JP3226504B2 - Phthalocyanine compound, its production method and its use - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a novel phthalocyanine compound, a method for producing the same, and its use. In detail, the present invention has a particularly high visible light transmittance, high cut efficiency of near infrared light, excellent near infrared absorption, excellent compatibility with resin, and heat resistance, light resistance,
The present invention relates to a phthalocyanine compound and a near-infrared absorbing dye excellent in properties such as weather resistance. The present invention also relates to a method for producing the phthalocyanine compound efficiently and with high purity.

Further, the present invention relates to one of the uses of the phthalocyanine compound or the near-infrared absorbing dye,
The heat ray shielding material containing the phthalocyanine compound or the near-infrared absorbing dye is described in detail. The present invention relates to a heat ray shielding material having a semi-transparent or transparent property and shielding heat rays.

[0003] The present invention also relates to another use invention of the phthalocyanine compound or the near-infrared absorbing dye, which is a filter for a plasma display comprising the phthalocyanine compound or the near-infrared absorbing dye. For details, see the near-infrared light (75
The present invention relates to a plasma display filter that cuts (0 to 1,100 nm) and prevents malfunction of peripheral electronic devices. More specifically, the present invention relates to a plasma display filter containing the phthalocyanine compound or the near-infrared absorbing dye which is a near-infrared absorbing agent, has a high visible light transmittance, and has a high efficiency of cutting off near-infrared light.

Further, the phthalocyanine compound or the near-infrared absorbing dye of the present invention is used as a near-infrared absorbing agent for a non-contact fixing toner such as flash fixing or a near-infrared absorbing agent for a heat-retaining thermal storage fiber. It has excellent effects.

The phthalocyanine compound or the near-infrared absorbing dye of the present invention is a near-infrared absorbing dye for writing or reading in an optical recording medium using a semiconductor laser, a liquid crystal display, an optical character reader, or the like. Infrared sensitizers, heat transfer agents such as thermal transfer / thermosensitive stencils, near-infrared absorption filters, anti-eye strain agents or photoconductive materials, etc. It exhibits excellent effects when used in therapeutic photosensitive dyes, color CRT selective absorption filters, color toners, ink-jet inks, barcode inks for falsification prevention, near-infrared absorption inks, and the like.

[0006]

2. Description of the Related Art In recent years, various uses of a heat ray shielding material that absorbs near infrared rays have been proposed, and materials having better performance are strongly demanded. The main uses are as follows.

Hitherto, materials such as methacrylic resin and polycarbonate resin have been used for so-called glazing applications such as windows, ceiling windows, doors or ceiling domes of buildings or vehicles due to their excellent transparency and weather resistance. However, since the heat ray transmittance in sunlight is high, for example, when exposed to direct sunlight, there is a disadvantage that the internal temperature rises significantly. For these reasons, what can suppress the rise in indoor temperature while sufficiently taking in visible light is desired.

[0008] At present, greenhouses and greenhouses are widely used in plant cultivation for the purpose of improving the harvest content of crops or changing the harvest time. One of the problems in these is to prevent the indoor temperature from rising, especially in summer. It is well known that light in the near-infrared region affects the regulation of plant growth, but the purpose of the regulation is to add an absorbing material in the near-infrared region. For these reasons, there is a need for an effective heat-shielding film that does not substantially block the transmission of visible light required for plant growth.

At present, near-infrared light is often used for driving or stopping electric products such as magnetic tapes, and it is necessary to shield external near-infrared light. Has been requested.

[0010] Infrared rays contained in sunlight or in rays emitted during display or welding of a computer terminal are harmful to human eyes. Therefore, sunglasses, general glasses, contact lenses, protective glasses, and the like having a heat ray shielding effect for the purpose of protecting human eyes are demanded.

[0011] Thus, some proposals have conventionally been made as heat ray shielding materials. As the resin used in that case, a transparent polycarbonate resin, an acrylic resin,
A vinyl chloride resin or the like is used depending on the purpose. On the other hand, as additives for shielding heat rays, for example, a large number of dyes and pigments having absorption in the near infrared region are known, and those using them are also proposed. However, all of them have a drawback that they have a strong absorption in the visible region and are therefore transparent.

In order to solve such a problem, for example, Japanese Patent Publication No. Sho 62-5190 proposes a method of adding a dye having a low absorption in the visible region. In order to obtain a heat ray shielding effect, a large amount must be added. Therefore, there is a problem that the transmittance of visible light is reduced and the transparency is impaired.
Also, JP-A-51-135886, JP-A-61-80
No. 106, Japanese Patent Application Laid-Open No. 62-903 and the like propose a method of adding a pigment having absorption in the near infrared region, but there is a problem in uniformity due to poor solubility and poor compatibility with the resin. Therefore, there is a problem that the use is limited.

[0013] In addition, a compound containing an inorganic pigment has been proposed, but it has a heat ray shielding effect, but its use is limited because haze remains and visible light transmittance is low. Further, Japanese Patent Application Laid-Open Nos. 1-161036, 3-227366, and the like also propose a method of containing tungsten hexachloride or the like. However, although these methods have good heat ray absorption effects, they have the drawback of poor light stability, and also have the problem that their application fields are limited due to their high cost.

Further, as can be seen from Japanese Patent Publication No. 43-25335, use of an infrared absorbing agent comprising an organic dye is considered. A heat ray shielding material using this infrared absorbing agent is transparent and has good workability. It is good. But,
As described in JP-B-43-25335, generally, organic infrared absorbing agents are decomposed at a temperature exceeding 200 ° C., and are restricted in handling such that they can be practically used only in cast polymerization. is there.

In order to solve the problem of the heat resistance of the infrared absorber, for example, as disclosed in JP-A-3-161644, an infrared absorber having a low heat resistance is added to a transparent resin having a low molding temperature. For example, a method has been considered in which a film is formed from a material, and a laminate is formed by heat laminating a transparent resin plate having a high molding temperature. However, this method does not substantially solve the problem of heat resistance of the infrared absorbent. Further, the film containing the infrared absorbent is made by cast polymerization, and is considerably expensive.

To solve the above-mentioned problems, Japanese Patent Application Laid-Open No. 6-264050 discloses a technique proposed by the present inventors.
JP-A-6-25548 and JP-A-5-345861 disclose a heat ray shielding material containing a phthalocyanine compound having excellent near-infrared absorption, excellent compatibility with resin, and excellent heat resistance and light resistance. It has been disclosed. The heat ray shielding material containing the phthalocyanine compound transmits visible light relatively well, and is excellent in heat ray shielding effect, and is used for a building or a vehicle window, a ceiling window, a door, a car garage, a ceiling dome,
Horticultural greenhouses, resin plates for the purpose of having a translucent or transparent and shielding heat rays, such as sunglasses or safety glasses,
It can be used as a sheet or a film (however, as described later, the present inventors have proposed in Japanese Patent Application Laid-Open Nos. Hei 6-264050, Hei 6-25548, Hei 5-3455861). As a result of examining the inventions disclosed in Japanese Patent Application Laid-Open No. H06-26450 in more detail, among the compounds whose specific examples and examples are not disclosed at all in the specification, JP-A-6-264050 and JP-A-6-255
No. 48, a phthalocyanine compound exhibiting a remarkable effect that the visible light transmittance is excellent as compared with the effects disclosed in JP-A-5-345861 and the like, and as a result of further intensive studies on these compounds In other technical fields (applications) shown below, it has been found that a remarkable effect of increasing transparency can be obtained. ).

On the other hand, separate from the above technical field,
No. 70129 discloses that 16 substitutable positions of a phthalocyanine nucleus are represented by 15 in any of SR and NHR (R is a substituted or unsubstituted organic group such as an alkyl group or an aryl group).
One that has been individually substituted is disclosed. It is stated that it is useful for absorbing electromagnetic radiation from a laser source and can be used, for example, for coating optical data storage disks. Further, Japanese Patent Application Laid-Open Nos. H6-264050 and H6-255.
As with the compounds disclosed in JP-A-48-48, JP-A-5-345861 and the like, the visible light transmittance is not sufficient.

Further, in recent years, plasma displays have attracted attention for use in large-size thin televisions and thin displays, and have begun to appear on the market. However, there is a problem that near-infrared light emitted from the plasma display acts on peripheral electronic devices such as a cordless phone and a VCR using a near-infrared remote control, thereby causing a malfunction. However, it is known to produce a near-infrared absorbing filter using a near-infrared absorbing dye, but a specific method for preventing a malfunction due to a display is not enough, and the metal complex is described in JP-A-9-230134. There has been proposed a method for solving such problems using a plasma display filter containing a compound, but the metal complex compound has poor solubility and can be melt-kneaded at a high temperature of 260 ° C. or 280 ° C. It is not easily compatible, so there is a problem with the compatibility with the resin, and the amount of the resin added and the resin to be compatible are limited. While a plasma display filter to play is desired,
At present, no method has been proposed to address such a problem using a plasma display filter containing a phthalocyanine compound that can be a near-infrared absorber.

[0019]

SUMMARY OF THE INVENTION The present invention has been made in view of the above-mentioned circumstances of the prior art in each field of application (application) of phthalocyanine compounds.

That is, an object of the present invention is to solve the technical problems in each field of application (application) of such a phthalocyanine compound. In particular, the present invention has a high visible light transmittance and a high efficiency in cutting near infrared light. An object of the present invention is to provide a phthalocyanine compound and a near-infrared absorbing dye which are high, have excellent selective absorption in the near infrared region, have excellent compatibility with resins, and are also excellent in heat resistance, light resistance and weather resistance.

