JP2000229980A - Phthalocyanine-based compound and its use - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a new phthalocyanine-based compound excellent in absorptivity of near infrared rays, light stability and compatibility with solvent and resin, and useful as a near infrared rays-absorbing material for optical cards or the like. SOLUTION: This new phthalocyanine-based compound is expressed by formula I [wherein, R1-R8 are each H, a (substituted)alkyl, a (substituted)aryl, a (substituted)alkoxy or a (substituted)aryloxy; X is O, S or N-R9 (wherein, R9 is H, an alkyl or the like); Y is H, a halogen, hydroxyl group, a (substituted) alkoxy, a (substituted)aryloxy or the like; (n) is 1-8, (l) is 0-14 and (m) is 0-14 with proviso that 2(n)+(l)+(m)=16; and M is 2H, a divalent metal atom, a tri-or tetra-valent (substituted)metal or an oxymetal], e.g. a compound of formula II. The compound of formula I is obtained by reacting a phthalocyanine compound of formula III with at least one of compounds of formula IV and V in a solvent such as dimethylformamide in the presence of a base such as sodium carbonate.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a phthalocyanine compound excellent in durability and excellent in solubility and easy to process. The present invention also relates to a near infrared absorbing resin composition containing the phthalocyanine compound and a near infrared absorbing material containing the compound. Specifically, optical cards, security inks, optical recording media, organic photoconductors, near-infrared absorbing filters, heat-shielding films, agricultural films,
It can be applied to applications that require near-infrared absorption, such as photothermal conversion materials.

[0002]

2. Description of the Related Art Phthalocyanine compounds are used for recording layers of optical recording media such as optical disks, and for photothermal conversion materials that absorb near infrared rays such as laser light, xenon lamps or infrared lamps and convert them to heat. Further, the ink can be used as a near-infrared absorbing ink which can be read by a near-infrared detector. In addition, by combining with a binder resin, it is made into a paint and coated on plastic or glass, or kneaded with the resin to form a near-infrared absorption filter (a near-infrared absorption filter for display materials such as plasma displays, a cut filter for CCD cameras, etc.). It can also be manufactured.

[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 region, it is possible to control the growth of plants as an agricultural film with selective use of light quality, to cut infrared rays from semiconductor light-receiving elements, to protect the human body from rays containing harmful infrared rays, or to display (plasma display). It can also be used for various filters to cut off the infrared rays generated from.

[0004] As a compound that absorbs near infrared rays, a cyanine compound has been well known. However, since the cyanine-based compound has extremely low light fastness, it is inevitably subject to many restrictions when it is used. Aminium compounds and dithiol metal complex compounds are insufficient in heat resistance and light resistance. Anthraquinone compounds also have heat resistance, but are insufficient in light absorption characteristics in the near infrared region.

Various phthalocyanine compounds having relatively good properties have been studied, but they have not yet been able to satisfy all of high light resistance, high solubility, and high near infrared absorption properties. . For example, in Japanese Patent Publication No. 4-75916 and JP-A-63-308073, a near-infrared absorbing compound is obtained by reacting a chlorinated copper phthalocyanine compound with 2-aminothiophenols. However, they have problems such as low solubility in organic solvents or resins and insufficient durability.

[0006]

An object of the present invention is to provide a novel phthalocyanine compound. Furthermore, it can be applied to applications that require near-infrared absorption such as optical cards, security inks, optical recording media, organic photoconductors, near-infrared absorption filters, heat ray shielding films, agricultural films, and photothermal conversion materials. Another object of the present invention is to provide a near-infrared absorbing compound effective as a suitable near-infrared absorbing material.

[0007]

Means for Solving the Problems The present inventors have conducted intensive studies to solve the above-mentioned problems, and as a result, by introducing at least one mercaptobenzimidazole into a phthalocyanine skeleton, a phthalocyanine-based compound having high light resistance has been obtained. The present inventors have found that a novel phthalocyanine-based compound having high solubility can be obtained by introducing a compound and further a compound having a nitrogen atom having a substituent, and have completed the present invention.

That is, the present invention relates to a novel phthalocyanine compound represented by the following general formula (1).

