction was carried out in MI (200 ml) at 170 ° C. for 2 hours. The reaction mixture was cooled to room temperature and then methanol (500
ml). After collecting the precipitate by suction filtration,
After washing with methanol, washing with water, and drying, a near-infrared absorber (15.3 g) containing the following formula (16) was obtained.

[0103]

[Chemical formula 22]

The absorption spectrum of the mixture in chloroform is shown in (FIG. 6). As is clear from the figure, the absorption peak of the mixture is sharper than the absorption peaks of the near-infrared absorbing agents of the examples, and the absorption at 1000 nm or more is small.

Comparative Example 2 In Comparative Example 1, 2- (benzylamino) thiophenol (34.4 g, 159.66 mmol, 18 times equivalent) was used in place of 2- (n-octylamino) thiophenol. Was subjected to the same reaction and post-treatment as in Comparative Example 1 to obtain a near-infrared absorber (15.6 g).

The absorption spectrum of the mixture in chloroform is shown in (FIG. 7). As is clear from the figure, the absorption peak of the mixture is sharper than the absorption peaks of the near-infrared absorbing agents of the examples, and the absorption at 1000 nm or more is small.

Comparative Example 3 Instead of the near-infrared absorber produced in Example 1, Comparative Example 1
A heat ray-absorbing film was produced in the same manner as in Example 6 except that the near-infrared ray absorbing agent produced in 1. was used. The transmittance spectrum of the film is shown in (FIG. 8). As is clear from the figure, the absorption peak of the film is sharper than the absorption peaks of the films of Examples, and the absorption at 1000 nm or more is small.

Comparative Example 4 Copper phthalocyanine represented by the following formula (17) was synthesized according to the method described in JP-A-3-062878.

[0109]

[Chemical formula 23]

The absorption spectrum of the compound in chloroform is shown in (FIG. 9). As is clear from the figure, the absorption peak of the compound is sharper than the absorption peaks of the near-infrared absorbents of the examples, and the absorption at 1000 nm or more is small.

Comparative Example 5 Comparative Example 4 was used in place of the near infrared ray absorbent prepared in Example 2.
A heat ray absorbing film was produced in the same manner as in Example 7 except that the phthalocyanine produced in 1. was used. The transmittance spectrum of the film is shown in (FIG. 10). As is clear from the figure, the absorption peak of the film is sharper than that of the films of Examples, and is 1000 nm.
The above absorption is not seen.

Comparative Example 6 Penta (phenyl-1-amino-2-thio-ylene) -penta (2-aminophenylthio) -copper phthalocyanine was produced according to the method of JP-B-4-75916. Using the compound according to the method of Example 6 and Example 7,
Attempts were made to prepare a PET kneading film and a PET coating film, but the solubility of the compound in the resin was low, and a transparent film could not be formed due to the clouding phenomenon.

[0113]

INDUSTRIAL APPLICABILITY The present invention has a high light resistance and a high dissolution type, has a wide absorption in the near infrared region of 700 to 1800 nm, and produces a near infrared absorbing resin composition or a heat ray absorbing filter. It is intended to provide a method for simply producing a phthalocyanine-based near-infrared absorbing compound that is effective for, and is an extremely valuable method in practical use.

[Brief description of drawings]

FIG. 1 is an absorption spectrum of the near-infrared absorption mixture obtained in Example 1.

FIG. 2 is an absorption spectrum of the near-infrared absorption mixture obtained in Example 2.

FIG. 3 is an absorption spectrum of the near-infrared absorption mixture obtained in Example 3.

FIG. 4 is a transmittance spectrum of the heat ray absorbing film obtained in Example 6.

5 is a transmittance spectrum of the heat ray absorbing film obtained in Example 7. FIG.

FIG. 6 is an absorption spectrum of the near-infrared absorption mixture obtained in Comparative Example 1.

FIG. 7 is an absorption spectrum of the near-infrared absorption mixture obtained in Comparative Example 2.

FIG. 8 is a transmittance spectrum of the heat ray absorbing film obtained in Comparative Example 3.

FIG. 9 is an absorption spectrum of the near-infrared absorption mixture obtained in Comparative Example 4.