Similarly, the object of the present invention is to provide a near-infrared region (75
(Absorption wavelength range from 0 to 1100 nm), the absorption wavelength can be controlled according to the purpose, and a solvent according to the application, for example, a hydrophilic solvent; an alcoholic solvent or a lipophilic solvent; ketones, aromatic hydrocarbons It is intended to provide a phthalocyanine compound and a near-infrared absorbing dye excellent in solubility in a system solvent.

Another object of the present invention is to provide a method for producing the phthalocyanine compound efficiently and with high purity.

Still another object of the present invention is to selectively absorb light in the near-infrared region and effectively block heat from sunlight while keeping the transmittance in the visible region relatively high. It is intended to provide an inexpensive heat ray shielding material. That is, by developing a transparent resin containing a novel phthalocyanine compound excellent in selective absorption ability in the near infrared region, excellent in compatibility with the resin, and excellent in heat resistance, light resistance, and light resistance, the heat ray is developed. It is intended to provide a material that exhibits an excellent effect as a shielding material.

Still another object of the present invention is to provide a heat ray shielding material which can be widely used in various fields of application by using inexpensive organic materials as materials constituting the heat ray shielding material. is there. Further, by providing a phthalocyanine compound having excellent heat resistance, a heat ray shielding material that can be produced by a molding method having excellent productivity such as injection molding and extrusion molding using a general thermoplastic resin. To provide.

[0025] Still another object of the present invention is to provide:
It cuts light in the near-infrared region of 750 to 1,100 nm, preferably 800 to 1000 nm, which is a near-infrared region that causes malfunctions of peripheral electronic devices appearing on the display, and has a high visible light transmittance so as not to impair the sharpness of the display. An object of the present invention is to provide a practical plasma display filter.

[0026]

As described above, the present inventors have conducted intensive studies to solve the technical problems of the prior art in each field of application (application) of phthalocyanine compounds, and as a result, have completed the present invention. It has been reached.

That is, the objects of the present invention are as follows:
This can be achieved by the method described in (8).

(1) The following general formula (1)

[0029]

Embedded image

(Where Z ₂ , Z ₃ , Z ₆ , Z ₇ , Z ₁₀ ,
Z ₁₁ , Z ₁₄ and Z ₁₅ independently represent SR ¹ , OR ² or a fluorine atom, and at least one of them represents SR ¹ or O
R ² represents Z ₁ , Z ₄ , Z ₅ , Z ₈ , Z ₉ , Z ₁₂ ,
Z ₁₃ and Z ₁₆ independently represent NHR ³ , SR ¹ , OR ² or a fluorine atom, and at least one represents NHR ³ , and at least one of Z _{1 to} Z ₁₆ represents a fluorine atom or OR ² And R ¹ , R ² , and R ^{3 each} independently may have a phenyl group which may have a substituent, an aralkyl group which may have a substituent or a substituent. Represents an alkyl group having 1 to 20 carbon atoms,
Represents a non-metal, a metal, a metal oxide or a metal halide. The phthalocyanine compound represented by).

(2) In the general formula (1),
The above (1), wherein four or all eight of Z ₂ , Z ₃ , Z ₆ , Z ₇ , Z ₁₀ , Z ₁₁ , Z ₁₄ , and Z ₁₅ are SR ¹ or OR ^2. The phthalocyanine compound according to the above.

(3) In the measurement of the transmission spectrum,
The above (1) or (2), wherein the visible light transmittance is 65% or more in a solution in which the concentration of the phthalocyanine compound is adjusted so that the minimum value of the transmittance at 750 to 1,100 nm is 5 to 6%. A near-infrared absorbing dye comprising the phthalocyanine compound described in 1. above.

(4) General formula (2)

[0034]

Embedded image

(Wherein Y represents SR ¹ or OR ² , and R ¹ and R ² independently represent a phenyl group which may have a substituent or an aralkyl which may have a substituent. 1-20 carbon atoms which may have a group or a substituent
Represents an alkyl group, ad is independently an integer of 0 to 2, and the sum of ad is an integer of 1 to 8,
M represents a metal, a metal, a metal oxide or a metal halide), a phthalocyanine compound represented by the formula:
₂ R ³ (where R ³ represents a phenyl group which may have a substituent, an aralkyl group which may have a substituent, or a carbon atom having 1 to 20 carbon atoms which may have a substituent. Characterized by reacting with an amino compound represented by the general formula (3):

[0036]

Embedded image

Wherein Z ₂ , Z ₃ , Z ₆ , Z ₇ , Z ₁₀ ,
Z ₁₁ , Z ₁₄ and Z ₁₅ independently represent SR ¹ , OR ² or a fluorine atom, and at least one of them represents SR ¹ or O
R ² represents Z ₁ , Z ₄ , Z ₅ , Z ₈ , Z ₉ , Z ₁₂ ,
Z ₁₃ and Z _{16 each} independently represent NHR ³ , SR ¹ , OR ² or a fluorine atom, and at least one represents NHR ³ , and R ¹ , R ² and R ³ independently represent a substituent. A phenyl group which may have, an aralkyl group which may have a substituent or an alkyl group having 1 to 20 carbon atoms which may have a substituent, wherein M is a metal-free, metal, Represents metal oxides or metal halides. )).

(5) Any one of the phthalocyanine compounds or near-infrared absorbing dyes described in (1) to (3) or the phthalocyanine compound represented by the above general formula (3) is added in an amount of 0 to 100 parts of the resin. A heat ray shielding material made of a resin containing 0.0005 to 20 parts by weight.

(6) The heat ray shielding material according to the above (5), wherein the resin is a transparent resin.

(7) The transparent resin is at least one selected from the group consisting of polycarbonate resin, poly (meth) acrylic resin, polyethylene resin, polyester resin, polystyrene resin and vinyl chloride resin. The heat ray shielding material according to the above (5) or (6), characterized in that:

(8) A plasma display filter containing any of the phthalocyanine compounds or near-infrared absorbing dyes described in (1) to (3) or the phthalocyanine compound represented by the general formula (3).

[0042]

BEST MODE FOR CARRYING OUT THE INVENTION The phthalocyanine compound of the present invention has the following general formula (1)

[0043]

Embedded image

(Where Z ₂ , Z ₃ , Z ₆ , Z ₇ , Z ₁₀ ,
Z ₁₁ , Z ₁₄ and Z ₁₅ independently represent SR ¹ , OR ² or a fluorine atom, and at least one of them represents SR ¹ or O
R ² represents Z ₁ , Z ₄ , Z ₅ , Z ₈ , Z ₉ , Z ₁₂ ,
Z ₁₃ and Z ₁₆ independently represent NHR ³ , SR ¹ , OR ² or a fluorine atom, and at least one represents NHR ³ , and at least one of Z _{1 to} Z ₁₆ represents a fluorine atom or OR ² And R ¹ , R ² , and R ^{3 each} independently may have a phenyl group which may have a substituent, an aralkyl group which may have a substituent or a substituent. Represents an alkyl group having 1 to 20 carbon atoms,
Represents a non-metal, a metal, a metal oxide or a metal halide. ) And the following general formula (3)

[0045]

Embedded image

(Wherein Z ₂ , Z ₃ , Z ₆ , Z ₇ , Z ₁₀ ,
Z ₁₁ , Z ₁₄ and Z ₁₅ independently represent SR ¹ , OR ² or a fluorine atom, and at least one of them represents SR ¹ or O
R ² represents Z ₁ , Z ₄ , Z ₅ , Z ₈ , Z ₉ , Z ₁₂ ,
Z ₁₃ and Z _{16 each} independently represent NHR ³ , SR ¹ , OR ² or a fluorine atom, and at least one represents NHR ³ , and R ¹ , R ² and R ³ independently represent a substituent. A phenyl group which may have, an aralkyl group which may have a substituent or an alkyl group having 1 to 20 carbon atoms which may have a substituent, wherein M is a metal-free, metal, Represents metal oxides or metal halides. ), A phthalocyanine compound represented by the formula:
Hereinafter, this will be described in detail.

In the above general formula (1) or (3), R ¹ ,
R ² and R ³ are each independently a phenyl group which may have a substituent, an aralkyl group which may have a substituent, or a carbon atom having 1 to 20 carbon atoms which may have a substituent. Represents an alkyl group.

Examples of the substituent which may be present on the phenyl group or the aralkyl group include, for example, a halogen atom, an acyl group, an alkyl group, an alkoxy group, a halogenated alkyl group, a halogenated alkoxy group, a nitro group, and an amino group. Examples include, but are not limited to, groups, alkylamino groups, alkylcarbonylamino groups, arylamino groups, arylcarbonylamino groups, carbonyl groups, and alkoxycarbonyl groups. These substituents can be substituted on the phenyl group or the aralkyl group (the benzene nucleus) by 1 to 5 substituents. When a plurality of these substituents are substituted, they may be the same or different. In one example, the number of carbon atoms is 1 to
A phenyl or aralkyl group substituted with 1 to 3 alkyl groups, a phenyl or aralkyl group substituted with 1 to 2 alkoxy groups having 1 to 4 carbon atoms, a chlorine atom, a fluorine atom, etc. Examples thereof include a phenyl group or an aralkyl group substituted with 1 to 5 halogen atoms,
Some of the above substituents are shown below with more specific examples.