[0009]

Embedded image

[Wherein, R _{1 to} R ₈ each independently represent a hydrogen atom, an optionally substituted alkyl group, an optionally substituted aryl group, an optionally substituted alkoxy group, or a substituted X represents an oxygen atom, a sulfur atom, or N—R ₉ each independently, and R ₉ each independently represents a hydrogen atom, an optionally substituted alkyl Group, an optionally substituted aryl group, an optionally substituted alkylcarbonyl group, and an optionally substituted arylcarbonyl group, each of which independently represents a hydrogen atom, a halogen atom, a hydroxyl group, An optionally substituted alkoxy group, an optionally substituted aryloxy group, an optionally substituted alkylthio group, an optionally substituted arylthio group, an optionally substituted Kiruamino group, substituted indicates which may arylamino group, adjacent Y may form a 5- or 6-membered ring through two hetero atoms. n represents an integer of 1 to 8, 1 represents an integer of 0 to 14, m represents an integer of 0 to 14, and 2n + 1 + m = 16. M represents two hydrogen atoms, a divalent metal atom or 3
It represents a substituted or tetravalent substituted metal or oxymetal. ]

Further, the present invention relates to a near infrared absorbing resin composition and a near infrared absorbing material containing the phthalocyanine compound.

[0012]

BEST MODE FOR CARRYING OUT THE INVENTION In the phthalocyanine compound represented by the general formula (1), R _{1 to} R ₈ each independently represent a hydrogen atom, an alkyl group which may be substituted, X represents an optionally substituted aryl group, an optionally substituted alkoxy group, or an optionally substituted aryloxy group, and X independently represents an oxygen atom, a sulfur atom, or NR ₉ ; ₉ each independently represents a hydrogen atom, an alkyl group which may be substituted, an aryl group which may be substituted, an alkylcarbonyl group which may be substituted, an arylcarbonyl group which may be substituted; Y is each 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 An arylthio group which may be substituted, an alkylamino group which may be substituted, and an arylamino group which may be substituted, wherein adjacent Y forms a 5- or 6-membered ring through two heteroatoms; You may. n represents an integer of 1 to 8, 1 represents an integer of 0 to 14, m represents an integer of 0 to 14, 2n + 1 + m
= 16. M represents two hydrogen atoms, a divalent metal atom, or a trivalent or tetravalent substituted metal or oxymetal.

The halogen atom includes fluorine, chlorine, bromine and iodine.

The alkyl group which may be substituted is not particularly restricted but includes, for example, 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, 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, 2- (4-
Morpholinyl) propyl group, 3- (4-morpholinyl) ethyl group, 2- (1-pyrrolidinyl) ethyl group,
-A pyridylmethyl group, a furfuryl group and the like.

The aryl group which may be substituted is not particularly restricted but includes, for example, a phenyl group,
Examples thereof include a 2-mercaptophenyl group, a 3-mercaptophenyl group, a 4-mercaptophenyl group, a 2-methylphenyl group, a 3-methylphenyl group, a 4-methylphenyl group, and a naphthyl group.

The alkoxy group which may be substituted is not particularly restricted but includes, for example, a methoxy group, an ethoxy group, an n-propoxy group, an iso-propoxy group, an n-butoxy group, an 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, 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. No.

The alkylcarbonyl group which may be substituted is not particularly restricted but includes, for example, acetyl, propionyl, butyryl, iso-butyryl, valeryl, iso-valeryl and trimethylacetyl. , A hexanoyl group, a t-butylacetyl group,
Heptanoyl, octanoyl, 2-ethylhexanoyl, nonanoyl, decanoyl, undecanoyl, lauroyl, tridecanoyl, tetradecanoyl, pentadecanoyl, hexadecanoyl, heptadecanoyl, octadecanoyl , Oleoyl group,
Cyclopentanecarbonyl group, cyclohexanecarbonyl group, 6-chlorohexanoyl group, 6-bromohexanoyl group, trifluoroacetyl group, pentafluoropropionyl group, perfluorooctanoyl group, 2,2,2
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 restricted but includes, for example, a benzoyl group, an o-chlorobenzoyl group, an m-chlorobenzoyl group, a p-chlorobenzoyl group and an o-fluorobenzoyl group. 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, Examples include an o-methylbenzoyl group, an m-methylbenzoyl group, a p-methylbenzoyl group, a pentafluorobenzoyl group, a 4- (trifluoromethyl) benzoyl group, and the like.

The alkylthio group which may be substituted is not particularly restricted but includes, for example, 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, cyclohexylthio, n-heptylthio, 2-ethylhexylthio, n-octylthio, n-nonylthio, methoxyethylthio, ethoxyethylthio, propoxyethylthio, butoxyethylthio, aminoethyl Thio group, n-butylaminoethylthio group, benzylaminoethylthio group, methylcarbonylaminoethylthio group, phenylcarbonylaminoethylthio, methylsulfonylaminoethylthio group, phenylsulfonylaminoethylthio group, dimethylaminoethylthio group, And a diethylaminoethylthio group.