10 is a transmittance spectrum of the heat ray absorption film obtained in Comparative Example 5. FIG.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁶ Identification code Internal reference number FI Technical display location G02C 7/10 G02C 7/10 G11B 7/24 516 8721-5D G11B 7/24 516 (72) Invention Person Keisuke Soma, 1190 Kasama-cho, Sakae-ku, Yokohama-shi, Kanagawa Mitsui Toatsu Chemical Co., Ltd.

Claims (9)

[Claims] 1. A phthalocyanine-based near-infrared absorber having a wide absorption in the near-infrared region represented by the general formula (1). Embedded image [In the formula, R ¹ and R ² represent a hydrogen atom, a substituted or unsubstituted alkyl group, or a substituted or unsubstituted arule group, and Y is independently a substituted or unsubstituted alkyl group,
A substituted or unsubstituted aryl group, a substituted or unsubstituted alkoxy group, or a substituted or unsubstituted aryloxy group, m represents an integer of 0 to 4, Pc represents a phthalocyanine nucleus, and Z represents -SH. Group or a —NHR ³ group (R ³ represents a hydrogen atom, a substituted or unsubstituted alkyl group, or a substituted or unsubstituted aryl group), and Xs are each independently a halogen atom, a hydroxyl group, a substituted or unsubstituted group. An alkoxy group, a substituted or unsubstituted aryloxy group, a substituted or unsubstituted alkylthio group, a substituted or unsubstituted arylthio group, a substituted or unsubstituted alkylamino group, a substituted or unsubstituted arylamino group, a substituted or unsubstituted It represents a substituted alkylarylamino group, and adjacent Xs may form a 5-membered ring or a 6-membered ring through two hetero atoms, and Represents a divalent metal atom or a trivalent or tetravalent substituted metal or oxymetal, and p is 1
Is an integer of 0 to 16, q is an integer of 0 to 8, r is an integer of 0 to 8, and p + 2q + r ≦ 16. ] 2. A near infrared region obtained by reacting a phthalocyanine represented by the general formula (2) with at least one 2-aminothiophenol derivative represented by the general formula (3) in the presence of a base. The method for producing a phthalocyanine-based near-infrared absorbing agent according to claim 1, which has a wide absorption in. Embedded image [In the formula, each X independently represents a halogen atom, a hydroxyl group, a substituted or unsubstituted alkoxy group, a substituted or unsubstituted aryloxy group, a substituted or unsubstituted alkylthio group, a substituted or unsubstituted arylthio group, a substituted or unsubstituted It represents a substituted alkylamino group, a substituted or unsubstituted arylamino group, a substituted or unsubstituted alkylarylamino group, and adjacent Xs may form a 5-membered ring or a 6-membered ring through two heteroatoms, n represents an integer of 4 to 16, and M represents a divalent metal atom or a trivalent or tetravalent substituted metal or oxymetal. However, at least four of X are halogen atoms. ] [Chemical 3] [Wherein, R ¹ and R ² represent a hydrogen atom, a substituted or unsubstituted alkyl group, or a substituted or unsubstituted aryl group, and Y's each independently represent a substituted or unsubstituted alkyl group,
Substituted or unsubstituted aryl group, a substituted or unsubstituted alkoxy group, or a substituted or unsubstituted aryloxy group, Z is -SH group or -NHR ³ group (R ³ is a hydrogen atom, a substituted or unsubstituted Alkyl group of, or
Represents a substituted or unsubstituted aryl group), and m is 0.
~ Represents an integer of 4] 3. The method for producing a near infrared absorbent according to claim 2, wherein the 2-aminothiophenol derivative is a compound represented by the following formula (4). [Chemical 4] [In the formula, R ¹ and R ² represent a hydrogen atom, a substituted or unsubstituted alkyl group, or a substituted or unsubstituted aryl group. ] 4. M is Cu, AlCl, TiO or VO
The method for producing a near-infrared absorber according to claim 2. 5. The method for producing a near infrared absorbent according to claim 2, wherein X is a halogen atom. 6. The phthalocyanine represented by the general formula (2) 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 absorber according to claim 5. 7. A phthalocyanine-based near-infrared absorber having a wide absorption in the near-infrared region, which is produced by the production method according to claim 2. 8. A near infrared absorbing resin composition containing the near infrared absorbing agent according to claim 1. 9. A heat ray absorption filter containing the near-infrared ray absorbing agent according to claim 1.