First, among the substituents that may be present on the phenyl group or the aralkyl group, the halogen atom is a fluorine atom, a chlorine atom, a bromine atom or an iodine atom, of which a fluorine atom is preferred.

Among the substituents that may be present on the phenyl group or the aralkyl group, acyl groups include acetyl, ethylcarbonyl, propylcarbonyl, butylcarbonyl, pentylcarbonyl,
Examples include a hexylcarbonyl group, a benzoyl group and a pt-butylbenzoyl group.

The alkyl group among the substituents optionally present on the phenyl group or the aralkyl group is a linear, branched or cyclic alkyl group having 1 to 20 carbon atoms. It is an alkyl group having 1 to 8 atoms. Specifically, a methyl group, an ethyl group, n
-Propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert-butyl group, n-
Pentyl group, isopentyl group, neopentyl group, 1,2
-Dimethylpropyl group, n-hexyl group, cyclohexyl group, 1,3-dimethylbutyl group, 1-isopropylpropyl group, 1,2-dimethylbutyl group, n-heptyl group, 1,4-dimethylpentyl group, 2- Examples thereof include a methyl-1-isopropylpropyl group, a 1-ethyl-3-methylbutyl group, an n-octyl group, and a 2-ethylhexyl group.

Among the substituents which may be present on the phenyl group or the aralkyl group, the alkoxy group is a linear, branched or cyclic alkoxy group having 1 to 20 carbon atoms, preferably a carbon atom having 1 to 20 carbon atoms. 1 to 8 alkoxy groups. Specifically, a methoxy group, an ethoxy group,
n-propoxy group, isopropoxy group, n-butoxy group, isobutoxy group, sec-butoxy group, tert-
Butoxy group, n-pentyloxy group, isopentyloxy group, neopentyloxy group, 1,2-dimethyl-propoxy group, n-hexyloxy group, cyclohexyloxy group, 1,3-dimethylbutoxy group, 1-isopropylpropoxy And the like.

Among the substituents which may be present on the phenyl group or the aralkyl group, a halogenated alkyl group means a straight-chain, branched-chain or cyclic alkyl group having 1 to 20 carbon atoms in which a part of halogen is substituted. It is a
Preferably, the alkyl group having 1 to 8 carbon atoms is partially halogenated. Specific examples include a chloromethyl group, a bromomethyl group, a trifluoromethyl group, a chloroethyl group, a 2,2,2-trichloroethyl group, a bromoethyl group, a chloropropyl group, and a bromopropyl group.

Among the substituents which may be present on the phenyl group or the aralkyl group, a halogenated alkoxy group means a straight-chain, branched-chain or cyclic alkoxy group having 1 to 20 carbon atoms in which a part of halogen is substituted. And preferably a part of an alkoxy group having 1 to 8 carbon atoms is halogenated. Specific examples include a chloromethoxy group, a bromomethoxy group, a trifluoromethoxy group, a chloroethoxy group, a 2,2,2-trichloroethoxy group, a bromoethoxy group, a chloropropoxy group, and a bromopropoxy group.

Among the substituents that may be present on the phenyl group or the aralkyl group, an alkylamino group is an alkylamino group having an alkyl moiety having 1 to 20 carbon atoms, preferably having 1 to 8 carbon atoms. It is an alkylamino group having two alkyl moieties. In particular,
Methylamino group, ethylamino group, n-propylamino group, n-butylamino group, sec-butylamino group, n
-Pentylamino group, n-hexylamino group, n-heptylamino group, n-octylamino group, 2-ethylhexylamino group and the like.

Among the substituents that may be present on the phenyl group or the aralkyl group, an alkoxycarbonyl group specifically means a methoxycarbonyl group, an ethoxycarbonyl group, an n-propoxycarbonyl group, an isopropoxycarbonyl group, and n-butoxycarbonyl, isobutoxycarbonyl, sec-butoxycarbonyl, tert-butoxycarbonyl and the like.

On the other hand, the unsubstituted alkyl group having 1 to 20 carbon atoms may be any of a linear, branched or cyclic alkyl group having 1 to 20 carbon atoms, and preferably has 1 to 20 carbon atoms. 1 to 8 alkyl groups. Specifically, a methyl group, an ethyl group, an n-propyl group, an isopropyl group,
n-butyl group, isobutyl group, sec-butyl group, te
rt-butyl group, n-pentyl group, isopentyl group, neopentyl group, 1,2-dimethylpropyl group, n-hexyl group, cyclohexyl group, 1,3-dimethylbutyl group, 1-isopropylpropyl group, 1,2- Examples thereof include a dimethylbutyl group, an n-heptyl group, a 1,4-dimethylpentyl group, a 2-methyl 1-isopropylpropyl group, a 1-ethyl-3-methylbutyl group, an n-octyl group, and a 2-ethylhexyl group.

Examples of the substituent which may be present in the alkyl group having 1 to 20 carbon atoms include, for example, a halogen atom, an alkoxy group, a hydroxyalkoxy group, an alkoxyalkoxy group and a halogenated alkoxy group. Can be Specific examples of these substituents are the same as the substituents optionally present on the phenyl group or the aralkyl group.

Next, in the above general formula (1) or (3), M represents a non-metal, a metal, a metal oxide or a metal halide. Here, “metal-free” means an atom other than a metal, for example, two hydrogen atoms. Examples of the metal include iron, magnesium, nickel, cobalt, copper, palladium, zinc, vanadium, titanium, indium, and tin. Examples of the metal oxide include titanyl and vanadyl. Examples of the metal halide include aluminum chloride, indium chloride, germanium chloride, tin chloride, and silicon chloride. M is preferably a metal, a metal oxide or a metal halide, and specifically, for example, copper, zinc, cobalt, nickel, iron, vanadyl, titanyl, chloroindium, and dichlorotin are preferably used. It is preferred to use copper, zinc, cobalt, vanadyl, dichlorotin. More preferably, it is preferable to use zinc, cobalt, vanadyl, and dichlorotin.

The above general formula (1) or (3)
In the phthalocyanine compound, Z _Two, Z_Three, Z₆, Z
₇, Z_Ten, Z₁₁, Z₁₄, Z_Fifteen(In this specification,
(It is also referred to as a substituent that substitutes at 8 positions in the anine nucleus.)
Is independently SR¹, OR^TwoOr a fluorine atom
And at least one is SR¹Or OR^TwoRepresented by
Things. In the present invention, eight positions of the phthalocyanine nucleus
At least one of SR
¹Or OR^Two(And the rest
Long wavelength of absorption wavelength)
And control of substitution position when substituting with amino compound later
And excellent compatibility with resin
Yes, preferably at the β-position of the phthalocyanine nucleus
4 or more SR as a substituent¹Or OR^TwoHave
And particularly preferably the β-position of the phthalocyanine nucleus.
And all eight substituents are¹Or OR^TwoPut in
What is replaced is desirable. Also, SR¹Replace with
OR than^TwoIt is preferable to replace with, because heat resistance is improved.
SR in β position in advance¹Or OR^TwoIf you replace with 8
When substituting with an amino compound later, good fluorine substitution
The amino compound is selectively substituted at the α-position from
Is more controllable, so that the absorption wavelength is more controllable.
New Note that SR¹Or OR^TwoOther substituents other than
Fluorine atoms replace hydrogen atoms and other halogen atoms.
Compared to resin, it has an excellent effect of improving compatibility with resin
In addition, it is due to the improvement of light resistance and heat resistance.

Similarly, Z₁, Z_Four, Z_Five, Z₈, Z₉,
Z₁₂, Z₁₃, Z₁₆(In this specification, the phthalocyanine nucleus
Eight substituents at the α-position) are independently
NHR^Three, SR¹, OR^TwoOr represents a fluorine atom,
And at least one is NHR ^ThreeIs represented by
You. In the present invention, the phthalocyanine nucleus is located at eight α-positions.
At least one NHR^ThreeHave
(And the rest is SR¹, OR^TwoOr
By limiting to fluorine atoms), longer absorption wavelength
And the effect of improving compatibility with the resin.
Preferably, the substitution at the α-position of the phthalocyanine nucleus
As a substituent, 3 to 8 NHRs^ThreeBy having
In addition, the absorption wavelength can be increased, and the compatibility with resin can be improved.
It has a remarkable effect on the top and is more desirable
It is.

Further, when the β-positions at the eight positions of the phthalocyanine nucleus are all substituted with SR ¹ and OR ² and all α-positions are substituted with NHR ³ , the absorption wavelength becomes extremely long, the absorption waveform becomes sharp, and visible light becomes visible. The transmittance is improved, which is preferable. In particular, it is preferable to replace all of the β-positions with OR ² and all of the α-positions with NHR ³ , because heat resistance is improved.

In the general formula (1), at least one of Z _{1 to} Z ₁₆ described above represents a fluorine atom, and is preferably a substituent substituted at eight α-positions of the phthalocyanine nucleus. It is preferable that the remaining 5 to 1 having ³ to 7 NHR ³ are all fluorine atoms. This is because the substitution of the fluorine atom as described above not only brings about an excellent effect of improving the compatibility with the hydrogen atom and other resins, but also improves the light resistance and heat resistance.

The substituents other than NHR ³ are replaced with SR ¹ , O
The use of R ² or a fluorine atom, and more preferably all of the remainder is a fluorine atom, has the effect of controlling the absorption wavelength (lengthening the wavelength), and can be easily synthesized and inexpensively manufactured. In addition to the effect of improving the compatibility with the resin as compared with a hydrogen atom or another halogen atom, the light resistance and the heat resistance are improved.