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,
4-ethylphenylthio group, 4-propylphenylthio group, 4-t-butylphenylthio group, 4-methoxyphenylthio group, 4-ethoxyphenylthio group, 4-aminophenylthio group, 4-alkylaminophenylthio Group,
4-dialkylaminophenylthio, 4-phenylaminophenylthio, 4-diphenylaminophenylthio, 4-hydroxyphenylthio, 4-chlorophenylthio, 4-bromophenylthio, 2-methylphenylthio , 2-ethylphenylthio, 2-propylphenylthio, 2-t-butylphenylthio, 2
-Methoxyphenylthio 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-
And a phenylsulfonylaminophenylthio group.

The alkylamino group which may be substituted is not particularly limited. Examples thereof include a methylamino group, an ethylamino group, an n-propylamino group and an i-amino group.
Examples thereof include a so-propylamino group, a butylamino group, a pentylamino group, a dipentylamino group, a hexylamino group, a heptylamino group, an octylamino group, a nonylamino group, and a benzylamino group.

The arylamino group which may be substituted is not particularly restricted but includes, for example, phenylamino, 4-methylphenylamino, 4-methoxyphenylamino, hydroxyphenylamino, naphthylamino Group, phenylmethylamino group, phenylethylamino group, phenylpropylamino group and the like.

The substituents in which adjacent Y may form a 5- or 6-membered ring via two heteroatoms include the substituents represented by the following formulas.

[0025]

Embedded image

Although the divalent metal is not particularly limited, for example, Cu (II), Zn (II), Fe (I
I), Co (II), Ni (II), Ru (II), Rh (I
I), Pd (II), Pt (II), Mn (II), Mg (I
I), Ti (II), Be (II), Ca (II), Ba (I
I), Cd (II), Hg (II), Pb (II), Sn (I
I) and the like.

The monosubstituted trivalent metal is particularly limited.
Although not necessarily, for example, Al-Cl, Al-Br, A
1-F, Al-I, Ga-Cl, Ga-F, Ga-I,
Ga-Br, In-Cl, In-Br, In-I, In
-F, Tl-Cl, Tl-Br, Tl-I, Tl-F,
Al-C₆H_Five, Al-C₆H_Four(CH_Three), In-C
₆H _Five, In-C₆H_Four(CH_Three), In-C₆H_Five, Mn
(OH), Mn (OC₆H_Five), Mn [OSi (C
H_Three)_Three], Fe-Cl, Ru-Cl and the like.

The disubstituted tetravalent metal is particularly limited.
Although not necessarily, for example, CrCl _Two, SiCl_Two, Si
Br_Two, SiF_Two, SiI_Two, ZrCl_Two, GeCl_Two, G
eBr_Two, GeI_Two, GeF_Two, SnCl_Two, SnBr_Two,
SnF_Two, TiCl_Two, TiBr_Two, TiF_Two, Si (O
H)_Two, Ge (OH)_Two, Zr (OH)_Two, Mn (O
H)_Two, Sn (OH)_Two, TiR_Two, CrR_Two, SiR_Two,
SnR_Two, GeR_Two[R is an alkyl group, a phenyl group, a naph
Tyl group and its derivatives], Si (O
R ')_Two, Sn (OR ')_Two, Ge (OR ')_Two, Ti
(OR ')_Two, Cr (OR ')_Two[R 'is an alkyl group;
Phenyl, naphthyl, trialkylsilyl, dial
Alkylalkoxysilyl group and its derivative], S
n (SR ")_Two, Ge (SR ")_Two(R ″ is an alkyl group,
Phenyl, naphthyl, and derivatives thereof)
And so on.

The oxymetal is not particularly restricted but includes, for example, VO, MnO, TiO and the like. In a more preferred phthalocyanine compound of the formula (1), Y is each independently a hydrogen atom or a halogen atom, and R _{1 to} R ₈ are each independently a hydrogen atom or an optionally substituted alkyl group, 2l + m is 2
16, M is two hydrogen atoms, Cu, Fe, Pd,
AlCl, TiO or VO.

The phthalocyanine-based compound of the present invention comprises 70
It has an absorption maximum at 0 to 1000 nm, and the absorption maximum wavelength can be controlled according to the application. In particular, for applications using semiconductor lasers, 7
A phthalocyanine-based compound having an absorption maximum wavelength in the range of 00 to 1200 nm is preferable.