From the above constitutional requirements for Z _{1 to} Z ₁₆ , it is preferable that four or all eight substituents, particularly preferably eight, are substituted at the eight β-positions of the phthalocyanine nucleus.
All of them are SR ¹ or OR ² (for example, phenylthio group or phenoxy group), and the substituents to be substituted at the eight α-positions of the phthalocyanine nucleus are 3 to 8 amino compounds represented by NHR ³ , and the remaining 5 to 5 It is desirable that all zero atoms be fluorine atoms.

The phthalocyanine compound represented by the general formula (1)
Of which M is a non-metal (however,
Anine compounds are not limited to this, but
The exemplified phthalocyanine compound is a suitable gold other than metal-free
Metals, metal oxides or metal halides
To be specific, it goes without saying that
And the first and second groups described above. The following
In the compound of formula (3), positions 3 and 6
Position (Z₁, Z_Four, Z_Five, Z₈, Z₉, Z₁₂, Z ₁₃, Z₁₆
At the 4th and 5th positions.
Β position of the cyanine nucleus (Z_Two, Z_Three, Z₆, Z₇, Z_Ten, Z
₁₁, Z₁₄, Z_FifteenAt the substitution position). under
In the abbreviations of the above compounds, Pc represents a phthalocyanine nucleus.
Wherein Pc represents eight substituents which are later substituted at the β-position.
Followed by eight substituents substituted at the α-position. Group 1; (SR¹) And (NHR)^Three) Replaced lid
Russiannin · 4,5-octakis (phenylthio) -3,6- (pe
Abbreviated name: Pt (PhS)₈(PhNH)_FiveF_Three ・ 4,5-octakis (phenylthio) -3,6- (te
Trakisanilino-tetrafluoro) phthalocyanine Abbreviation; Pc (PhS)₈(PhNH)_FourF_Four ・ 4,5-octakis (phenylthio) -3,6- (g
Lisanilino-pentafluoro) phthalocyanine Abbreviation; Pc (PhS)₈(PhNH)_ThreeF_Five ・ 4,5-octakis (phenylthio) -3,6- (pe
Ntakis anisidino-trifluoro) phthalocyanine Abbreviation: Pc (PhS)₈(P-CH_ThreeOPhNH)_FiveF
_Three ・ 4,5-octakis (phenylthio) -3,6- (g
Lisanisidino-pentafluoro) phthalocyanine Abbreviation: Pc (PhS)₈(P-CH_ThreeOPhNH)_ThreeF
_Five ・ 4,5-octakis (phenylthio) -3,6- (f
Ptakisbenzylamino-monofluoro) phthalocyanine
Abbreviated name; Pc (PhS)₈(PhCH_TwoNH)₇F · 4,5-octakis (phenylthio) -3,6- (f
Xakisbenzylamino-difluoro) phthalocyanine Abbreviation: Pc (PhS)₈(PhCH_TwoNH)₆F_Two ・ 4,5-octakis (phenylthio) -3,6- (pe
(Nantakisbenzylamino-trifluoro) phthalocyanine
Abbreviated name; Pc (PhS)₈(PhCH_TwoNH)_FiveF_Three ・ 4,5-octakis (phenylthio) -3,6- (te
Trakisbenzylamino-tetrafluoro) phthalocyanine
Nin Abbreviation; Pc (PhS)₈(PhCH_TwoNH)_FourF_Four ・ 4,5-octakis (phenylthio) -3,6- (f
Ptakisbutylamino-monofluoro) phthalocyanine Abbreviation: Pc (PhS)₈(BuNH)₇F · 4,5-octakis (phenylthio) -3,6- (pe
Abbreviation; Pt (PhS)₈(BuNH)_FiveF_Three ・ 4,5-octakis (phenylthio) -3,6- (f
Xakisethoxyethanolamino-difluoro) lid
Russian Nin Abbreviation; Pc (PhS)₈(OHEtOEtNH)₆F_Two ・ 4,5-octakis (phenylthio) -3,6- (pe
N-butyl carbonylphenylamino-trifluoro
B) Phthalocyanine Abbreviation; Pc (PhS)₈(P-BuOOCPhNH)_Five
F_Three ・ 4,5-octakis (p-toluenethio) -3,6-
(Pentakisanilino-trifluoro) phthalocyanine Abbreviation: Pc (p-CH_ThreePhS)₈(PhNH)_FiveF_Three ・ 4,5-octakis (p-toluenethio) -3,6-
(Heptakisbenzylamino-monofluoro) phthalosi
Anine Abbreviation; Pc (p-CH_ThreePhS)₈(PhCH_TwoNH)
₇F · 4,5-octakis (p-toluenethio) -3,6-
(Hexakisbenzylamino-difluoro) phthalocyanine
Nin Abbreviation; Pc (p-CH_ThreePhS)₈(PhCH_TwoNH)
₆F_Two ・ 4,5-octakis (p-toluenethio) -3,6-
(Pentakisbenzylamino-trifluoro) phthalosi
Anine Abbreviation; Pc (p-CH_ThreePhS)₈(PhCH_TwoNH)
_FiveF_Three ・ 4,5-octakis (p-toluenethio) -3,6-
(Tetrakisbenzylamino-tetrafluoro) phthalo
Cyanine Abbreviation; Pc (p-CH_ThreePhS)₈(PhCH_TwoNH)
_FourF_Four ・ 4,5-octakis (butylthio) -3,6- (pen
Takisanilino-trifluoro) phthalocyanine Abbreviation: Pc (BuS)₈(PhNH)_FiveF_Three ・ 4,5-octakis (butylthio) -3,6-dis
(Butylthio) -3,6- (trisanilino-trifur
Oro) phthalocyanine Abbreviation; Pc (BuS)₈(BuS)_Two(PhNH)_ThreeF
_Three * 4,5- (trisbutylthio-pentafluoro)-
3,6- (heptakisbenzylamino-monofluoro)
Phthalocyanine Abbreviation: Pc (BuS)_ThreeF_Five(PhCH_TwoNH)₇F • 4,5- (tetrakisbutylthio-tetrafluoro)
-3,6- (pentakisbenzylamino-trifluoro)
B) Phthalocyanine Abbreviation: Pc (BuS)_FourF_Four(PhCH_TwoNH)_FiveF_Three • 4,5- (hexakisbutylthio-difluoro)-
3,6- (heptakisbutylamino-monofluoro) phenyl
Talocyanine Abbreviation: Pc (BuS)₆F_Two(BuNH)₇F • 4,5- (Heptakisbutylthio-fluoro) -3,
6- (pentakisbutylamino-trifluoro) phthalo
Cyanine Abbreviation; Pc (BuS)₇F (BuNH)_FiveF_Three ・ 4,5-octakis (phenylthio) -3,6- (f
Ptakisphenylethylamino-fluoro) phthalocyanine
Nin Abbreviation; Pc (PhS)₈(PhCH_TwoCH_TwoNH)₇F · 4,5-octakis (phenylthio) -3,6- (pe
Nantakisphenylethylamino-trifluoro) phthalo
Cyanine Abbreviation; Pc (PhS)₈(PhCH_TwoCH_TwoNH)_FiveF
_Three ・ 4,5-octakis (phenylthio) -3,6- ｛he
Ptakis (DL-1-phenylethylamino) -fluoro
Lophthalocyanine Abbreviation: Pc (PhS)₈｛Ph (CH_Three) CHNH｝₇
F · 4,5-octakis (phenylthio) -3,6- ｛pe
Nantakis (DL-1-phenylethylamino) -trif
Fluorophthalocyanine Abbreviation; Pc (PhS)₈｛Ph (CH_Three) CHNH｝_Five
F_Three ・ 4,5-octakis (phenylthio) -3,6- (f
Putakisbenzhydrylamino-fluoro) phthalocyanine
Nin Abbreviation; Pc (PhS)₈｛(Ph)_TwoCHNH｝₇F · 4,5-octakis (phenylthio) -3,6- (pe
Nantakis benzhydrylamino-trifluoro) phthalo
Cyanine Abbreviation; Pc (PhS)₈｛(Ph)_TwoCHNH｝_FiveF_Three ・ 4,5-octakis (phenylthio) -3,6- ｛te
Thrakis (DL-1-phenylethylamino) -tetra
Fluorophthalocyanine Abbreviation: Pc (PhS)₈｛Ph (CH_Three) CHNH｝_Four
F_Four ・ 4,5-octakis (phenylthio) -3,6- ｛te
Trakis (1,1,3,3-tetramethylbutylamido
D) -tetrafluorodiphthalocyanine Abbreviation: Pc (PhS)₈｛(CH_Three)_ThreeCH_TwoC (CH
_Three)_TwoNH｝_FourF_Four Group 2; (OR^Two) And (NHR)^Three) Replaced lid
Russiannin 4,5-octakis (phenoxy) -3,6- (pen
Takisanilino-trifluoro) phthalocyanine Abbreviation: Pc (PhO)₈(PhNH)_FiveF_Three ・ 4,5-octakis (phenoxy) -3,6- (tet
Lakisanilino-tetrafluoro) phthalocyanine Abbreviation; Pc (PhO)₈(PhNH)_FourF_Four 4,5-octakis (phenoxy) -3,6- (tri
Suanilino-pentafluoro) phthalocyanine Abbreviation; Pc (PhO)₈(PhNH)_ThreeF_Five ・ 4,5-octakis (phenoxy) -3,6- (pen
Takisanisidino-trifluoro) phthalocyanine Abbreviation: Pc (PhO)₈(P-CH_ThreeOPhNH)_FiveF
_Three 4,5-octakis (phenoxy) -3,6- (tri
Suanisidino-pentafluoro) phthalocyanine Abbreviation: Pc (PhO)₈(P-CH_ThreeOPhNH)_ThreeF
_Five ・ 4,5-octakis (phenoxy) -3,6- (hepc
Taxibenzylamino-monofluoro) phthalocyanine Abbreviation: Pc (PhO)₈(PhCH_TwoNH)₇F · 4,5-octakis (phenoxy) -3,6- (hex
(Sakisbenzylamino-difluoro) phthalocyanine Abbreviation: Pc (PhO)₈(PhCH_TwoNH)₆F_Two ・ 4,5-octakis (phenoxy) -3,6- (hex
(Sakisbenzylamino-difluoro) phthalocyanine Abbreviation: Pc (PhO)₈(PhCH_TwoNH)₆F_Two ・ 4,5-octakis (phenoxy) -3,6- (pen
Taxibenzylamino-trifluoro) phthalocyanine Abbreviation: Pc (PhO)₈(PhCH_TwoNH)_FiveF_Three ・ 4,5-octakis (phenoxy) -3,6- (tet
Lakisbenzylamino-tetrafluoro) phthalocyanine
Abbreviated name; Pc (PhO)₈(PhCH_TwoNH)_FourF_Four ・ 4,5-octakis (phenoxy) -3,6- (hepc
Taxibutylamino-monofluoro) phthalocyanine Abbreviation: Pc (PhO)₈(BuNH)₇F · 4,5-octakis (phenoxy) -3,6- (pen
Taxibutylamino-trifluoro) phthalocyanine Abbreviation: Pc (PhO)₈(BuNH)_FiveF_Three ・ 4,5-octakis (phenoxy) -3,6- (hex
Sakisethoxyethanolamino-difluoro) phthalo
Cyanine Abbreviation; Pc (PhO)₈(OHEtOEtNH)₆F_Two ・ 4,5-octakis (phenoxy) -3,6- (pen
Taxbutylcarbonylphenylamino-trifluoro
B) Phthalocyanine Abbreviation; Pc (PhO)₈(P-BuOOCPhNH)_Five
F_Three ・ 4,5-octakis (butoxy) -3,6- (penta
Quisanilino-trifluoro) phthalocyanine Abbreviation: Pc (BuO)₈(PhNH)_FiveF_Three ・ 4,5-octakis (butoxy) -3,6- (tris
Anilino-pentafluoro) phthalocyanine Abbreviation: Pc (BuO)₈(PhNH)_ThreeF_Five ・ 4,5-octakis (butoxy) -3,6- (hepta)
Kisbenzylamino-monofluoro) phthalocyanine Abbreviation: Pc (BuO)₈(PhCH_TwoNH)₇F • 4,5-octakis (butoxy) -3,6- (penta
Kisbenzylamino-trifluoro) phthalocyanine Abbreviation: Pc (BuO)₈(PhCH_TwoNH)_FiveF_Three 4,5- (trisbutoxy-pentafluoro) -3,
6- (Heptakisbutylamino-monofluoro) phthalo
Cyanine Abbreviation; Pc (BuO)_ThreeF_Five(BuNH)₇F · 4,5- (tetrakisbutoxy-tetrafluoro)-
3,6- (pentakisbutylamino-trifluoro) phenyl
Talocyanine Abbreviation: Pc (BuO)_FourF_Four(BuNH)_FiveF_Three, And
And 4,5- (tetrakisphenoxy-tetrafluoro)
-3,6- (hexakisbenzylamino-difluoro)
Phthalocyanine Abbreviation; Pc (PhO)_FourF_Four(PhCH_TwoNH)₆F_Two 4,5-octakis (p-cyanophenoxy) -3,
6- (Heptakisphenylethylamino-fluoro) phenyl
Talocyanine Abbreviation: Pc (p-CNPhO)₈(PhCH_TwoCH_TwoN
H)₇F • 4,5-octakis (p-cyanophenoxy) -3,
6- (pentakisphenylethylamino-trifluoro)
B) Phthalocyanine Abbreviation; Pc (p-CNPhO)₈(PhCH_TwoCH_TwoN
H)_FiveF_Three 4,5-octakis (p-cyanophenoxy) -3,
6-Heptakis (DL-1-phenylethylamino)
-Fluorophthalocyanine Abbreviation; Pc (p-CNPhO)₈｛Ph (CH_Three) CH
NH｝₇F • 4,5-octakis (p-cyanophenoxy) -3,
6- ｛pentakis (DL-1-phenylethylamino)
-Trifluorodiphthalocyanine Abbreviation: Pc (p-CNPhO)₈｛Ph (CH_Three) CH
NH｝_FiveF_Three 4,5-octakis (p-cyanophenoxy) -3,
6- (Heptakisbenzhydrylamino-fluoro) phenyl
Talocyanine Abbreviation: Pc (p-CNPhO)₈｛(Ph)_TwoCHN
H｝₇F • 4,5-octakis (p-cyanophenoxy) -3,
6- (pentakisbenzhydrylamino-trifluoro)
B) Phthalocyanine Abbreviation; Pc (p-CNPhO)₈｛(Ph)_TwoCHN
H｝_FiveF_Three ・ 4,5-octakis (2,5-dichlorophenoxy)
-3,6- ｛pentakis (DL-1-phenylethyla
Mino) -trifluorodiphthalocyanine Abbreviation: Pc (2,5-Cl_TwoPhO)₈｛Ph (C
H_Three) CHNH｝_FiveF_Three ・ 4,5-octakis (2,5-dichlorophenoxy)
-3,6- ｛hexakis (DL-1-phenylethyla
Mino) -difluorodiphthalocyanine Abbreviation; Pc (2,5-Cl_TwoPhO)₈｛Ph (C
H_Three) CHNH｝₆F_Two ・ 4,5-octakis (2,5-dichlorophenoxy)
-3,6- (octakisbenzylamino) phthalocyanine Abbreviation: Pc (2,5-Cl_TwoPhO)₈(PhCH_TwoN
H)₈ Similarly, the phthalocyanine compound of the above general formula (3)
Specific examples of those in which M is metal-free are
Those shown in groups 1 and 2; and 4,5-octakis (phenylthio) -3,6- (o
Ctakisbenzylamino) phthalocyanine Abbreviation: Pc (PhS)₈(PhCH_TwoNH)₈ And the like.

Next, the near-infrared absorbing dye or phthalocyanine compound according to the present invention has a minimum transmittance of 5 to 6 nm at 750 to 1,100 nm in transmission spectrum measurement.
% In a solution in which the concentration of the phthalocyanine compound has been adjusted so as to have a visible light transmittance of 65% or more.

That is, the near-infrared absorbing dye or phthalocyanine compound of the present invention has high visible light transmittance, excellent near-infrared absorbing ability, and high cut-off efficiency for near-infrared light. Furthermore, since it is excellent in compatibility with the resin, and has excellent properties such as heat resistance, light resistance, and weather resistance, it can be usefully used for a heat ray shielding material and a plasma display filter described below, It is also very useful as a near-infrared absorber for non-contact fixing toner such as flash fixing or for heat-retaining thermal storage fibers.

The phthalocyanine compound or near red of the present invention
Phthalocyanines that can be used in external absorption dyes
The compound is represented by the general formula (1) or (3).
For measurement of transmission spectrum among phthalocyanine compounds
The minimum value of the transmittance at 750 to 1,100 nm is 5
The concentration of the phthalocyanine compound is adjusted to
In the prepared solution, the visible light transmittance is 65% or more.
Preferably it is 70% or more. Near-infrared absorption of the present invention
As a preferred dye or phthalocyanine compound
Is 4 or 8 at the 8 beta positions of the phthalocyanine nucleus
All, particularly preferably all eight SR¹Or OR^Twoso
What was substituted, specifically, ZnPc (PhS)₈
(PhNH)_ThreeF_Five, ZnPc (PhS)₈(PhN
H)_FourF_Four, ZnPc (PhS)₈(PhNH)
_FiveF_Three, ZnPc (PhS)₈(PhCH _TwoNH)_FourF
_Four, ZnPc (PhS)₈(PhCH_TwoNH)_FiveF_Three,
ZnPc (PhS)₈(PhCH_TwoNH)₆F_Two, Cu
Pc (PhS)₈(PhNH)₇F, CuPc (Ph
S)₈(PhNH)₆F_Two, CuPc (PhS)₈(P
hNH)_FiveF_Three, VOPc (PhO)₈(PhCH_TwoN
H)_FiveF_Three, VOPc (PhO)₈(PhCH_TwoNH)
₆F_Two, VOPc (PhO)₈(PhCH_TwoNH)₈You
And VOPc (PhS)₈(PhCH_TwoNH)₈Abbreviation for
And the like. What
In the near-infrared absorbing dye of the present invention, measurement of the transmission spectrum was performed.
750 to 1,100 nm
And solvents for defining visible light transmittance
For example, chloroform, toluene, tetrahydrofuran,
Acetone or the like can be used. When other solvents are used
750 to 1, slightly different from the above solvent
The minimum value of 100 nm transmittance and visible light transmittance
Are given for each solvent, and these and the present invention
It goes without saying that they are not essentially different. Ma
The near-infrared absorbing dye or phthalocyanine compound of the present invention
750 to 1,100 nm transmittance in solution
The minimum value and visible light transmittance were the requirements.
The state of the cyanine compound (for example,
), The absorption spectrum differs depending on
The minimum value of the transmittance at 1,100 nm and the visible light transmittance are also
Due to some differences, heat shielding materials, plasma
Display filter, non-contact fixing toner or heat retention
The near infrared absorbing dye or phthalocyanine on the heat storage fiber
The use state of the compound, that is, the compatibility state in which the resin is dispersed
Considering the minimum value of the transmittance in use and the visible light
Above the solution state where the one that matches (approximately) matches the excess rate is given
This is a requirement.