The phthalocyanine compound of the present invention includes, for example, a phthalocyanine compound represented by the following general formula (2) and a 2-mercaptobenzimidazole derivative represented by the following general formula (3), and a phthalocyanine compound represented by the following general formula (4) )) And a heterocyclic compound having a mercapto group. Specifically, the compound of the present invention includes a compound obtained by reacting a compound (2) with a compound (3), a compound obtained by reacting a compound (2) with a compound (4), a compound (2) and a compound (3) And then reacting the compound (4) with the compound (4), and simultaneously reacting the compound (2) with the compound (3) and the compound (4) to obtain a compound.

[0032]

Embedded image [In the above formula, R _{1 to} R ₈ , M, X, Y, and m are the same as defined above. ]

In the phthalocyanine compound represented by the general formula (2), those in which Y is a halogen atom are preferred. I. Pigment green
7, 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 reaction between the phthalocyanine compound represented by the general formula (2) and the heterocyclic compound represented by the general formula (3) and / or the general formula (4) is carried out by a conventional method,
Sodium hydroxide, potassium hydroxide, sodium carbonate,
The reaction can be performed in the presence of a base such as potassium carbonate, sodium hydride, potassium t-butoxide and the like. Alternatively, when the compound of formula (3) isolated as a sodium salt, a potassium salt or a zinc salt is used, the amount of the base used can be reduced or the reaction can be carried out without using the base at all.

This reaction is usually carried out in a solvent, and the solvent used in this case is a polar solvent such as dimethylformamide (DMF), dimethylsulfoxide (DMSO), N, N-dimethylimidazolidinone (DMI) or sulfolane. ,
Examples thereof include ketone solvents such as acetone and methyl ethyl ketone, and aromatic hydrocarbon solvents such as toluene, xylene, monochlorobenzene, and dichlorobenzene, which may be used alone or as a mixture.

The reaction is usually carried out by converting a phthalocyanine compound represented by the general formula (2) and a base (1 to 50 times equivalent to the phthalocyanine compound) in a solvent (1 to 100 times by weight to the phthalocyanine compound). After dissolving or suspending, and stirring, a heterocyclic compound represented by the general formula (3) and / or (4) (1 to 50 equivalents to the phthalocyanine compound) is added, and 50 ~ 250
Performed at ° C. The addition of the heterocyclic compound 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, after adding the heterocyclic compound and the base, the phthalocyanine compound may be added. One heterocyclic compound may be used, or several heterocyclic compounds may be mixed. The reaction may be carried out under normal pressure or under pressure. Further, when an amidation or imidation reaction is carried out, a method of adding an amidation reagent and / or an imidization reagent to a reaction mixture and subsequently performing a reaction, and a phthalocyanine compound once reacted with an intermediate 2-aminothiophenol derivative And then amidation or imidation reaction is performed.

In the former method, acetic anhydride, propionic anhydride, butanoic anhydride, pentanoic anhydride, hexanoic anhydride, heptanoic anhydride, heptanoic anhydride, and octanoic anhydride are used as amidating and / or imidizing reagents in the reaction mixture. Carboxylic acid anhydrides such as benzoic anhydride, carboxylic acid dianhydrides such as succinic anhydride, maleic anhydride, phthalic anhydride, ethyl acetate, propyl acetate, butyl acetate, ethyl propionate, ethyl butanoate, ethyl pentanoate Carboxylic acid esters such as ethyl hexanoate, ethyl heptanoate, ethyl octanoate diethyl succinate, diethyl maleate, diethyl phthalate, acetyl chloride, acetyl bromide, ethyl carbonyl chloride, propyl carbonyl chloride, butyl carbonyl chloride, pentyl carbonyl chloride , Cyclohexyl carbonyl chloride, may be heptyl carbonyl chloride (1-100 equivalents relative to the phthalocyanine compound) carboxylic acid halide such as benzoyl chloride is added, obtained by reacting. After the completion of the reaction, the desired compound is precipitated by discharging into water or an alcohol solution such as methanol, ethanol, propanol, butanol, pentanol and the like. The precipitated target substance is separated by suction filtration,
Further, washing with water and alcohol is performed to remove salts, residual bases, unreacted 2-aminothiophenol derivatives, unreacted amidating reagents or imidating reagents, etc.
The near infrared absorbing compound of the present invention is isolated.

In the latter method, the general formula (2)
And a reaction mixture of the heterocyclic compound represented by the general formula (3) and / or the general formula (4) was discharged into water or an alcohol solution of methanol, ethanol, propanol, butanol, pentanol, or the like to react. The phthalocyanine compound is precipitated. The precipitated compound is separated by suction filtration and further washed with water and alcohol to remove salt, residual base, unreacted heterocyclic compound represented by the general formula (3) and / or general formula (4), and the like. Remove, dry and isolate. Subsequently, the amidation or imidation reaction 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 raw material phthalocyanine compound is added in an amount of 1 to 100 times equivalent), and stirred and reacted in a temperature range of about 0 to 150 ° C. At this time, a reaction accelerator such as dimethylaminopyridine may be added. After completion of the reaction, the desired product is isolated in the same manner as in the former method.