The method for producing the phthalocyanine compound represented by the general formula (3) is not particularly limited, and it can be produced by appropriately utilizing a conventionally known method for producing a phthalocyanine compound. Is defined by the general formula (2)

[0071]

Embedded image

(Wherein Y represents SR ¹ or OR ² , and R ¹ and R ² are each independently a phenyl group which may have a substituent or an aralkyl which may have a substituent. 1-20 carbon atoms which may have a group or a substituent
Represents an alkyl group, ad is independently an integer of 0 to 2, and the sum of ad is an integer of 1 to 8,
M represents a metal, a metal, a metal oxide or a metal halide), a phthalocyanine compound represented by the formula:
₂ R ³ (where R ³ represents a phenyl group which may have a substituent, an aralkyl group which may have a substituent, or a carbon atom having 1 to 20 carbon atoms which may have a substituent. The compound can be synthesized by reacting with an amino compound represented by the following formula:

[0073] In the phthalocyanine compound of general formula (2), R ¹ and R ² as well as M of SR ¹ and OR ² are the general formula SR ¹ and OR ² in (3) R
¹ and the same as R ² and M. Further, R ³ of the amino compound NH ₂ R ³ used in the above manufacturing method is the same as R ³ of NHR ³ in the general formula (3).

In the above reaction, if necessary, the compound used in the reaction is mixed in the presence of an inert liquid which is not reactive,
It can be done by heating to a certain temperature,
Preferably, the reaction is carried out by heating to a certain temperature in the amino compound to be reacted. As the inert liquid, for example, nitriles such as benzonitrile and acetonitrile and amides such as N-methylpyrrolidone and dimethylformamide can be used.

In the above-mentioned reaction, a suitable optimum is introduced so that a desired substituent can be introduced as designed into the desired substitution position of Z _{1 to} Z ₁₆ of the phthalocyanine compound represented by the above general formula (3). Usually, the amino compound NH ₂ R ³ is equimolar to 1 mol of the phthalocyanine compound represented by the general formula (2) obtained by the reaction of the phthalonitrile compound with the metal compound. In the above range, inorganic components such as calcium carbonate, calcium fluoride and calcium hydroxide were added thereto, and 1 mole of the phthalocyanine compound represented by the above general formula (2) for trapping generated hydrogen fluoride. When the alkylamino compound is reacted in the range of 1 to 16 mol, preferably 3 to 8 mol based on the reaction temperature, the reaction temperature is 20 to 200 mol.
C., preferably 30-150.degree. C., and 80-250.degree. C., preferably 10
The reaction is performed in the range of 0 to 200 ° C. After the reaction, the inorganic component is filtered and the amino compound is distilled off (washed) according to a conventionally known synthesis method based on a substitution reaction of the phthalocyanine compound, thereby obtaining the desired phthalocyanine represented by the general formula (3). The compound can be obtained efficiently and with high purity without going through complicated production steps.

The method for synthesizing the phthalocyanine compound of the general formula (2) is not particularly limited, and it can be produced by appropriately utilizing a conventionally known method for synthesizing a phthalocyanine compound. Is obtained by applying a so-called phthalonitrile method in which phthalonitrile and a metal salt are reacted in a molten state or in an organic solvent. The following general formula (4)

[0077]

Embedded image

(Wherein Y represents SR ¹ or OR ² , and R ¹ and R ² are each independently a phenyl group which may have a substituent or an aralkyl which may have a substituent. 1-20 carbon atoms which may have a group or a substituent
Phthalonitrile compound or a precursor of a phthalocyanine compound derived from phthalonitrile, and a metal, a metal oxide or a metal halide. Is preferably synthesized by reacting

The phthalonitrile compound of the above general formula (4)
In, SR¹And OR^TwoR ¹And R^TwoIs on
SR of the general formula (3)¹And OR^TwoR¹And R^Two
Is the same as In the above general formula (4) which is the starting material,
The phthalonitrile compound shown is prepared by a known method, for example,
For example, nitrile solutions such as acetonitrile and benzonitrile
H which generates potassium fluoride, calcium carbonate, etc. in the medium
HSR used as a trapping agent for F¹, HOR^TwoThe nucleophile
Can be combined. Also, Japanese Unexamined Patent Publication No.
Can be produced by the method disclosed in US Pat.
You can also use commercially available ones.
You.

As the metal, metal oxide or metal halide (hereinafter also referred to as metal compound) used in the above-mentioned production method, those corresponding to M of the phthalocyanine compound of the general formula (3) obtained after the reaction can be used. It is not particularly limited as long as it can be obtained, for example, chloride, bromide, metal halide compounds such as iodide, metal oxides, organic acid metal salts such as acetates, complex compounds such as acetylacetonate , Metal carbonyl compounds, metal powders and the like.

In the process for producing a novel phthalocyanine compound of the present invention, the reaction between the phthalonitrile compound of the above general formula (4) and the above metal compound can be carried out without a solvent, but is preferably carried out using an organic solvent. . The organic solvent may be any inert solvent that is not reactive with the starting materials, for example, benzene, toluene, xylene,
Nitrobenzene, monochlorobenzene, dichlorobenzene, trichlorobenzene, 1-chloronaphthalene, 1-
Inert solvents such as methylnaphthalene, ethylene glycol, benzonitrile and the like or pyridine, N, N-dimethylformamide, N-methyl-2-pyrrolidinone, N, N
-Dimethylacetophenone, triethylamine, tri-
An aprotic polar solvent such as n-butylamine, dimethylsulfoxide, and sulfolane can be used, and preferred are 1-chloronaphthalene, 1-methylnaphthalene, and benzonitrile. Particularly preferred is benzonitrile.

In the reaction between the phthalonitrile compound of the general formula (4) and the metal compound, the phthalonitrile compound is preferably used in an amount of 2 to 40 parts, and more preferably 100 parts (hereinafter referred to as “parts by weight”) with the organic solvent. Is in the range of 20 to 35 parts,
The metal compound is added in an amount of 1 to 4 moles of the phthalonitrile compound.
To 2 mol, preferably 1.1 to 1.5 mol, and the reaction temperature is 30 to 250 ° C., preferably 80 to 20 mol.
React in the range of 0 ° C. After the reaction, the phthalocyanine compound that can be used in the next step can be obtained efficiently and with high purity by filtering, washing and drying according to a conventionally known method for synthesizing a phthalocyanine compound.

In the production method of the present invention, the above general formula (4)
The desired phthalocyanine compound represented by the general formula (3) can be produced by reacting the phthalocyanine compound of the general formula (2) synthesized from the phthalonitrile compound of the formula (1) with an amino compound. -SR ¹ or -OR ² group at β-position, -NH at α-position
It is characterized in that the R ³ group can be introduced accurately and the substitution position of the substituent can be controlled. Furthermore, in the production method of the present invention, as described above, the desired phthalocyanine compound represented by the general formula (3) can be produced efficiently and with high purity without going through complicated production steps. .

Next, the heat ray shielding material according to the present invention is a phthalocyanine compound represented by the general formula (1) or (3) (the phthalocyanine compound according to claim 2 and the phthalocyanine compound according to claim 6). (Including the near-infrared absorbing dye, hereinafter the same).

Use in the heat ray shielding material of the present invention
The phthalocyanine compound which can be obtained is represented by the above general formula (1)
Or a phthalocyanine compound represented by (3).
Although it may be shifted, it is preferable that the 8
4 or all 8 at the β-position, particularly preferably 8
Everything is SR¹Or OR^TwoIs replaced with
Contains ZnPc (PhS)₈(PhNH)_ThreeF_Five, Zn
Pc (PhS)₈(PhNH)_FourF_Four, ZnPc (Ph
S)₈(PhNH)_FiveF_Three, ZnPc (PhS)₈(P
hCH_TwoNH)_FourF_Four, ZnPc (PhS)₈(PhC
H_TwoNH)_FiveF _Three, ZnPc (PhS)₈(PhCH_Two
NH)₆F_Two, CuPc (PhS)₈(PhNH)
₇F, CuPc (PhS)₈(PhNH)₆F_Two, Cu
Pc (PhS)₈(PhNH)_FiveF_Three, VOPc (Ph
O)₈(PhCH_TwoNH)_FiveF_Three, VOPc (PhO)
₈(PhCH_TwoNH)₆F_Two, VOPc (PhO)
₈(PhCH_TwoNH)₈, VOPc (PhS)₈(Ph
CH_TwoNH)₈Phthalocyanine compound represented by the abbreviation
And so on. These selectively absorb light, especially in the near infrared region.
From sunlight while keeping the transmittance in the visible range relatively high.
To the heat ray shielding material to effectively block the heat of
It can be. This is the phthalocyanine
Compounds have excellent selective absorption in the near infrared region and are compatible with resins.
Excellent solubility and excellent heat resistance, light resistance, and light resistance
And has excellent properties as a heat ray shielding material without impairing its characteristics.
It is because the
You. Further, the phthalocyanine compound is used as a heat ray shielding material.
It can be provided as an inexpensive organic material that constitutes
It can be widely used for heat ray shielding.
Further, the phthalocyanine compound has excellent heat resistance.
Injection molding and extrusion using ordinary thermoplastic resin
It can be made by a molding method with excellent productivity such as molding.
Can, and can exhibit many excellent properties
Things.