The degree of progress of the reaction can be determined, for example, by measuring the maximum absorption wavelength λmax of the reaction solution.

The phthalocyanine compound of the general formula (1) of the present invention can be obtained as a single compound or as a mixture of several compounds having different numbers of n and m in the general formula (1). However, if necessary, it can be purified by column chromatography and used as a single compound. The phthalocyanine-based compound of the present invention is a compound having high light resistance, a high solubility type in a resin, a solvent, and the like, and a high dispersion type. Further, in the production method, an inexpensive pigment can be used as a starting material, and the reaction is simple.

Although the phthalocyanine compound of the present invention obtained by the above-mentioned production method is excellent in near-infrared absorbing ability even as a single compound, it can absorb a broader near-infrared wavelength region by mixing several kinds. Is possible, and shows a better near-infrared absorption ability. That is, by being composed of one or several kinds of the above-mentioned phthalocyanine-based compounds, application to a near-infrared absorbing paint or a near-infrared absorbing filter becomes easy, and it has excellent properties as a heat ray absorbing material. .

The method for producing a near-infrared resin composition or a near-infrared absorbing material using the above-mentioned phthalocyanine compound is not particularly limited.
Two methods are available. (1) A method in which a phthalocyanine-based compound is kneaded with a resin, and the mixture is heated and formed into a resin plate or film. (2) A method in which a paint containing a phthalocyanine compound is prepared and coated on a transparent resin plate, a transparent film, or a transparent glass plate. (3) A phthalocyanine compound is contained in the adhesive,
A method for producing a laminated resin plate, laminated resin film, laminated glass, and the like.

First, in the method (1) in which a phthalocyanine compound is kneaded with a resin and heat-molded, the resin material is preferably as transparent as possible when formed into a resin plate or a resin film. , Polystyrene, polyacrylic acid, polyacrylic acid ester, polyvinyl acetate, polyacrylonitrile, polyvinyl chloride, polyvinyl fluoride, and other vinyl resins, and addition polymers of vinyl compounds, polymethacrylic acid, polymethacrylic acid ester, polyvinylidene chloride , Polyvinylidene fluoride, polyvinylidene cyanide, vinylidene fluoride / trifluoroethylene copolymer, vinylidene fluoride /
Copolymers of vinyl compounds or fluorine compounds such as tetrafluoroethylene copolymers, vinylidene cyanide / vinyl acetate copolymers, and resins containing fluorine such as polytrifluoroethylene, polytetrafluoroethylene, and polyhexafluoropropylene; Nylon 6, polyamide 66 such as nylon 66, polyimide, polyurethane, polypeptide,
Examples include polyesters such as polyethylene terephthalate, polyethers such as polycarbonate, polyoxymethylene, polyethylene oxide, and polypropylene oxide, epoxy resins, polyvinyl alcohol, polyvinyl butyral, and the like, but are not limited to these resins.

Although the processing temperature, film forming conditions, and the like are somewhat different depending on the base resin used, the phthalocyanine compound is usually added to powder or pellets of the base resin, and heated and dissolved at 150 to 350 ° C. After molding or extrusion molding to a thickness of 0.1-100
mm near infrared absorbing plate, 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. to 2 to 5 times. It is obtained by a method of forming a film having a thickness of 10 to 200 μm. In addition, the near-infrared absorbing material can be produced by cast polymerization of the phthalocyanine compound of the present invention with 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 addition amount of the phthalocyanine compound is
Although it depends on the thickness of the product to be manufactured, the desired absorption intensity, the desired heat ray transmittance, the desired visible transmittance, etc., it is usually 1 pp.
m to 10%.

In the method (2) for coating after coating, a method of dissolving the phthalocyanine compound of the present invention in a binder resin and an organic solvent to form a coating, and a method of pulverizing the phthalocyanine compound to several μm or less. ,
There is a method of using a water-based paint dispersed in an acrylic emulsion. The former method is usually an aliphatic ester resin, acrylic resin, melamine resin, urethane resin, aromatic ester resin, polycarbonate resin, aliphatic polyolefin resin, aromatic polyolefin resin, polyvinyl resin, polyvinyl alcohol resin, polyvinyl A modified resin (PVB, EVA, etc.) or a copolymer thereof is used as a binder. As the solvent, a halogen-based, alcohol-based, ketone-based, ester-based, aliphatic hydrocarbon-based, aromatic hydrocarbon-based, ether-based solvent, or a mixture thereof is used. The concentration of the phthalocyanine compound varies depending on the thickness of the coating, the desired absorption intensity, the desired heat ray transmittance, the desired visible transmittance, and the like, but is usually 0.1 to 100% based on the weight of the binder resin.
Also, the binder resin concentration is usually 1 to
50%. Similarly, the acrylic emulsion-based water-based paint can be obtained by dispersing a finely pulverized (50 to 500 nm) phthalocyanine-based compound in an uncolored acrylic emulsion paint. Additives such as an ultraviolet absorber and an antioxidant which are usually used in paints may be added to the paints. The paint prepared by the above method is a transparent resin film, a transparent resin, a transparent coater, a bar coater, a blade coater, a spin coater, a reverse coater,
A heat ray absorbing filter is prepared by coating with a die coater or spray. It is also possible to provide a protective layer to protect the coating surface, or to bond the coating surface to a transparent resin plate, a transparent resin film, or the like. A cast film is also included in the method.

In the method (3) for producing a laminated resin plate, a laminated resin film, a laminated glass, etc. by incorporating a phthalocyanine compound into an adhesive, the adhesive may be a common silicone, urethane or acrylic. Polyvinyl butyral adhesive (PVB), ethylene-vinyl acetate adhesive (E
Known transparent adhesives for laminated glass such as VA) can be used. Resin plates, a resin plate and a resin film, using an adhesive containing 0.1 to 50% of a phthalocyanine compound;
A heat ray absorbing filter is manufactured by bonding a resin plate and glass, a resin film, a resin film and glass, and a glass. There is also a method of thermocompression bonding.

The near-infrared absorbing material produced as described above is actually provided with an ultraviolet cut layer on one or both sides thereof.
A more practical filter can be obtained by providing a hard coat layer and an anti-reflection layer, and by providing an adhesive layer. In addition, if necessary, an infrared reflective layer in which metal oxides such as indium oxide, tin oxide, and zinc oxide and metals such as gold and silver are alternately laminated by sputtering, or a copper salt or a metal containing zinc oxide as a main component. Mixture, tungsten compound,
YbPO ₄ , ITO (tin-doped indium oxide), AT
O (tin-doped antimony oxide) or the like with an average particle size of 100 μm
Infrared reflective coatings made by atomizing below can also be combined with the near infrared absorbing material of the present invention.

[0048]

EXAMPLES Hereinafter, the present invention will be described in more detail with reference to Examples, but the present invention is not limited thereto. In the examples, "parts" indicates parts by weight.

Example 1 48.3 parts of a phthalocyanine compound represented by the following formula (a):
24 parts of mercaptobenzimidazole, potassium carbonate 2
2.1 parts were reacted in 483 parts of N, N-dimethyl-2-imidazolidinone at 130 ° C. for 15 hours. The reaction mixture was cooled to room temperature and then discharged into 500 parts of methanol. After collecting the precipitate by suction filtration, washing with methanol,
After washing with water and drying, 73 parts of a phthalocyanine compound represented by the following formula (b) were obtained. Further, purification was performed by column chromatography, and the maximum absorption wavelength (λmax) was measured, and it was 816 nm (solvent: DMF).

[0050]

Embedded image

[0051]

Embedded image

[0052]

[Table 1]

The phthalocyanine compound (b) was mixed with Unitika's polyethylene terephthalate pellets 1203 at a weight ratio of 0.03: 1, melted at 260 to 280 ° C., and extruded to form a 100 μm thick film. This film was biaxially stretched to produce a near-infrared absorbing filter having a thickness of 25 μm. According to JIS-R-3106, spectrophotometer UV-3100 manufactured by Shimadzu Corporation
When Tv (visible light transmittance) and Te (solar transmittance) of the filter were measured, they were 60% and 54%, respectively, and light of 700 to 900 nm was well absorbed. Also,
When a light fastness test was conducted with a carbon arc lamp (63 ° C.) for 1000 hours, almost no decrease in absorption due to decomposition of the dye was observed, and the light fastness was good.

Example 2 10 parts of the phthalocyanine compound (b) and 10,000 parts of polymethyl methacrylate (PMMA) (“Delpet 80N” (trade name), manufactured by Asahi Kasei Kogyo Co., Ltd.) were mixed.
The mixture was melted at 260 to 280 ° C., and a near-infrared absorbing filter having a thickness of 3 mm was prepared with an extruder. T of the filter
When v and Te were measured, they were 59% and 53%, respectively.
And well absorbed light of 700 to 900 nm. When a light resistance test was performed in the same manner as in Example 1, almost no decrease in absorption due to the decomposition of the dye was observed, and the light resistance was good.