The resin which can be used in the heat ray shielding material of the present invention can be appropriately selected according to the intended use of the obtained heat ray shielding material. Is preferred. Specific examples thereof include: polycarbonate resin; (meth) acrylic resin such as methyl methacrylate; polystyrene;
Polyvinyl chloride; polyvinyl resins such as polyvinylidene chloride; polyolefin resins such as polyethylene and polypropylene; polybutyral resins; vinyl acetate resins such as polyvinyl acetate; polyester resins and polyamide resins. In addition, as long as the resin is substantially transparent, not only the above-described one kind of resin but also a blend of two or more kinds of resins can be used. .

Among these resins, polycarbonate resins, (meth) acrylic resins, which are excellent in weather resistance and transparency,
Polyester resin, polystyrene resin or polyvinyl chloride is preferable, and polycarbonate resin, methacrylic resin, polyethylene terephthalate (PET) resin or polyvinyl chloride is more preferable.

The polycarbonate resin is produced by reacting a dihydric phenol with a carbonate precursor by a solution method or a melting method. The following are typical examples of the dihydric phenol.

2,2-bis (4-hydroxyphenyl)
Propane [bisphenol A], 1,1-bis (4-hydroxyphenyl) ethane, 1,1-bis (4-hydroxyphenyl) cyclohexane, 2,2-bis (4-hydroxy-3,5-dimethylphenyl) propane , 2,
2-bis (4-hydroxy-3,5-dibromophenyl) propane, 2,2-bis (4-hydroxy-3-methylphenyl) propane, bis (4-hydroxyphenyl) sulfide, bis (4-hydroxyphenyl) And sulfone. Preferred dihydric phenols are bis (4-hydroxyphenyl) alkanes, especially those containing bisphenol as a main component.

Examples of the acrylic resin include methyl methacrylate alone, a polymerizable unsaturated monomer mixture containing 50% or more of methyl methacrylate, or a copolymer thereof. Examples of the polymerizable unsaturated monomer copolymerizable with methyl methacrylate include the following. Methyl acrylate, ethyl (meth) acrylate (meaning methyl methacrylate or methyl methacrylate; the same applies hereinafter), butyl (meth) acrylate, cyclohexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, (meth) ) Methoxyethyl acrylate, ethoxyethyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, N, N-diethylaminoethyl (meth) acrylate, glycidyl (meth) acrylate, tribromo (meth) acrylate Phenyl, tetrahydroxyfurfuryl (meth) acrylate, ethylene glycol di (meth) acrylate, triethylene glycol di (meth)
Acrylate, tripropylene glycol di (meth) acrylate, trimethylol ethane di (meth) acrylate, neopentyl glycol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, and the like.

As the vinyl chloride resin, not only a polymer containing only vinyl chloride monomer but also a copolymer containing vinyl chloride as a main component can be used. Monomers that can be copolymerized with vinyl chloride include vinylidene chloride, ethylene, propylene, acrylonitrile, vinyl acetate, maleic acid, itaconic acid, acrylic acid, methacrylic acid, and the like.

[0092] The heat ray shielding material of the present invention may contain various additives used in producing a normal transparent resin material. Examples of the additive include a colorant, a polymerization regulator, an antioxidant, an ultraviolet absorber, a flame retardant,
Examples thereof include a plasticizer, rubber for improving impact resistance, and a release agent. Examples of the method of mixing and containing the phthalocyanine compound in a transparent resin and molding include extrusion molding, injection molding, cast polymerization, press molding, calender molding, and cast film forming method.

Further, a heat ray shielding material can be prepared by preparing a film containing the phthalocyanine compound of the present invention and subjecting the film to a transparent resin material by hot pressing or heat laminating. Further, a heat ray shielding material can also be obtained by printing or coating an acrylic resin ink or paint containing the phthalocyanine compound of the present invention on a transparent resin material.

The phthalocyanine compound used in the heat ray shielding material of the present invention is different from a commercially available infrared absorber in that
Since it has excellent heat resistance, it can be molded by a molding method such as injection molding or extrusion molding using acrylic resin, polycarbonate resin or PET resin, in which the resin temperature rises to a high temperature of 220 to 350 ° C. Thus, it is possible to obtain a molded article having good transparency and excellent heat ray shielding performance. There is no problem if used at a molding temperature of less than 220 ° C.

There is no particular restriction on the shape of the heat ray shielding material.
In addition to the most common flat and film shapes, various shapes such as corrugated, spherical, and dome shapes are included. The phthalocyanine compound used in the heat ray shielding material of the present invention can vary the amount of the intended heat ray shielding material depending on the visible and near-infrared transmittance settings and the thickness of the heat ray shielding material. 0.0005 to 20 parts by weight, preferably 0.0015 to 10 parts by weight, based on 100 parts by weight of the transparent resin.

The optimum range of the amount of the phthalocyanine compound varies depending on the shape of the heat ray shielding material. For example, when a heat ray shielding plate having a thickness of 3 mm is formed,
The compounding amount is preferably 0.002 to 0.06 parts by weight, and more preferably 0.005 to 0.03 parts by weight.

When a heat ray shielding plate having a thickness of 10 mm is prepared, the amount is preferably 0.0005 to 0.02 parts by weight, more preferably 0.0010 to 0.01 parts by weight. When a heat ray shielding film having a thickness of 10 μm is prepared, the amount is preferably 0.5 to 20 parts by weight, more preferably 1.0 to 10 parts by weight. If the amount of the phthalocyanine compound is indicated irrespective of the thickness of the heat ray shielding material, it is considered to be 0.
Amount of 05~2.4g / m ^2, more preferably an 0.10~1.0g / m ^2.

When the blending amount of the phthalocyanine compound is 0.0
When it is less than 5 g / m ² , the heat ray shielding effect is small, and when it is more than 2.4 g / m ² , the cost becomes extremely high, and the transmission of visible light may be too small. Irregular shapes such as corrugated plates may be considered as weights in the projected area from above. The distribution of the concentration of the phthalocyanine compound may be uneven unless there is a problem in appearance. In addition, one or more phthalocyanine compounds can be used in combination. When two or more phthalocyanine compounds having different absorption wavelengths are used, the heat ray shielding effect may be improved.

Further, by using a specific amount of a phthalocyanine compound and a material capable of absorbing heat rays, such as carbon black, the heat ray shielding effect is equal and the amount of the phthalocyanine compound used can be reduced as compared with the case where the phthalocyanine compound is used alone. It can be reduced to less than half.

Next, the filter for plasma display according to the present invention comprises a phthalocyanine compound represented by the above general formula (1) or (3) (the phthalocyanine compound according to any one of claims 1 to 5 and the phthalocyanine compound according to claim 6). (Including the near-infrared absorbing dye according to the present invention, hereinafter the same)) in an amount of 0.0005 to 20 parts by weight based on 100 parts of the resin.

The phthalocyanine compound which can be used in the plasma display filter of the present invention may be any of the phthalocyanine compounds represented by the above formula (1) or (3), but is preferably a phthalocyanine nucleus. Wherein all or eight, particularly preferably all eight, are substituted with SR ¹ or OR ² at the eight β-positions. Specifically, ZnPc (PhS)
₈ (PhNH) ₃ F ₅ , ZnPc (PhS) ₈ (PhN
H) ₄ F ₄ , ZnPc (PhS) ₈ (PhNH)
₅ F ₃ , ZnPc (PhS) ₈ (PhCH ₂ NH) ₄ F
₄ , ZnPc (PhS) ₈ (PhCH ₂ NH) ₅ F ₃ ,
ZnPc (PhS) ₈ (PhCH ₂ NH) ₆ F ₂ , Cu
Pc (PhS) ₈ (PhNH) ₇ F, CuPc (Ph
S) ₈ (PhNH) ₆ F ₂ , CuPc (PhS) ₈ (P
hNH) ₅ F ₃ , VOPc (PhO) ₈ (PhCH ₂ N
H) ₅ F ₃ , VOPc (PhO) ₈ (PhCH ₂ NH)
₆ F ₂ , VOPc (PhO) ₈ (PhCH ₂ NH) ₈ ,
It is a phthalocyanine compound represented by an abbreviation such as VOPc (PhS) ₈ (PhCH ₂ NH) ₈ . These have particularly high visible light transmittance, large absorption at 750 to 1,100 nm, and high solubility, heat resistance and light resistance, and can exhibit many excellent properties.

The filter for a plasma display of the present invention contains a phthalocyanine compound represented by the above general formula (1) or (3) in a base material. Not only that it is contained inside the substrate, but also that it is applied to the surface of the substrate and that it is sandwiched between the substrates. Examples of the substrate include a transparent resin plate, a transparent film, and a transparent glass. The method for producing the plasma display filter of the present invention using the phthalocyanine compound is not particularly limited.
Two methods are available.