Example 3 The phthalocyanine compound (b) obtained in Example 1 was charged into 300 parts of pyridine, 7.0 parts of acetyl chloride was added, and the mixture was reacted at 50 ° C. for 2 hours. The reaction mixture was ice water 10
Discharged to 00 parts. The precipitate was collected by suction filtration, washed with water and methanol, and then dried to obtain 29.4 parts of a phthalocyanine compound represented by the following formula (c). Further purification was performed by column chromatography, and λmax was measured to be 820 nm (solvent: DMF).

[0056]

Embedded image

[0057]

[Table 2]

As the near-infrared absorbing material, a near-infrared absorbing filter having a thickness of 25 μm was prepared in the same manner as in Example 1. When Tv and Te of the filter were measured, they were 58% and 54%, respectively, and were 700 to 900 n.
m was well absorbed. When a light resistance test was performed in the same manner as in Example 1, almost no decrease in absorption due to the decomposition of the dye was observed, and the light resistance was good.

Example 4 73.5 parts of a phthalocyanine compound represented by the following formula (d):
105.7 parts of mercaptobenzimidazole and 97.2 parts of potassium carbonate were reacted in 451 parts of N, N-dimethyl-2-imidazolidinone at 130 ° C. for 10 hours.
The reaction mixture was cooled to room temperature and then discharged into 500 parts of methanol. The precipitate was collected by suction filtration, washed with methanol, washed with water, and dried to isolate 26.5 parts of a phthalocyanine compound represented by the following formula (e). Further, purification was performed by column chromatography, and λmax was measured to be 824 nm (solvent: DMF).

[0060]

Embedded image

[0061]

Embedded image

[0062]

[Table 3]

As the near infrared absorbing material, a near infrared absorbing filter having a thickness of 25 μm was prepared in the same manner as in Example 1. When Tv and Te of the filter were measured, they were 55% and 48%, respectively, and light of 700 to 900 nm was well absorbed. When a light resistance test was performed in the same manner as in Example 1, almost no decrease in absorption due to the decomposition of the dye was observed, and the light resistance was good.

Example 5 25.6 parts of the phthalocyanine compound (e) and 1.0 part of 4-dimethylaminopyridine were added to 300 parts of pyridine, 13.0 parts of benzoyl chloride was added thereto, and reacted at 50 ° C. for 2 hours. . The reaction mixture was discharged into 1000 parts of ice water. The precipitate was collected by suction filtration, washed with water and methanol, and dried to obtain 30.4 parts of a phthalocyanine compound of the following formula (f). Further purification was performed by column chromatography, and λmax was measured.
m (solvent; DMF).

[0065]

Embedded image

[0066]

[Table 4]

Using the phthalocyanine compound (f), a near-infrared absorbing filter having a thickness of 25 μm was prepared in the same manner as in Example 1. When Tv and Te of the filter were measured, they were 54% and 48%, respectively.
0 nm light was well absorbed. When a light resistance test was performed in the same manner as in Example 1, almost no decrease in absorption due to the decomposition of the dye was observed, and the light resistance was good.

Example 6 Instead of using benzoyl chloride in Example 5, p-trifluoromethylbenzoyl chloride was used.
Except that 3 parts were used, the same reaction as in Example 5 was carried out to obtain 29.8 parts of a phthalocyanine-based compound represented by the following formula (g). Further purification was performed by column chromatography, and λmax was measured to be 844 nm (solvent: DM
F).

[0069]

Embedded image

[0070]

[Table 5]

2.0 parts of a phthalocyanine compound (g),
100 parts of "Tinuvin 329" (trade name, a benzotriazole-based ultraviolet absorber manufactured by Ciba Geigy Co., Ltd.), 100 parts of "Seasolve 501" (trade name, an ultraviolet absorber by Cipro Kasei Co., Ltd.), and porcarbonate ("pan" Light K
-1300Z "(trade name), manufactured by Teijin Limited 10000
The parts were melt-kneaded at 260 to 280 ° C., and a near-infrared absorbing filter having a thickness of 2 mm was produced using an extruder. 50 μm containing the filter and an ultraviolet absorber
A thick acrylic film was heat laminated. (The acrylic film is a benzotriazole ultraviolet absorber "Tinuvin P" (trade name, manufactured by Ciba Geigy Co., Ltd.)) 100 parts,
And "Ubinal 30", a cyanoacetic acid ultraviolet absorber
39 "(trade name, manufactured by BASF Corporation) and 100 parts of polymethyl methacrylate (PMMA) (" Delpet 80 ").
N "(trade name), manufactured by Asahi Kasei Kogyo Co., Ltd. (10000 parts), melted at 260 to 280 ° C., and a 200 μm-thick raw film was produced with an extruder. This film was biaxially stretched. Produced.

When Tv and Te of the filter were measured, they were 52% and 45%, respectively, and were 700 to 100%.
0 nm light was well absorbed. When a light resistance test was performed in the same manner as in Example 1, almost no decrease in absorption due to the decomposition of the dye was observed, and the light resistance was good.

Examples 7 to 32 The phthalocyanine compounds shown in Table 1 were produced in the same manner as in the above examples. Further, the performance evaluation results of the near-infrared absorbing material produced by the same method as in the above-mentioned example are shown. As a result, the near-infrared absorbing material using the phthalocyanine compound of the present invention well absorbed light of 700 to 1000 nm. Also, in the light resistance test performed in the same manner as in Example 1, almost no decrease in absorption due to the decomposition of the dye was observed, and the light resistance was good.

[0074]

[Table 6]

[0075]

[Table 7]

[0076]

[Table 8]

[0077]

[Table 9]

[0078]

[Table 10]

[0079]

[Table 11]

[0080]

[Table 12]

[0081]

The phthalocyanine compound of the present invention is a compound having an absorption maximum at 700 to 1000 nm and excellent in near-infrared absorption ability, and excellent in compatibility with solvents and resins and light resistance. Further, a near-infrared absorbing material using the compound is also a material having excellent near-infrared absorbing ability and durability, and in particular, to provide an excellent material for an application that preferably has an absorption maximum wavelength of 700 to 1200 nm. Is possible.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) C07F 15/00 C07F 15/00 C 4J002 C08K 5/378 C08K 5/378 4J030 C08L 101/16 C09B 47/20 C09B 47/20 C09K 3/00 105 C09K 3/00 105 G02B 5/22 G02B 5/22 C08G 75/04 // C08G 75/04 C08L 101/00 (72) Inventor Ryu Ooi Kasama-cho, Sakae-ku, Yokohama, Kanagawa Prefecture 1190 Address Mitsui Chemicals, Inc. VR41 VU29 VW02 4H050 AA01 AB92 AB93 WB14 WB21 4J002 BB03X BC03X BD04X BD10X BD13X BD14X BD15X BD16X BE0 2X BE06X BF02X BG01X BG04X BG05X BG09X BG10X CB00X CD00X CF06X CF19X CG00X CH02X CK02X CL01X CM04X CN01W EV086 EZ006 FD20W FD206 GL00 GN00 GP00 GS00 4J030 BA03 BA31 BB03 BB00

Claims (4)

[Claims] 1. A phthalocyanine compound represented by the general formula (1). Embedded image [Wherein, R _{1 to} R ₈ each independently represent a hydrogen atom, an optionally substituted alkyl group, an optionally substituted aryl group, an optionally substituted alkoxy group, or an optionally substituted X represents an oxygen atom, a sulfur atom, or N—R ₉ each independently, and R ₉ each independently represents a hydrogen atom, an optionally substituted alkyl group, Represents an optionally substituted aryl group, an optionally substituted alkylcarbonyl group, or an optionally substituted arylcarbonyl group, and Y is each independently a hydrogen atom, a halogen atom, a hydroxyl group, or an optionally substituted Good alkoxy group, optionally substituted aryloxy group, optionally substituted alkylthio group, optionally substituted arylthio group, optionally substituted alkylamino , Optionally substituted aryl amino group, adjacent Y may form a 5- or 6-membered ring through two hetero atoms. n represents an integer of 1 to 8, 1 represents an integer of 0 to 14, m represents an integer of 0 to 14, and 2n + 1 + m = 16. M represents two hydrogen atoms, a divalent metal atom, or a trivalent or tetravalent substituted metal or oxymetal. ] 2. In the formula (1), Y is each independently a hydrogen atom or a halogen atom, R _{1 to} R ₈ are each independently a hydrogen atom or an optionally substituted alkyl group, and 2n + 1 is 2 The phthalocyanine compound according to claim 1, wherein M is two hydrogen atoms, Cu, Fe, Pd, AlCl, TiO, or VO. 3. A near-infrared absorbing resin composition containing the phthalocyanine compound according to claim 1. 4. A near-infrared absorbing material containing the phthalocyanine compound according to claim 1.