(1) A method of preparing a resin plate or film by kneading the resin with the above phthalocyanine compound and heat molding the resin, and (2) Producing a paint (liquid or paste-like material) containing the above phthalocyanine compound, Resin plate,
(3) a method in which the phthalocyanine compound is contained in an adhesive to produce a laminated resin plate, a laminated resin film, a laminated glass, and the like.

First, in the method (1) in which the above-mentioned 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. Is
Vinyl compounds such as polyethylene, polystyrene, polyacrylic acid, polyacrylic acid ester, polyvinyl acetate, polyacrylonitrile, polyvinyl chloride, polyvinyl fluoride, and addition polymers of those vinyl compounds, polymethacrylic acid, polymethacrylic acid ester Vinyl compounds such as polyvinylidene chloride, polyvinylidene fluoride, polyvinylidene cyanide, vinylidene fluoride / trifluoroethylene copolymer, vinylidene fluoride / tetrafluoroethylene copolymer, vinylidene cyanide / vinyl acetate copolymer and the like. Copolymers of fluorinated compounds, polytrifluoroethylene, polytetrafluoroethylene, resins containing fluorine such as polyhexafluoropropylene, polyamides such as nylon 6, nylon 66, polyimides,
Polyurethanes, polypeptides, 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 limited to these resins. Instead of glass, a resin having high hardness and high transparency to replace glass, a thermosetting resin such as thiourethane, ARTON (manufactured by Nippon Synthetic Rubber Co., Ltd.), ZEONEX (manufactured by Nippon Zeon Co., Ltd.), OPTOREZ ( Hitachi Chemical Co., Ltd.), O-
It is also preferable to use an optical resin such as PET (manufactured by Kanebo Co., Ltd.).

Although the processing temperature, film forming conditions, and the like are slightly different depending on the base resin used, the phthalocyanine compound of the present invention is usually added to powder or pellets of the base resin and heated to 150 to 350 ° C. After heating and dissolving, forming a resin plate by molding,
A method of forming a film by an extruder, making a raw material by an extruder, 2 to 5 times at 30 to 120 ° C.
And a method of stretching the film into a film having a thickness of 10 to 200 μm. At the time of kneading, additives used for ordinary resin molding, such as an ultraviolet absorber and a plasticizer, may be added. The addition amount of the phthalocyanine compound of the present invention varies depending on the thickness of the resin to be produced, the target absorption intensity, the target visible light transmittance, and the like, but is usually 1 ppm to 20%. Further, a resin plate and a resin film using a casting method by bulk polymerization of the phthalocyanine compound of the present invention and methyl methacrylate or the like can also be produced.

As the method (2) for forming a coating by coating, the phthalocyanine compound of the present invention is dissolved in a binder resin and an organic solvent to form a coating, and the phthalocyanine compound is atomized to several μm or less to form an acrylic emulsion. To obtain a water-based paint. In the former method, usually, aliphatic ester-based resin, acrylic resin, melamine resin, urethane resin, aromatic ester-based 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 resin. In addition, ARTON
Optical resins such as (Nippon Synthetic Rubber Co., Ltd.), ZEONEX (Nippon Zeon Co., Ltd.), OPTPOREZ (Hitachi Chemical Co., Ltd.), and O-PET (Kanebo Co., Ltd.) can also be used. As the solvent, halogen-based, alcohol-based, ketone-based, ester-based, aliphatic hydrocarbon-based,
Aromatic hydrocarbon solvents, ether solvents, or mixtures thereof can be used.

The concentration of the phthalocyanine compound of the present invention is as follows:
Although it depends on the thickness of the coating, the desired absorption intensity, the desired visible light transmittance, and the like, it is usually 0.1 to 30% based on the weight of the binder resin. Further, the binder resin concentration is usually 1 to 50% with respect to the whole paint. Similarly, in the case of acrylic emulsion-based water-based paint,
It is obtained by dispersing a phthalocyanine compound of the present invention which has been finely pulverized (950 to 500 nm) in an uncolored acrylic emulsion paint. Additives such as an ultraviolet absorber and an antioxidant which are used in ordinary paints may be added to the paint. The paint prepared by the above method is a transparent resin film,
The filter for plasma display of the present invention can be prepared by coating a transparent resin plate, a transparent glass or the like with a bar coder, a blade coater, a spin coater, a reverse coater, a die coater or a spray. A protective layer may be provided to protect the coating surface, or a transparent resin plate, a transparent resin film, or the like may be attached to the coating surface. Also, a cast film is included in the method.

In the method (3) in which the phthalocyanine compound is contained in an adhesive to produce a laminated resin plate, a laminated resin film, a laminated glass, and the like, in the method (3), a general silicone-based, urethane-based, acrylic Butyral adhesive (PVA) for resin or laminated glass, ethylene-vinyl acetate adhesive (E
Known transparent adhesives for laminated glass such as VA) can be used. A transparent resin plate, a resin plate and a resin film, a resin plate and a glass, a resin film and a transparent resin plate using an adhesive containing 0.1 to 30% by weight of the phthalocyanine compound of the present invention.
A filter is manufactured by bonding a resin film to glass and glass to each other. There is also a method of thermocompression bonding. further,
The film or plate produced by the above method can be attached to glass or a resin plate as needed.
The thickness of the filter varies depending on the specification of the plasma display to be manufactured, but is usually about 0.1 to 10 mm. In addition, a transparent film (UV cut film) containing a UV absorber can be attached to the outside to increase the light resistance of the filter.

As a malfunction prevention filter for a plasma display, the filter is installed in front of the display to cut off near infrared light emitted from the display.
The higher the visible light transmittance of the filter, the better, and it is required to be at least 60%, preferably at least 70%. Also,
The cut region of near-infrared light is 750 to 1,100 nm, preferably 8 nm, used for remote control and transmission optical communication.
It is designed so that the average light transmittance in that region is 15% or less, preferably 10% or less. If necessary, two or more phthalocyanine compounds represented by the above general formula (1) or (3) may be combined. It is also preferable to add another dye having absorption in the visible region in order to change the color tone of the filter. In addition, a filter containing only a color tone dye can be prepared and bonded later. Especially when an electromagnetic wave cut layer such as sputtering is provided, the color tone may be significantly different from the original filter color,
Color is important.

In order to make the filter obtained by the above method more practical, an electromagnetic wave cut layer, an antireflection (AR) layer and a non-glare (AG) layer for blocking electromagnetic waves emitted from the plasma display can be provided. . The method for producing them is not particularly limited. For example, for the electromagnetic wave cut layer, a sputtering method using a metal oxide or the like can be used. In general, In ₂ O ₃ (ITO) to which Sn is added is generally used, but a dielectric layer and a metal layer are formed on a substrate. Alternatively, by laminating alternately by sputtering or the like, it is possible to cut light of 1,100 nm or more from near infrared rays, far infrared rays to electromagnetic waves. As the dielectric layer, indium oxide,
It is a transparent metal oxide such as zinc oxide. As the metal layer, silver or a silver-palladium alloy is generally used. Usually, three layers, five layers, seven layers or one layer starting from a dielectric layer are formed.
About one layer is laminated. In this case, the heat generated from the display can be cut at the same time. However, the phthalocyanine compound of the present invention has an excellent heat ray shielding effect, so that the heat resistance effect can be further improved. As the substrate, the filter containing the phthalocyanine compound of the present invention may be used as it is, or may be sputtered on a resin film or glass and then bonded to the filter containing the phthalocyanine compound. When the electromagnetic wave is actually cut, it is necessary to provide an electrode for grounding. The anti-reflection layer is a metal oxide, a fluoride, a boride, a carbide,
A method of laminating inorganic substances such as nitrides and sulfides into a single layer or multiple layers by a vacuum evaporation method, a sputtering method, an ion plating method, an ion beam assist method, etc., and a resin having a different refractive index such as an acrylic resin or a fluororesin. And a method of laminating them in a single layer or a multilayer. Further, a film having been subjected to an anti-reflection treatment can be attached on the filter. Also, if necessary, non-glare (AG)
Layers can also be provided. The non-glare (AG) layer
In order to widen the viewing angle of the filter, a method of forming a fine powder of silica, melamine, acrylic, or the like into an ink and coating the surface thereof to scatter transmitted light can be used. The ink can be cured by heat curing or light curing. Further, a non-glare-treated film can be attached to the filter. If necessary, a hard coat layer may be provided.

The structure of the filter for plasma display can be changed as required. Usually, an antireflection layer is provided on a filter containing a near-infrared absorbing compound, and if necessary, a non-glare layer is provided on the opposite side of the antireflection layer. When an electromagnetic wave cut layer is combined, a filter containing a near infrared absorbing compound is used as a base material, and an electromagnetic wave cut layer is provided thereon, or a filter containing a near infrared absorbing compound and a filter having an electromagnetic wave cutting ability are used. It can be made by bonding. In that case, an antireflection layer can be further formed on both sides, or if necessary, an antireflection layer can be formed on one side and a non-glare layer can be formed on the opposite side. When a dye having absorption in the visible region is added for color correction, the method is not limited. The plasma display filter of the present invention has a high visible light transmittance, so that the sharpness of the display is not impaired. It does not adversely affect the wavelength used by system optical communication, etc.
These malfunctions can be prevented.

[0112]

The present invention will be described below in detail with reference to examples.

Synthesis Example 1 Abbreviation: Synthesis of ZnPc (PhS) ₈ F _{8 In} a 100 ml four-necked flask, 3,6-difluoro-
4,5-bisphenylthiophthalonitrile 10 g (2
6.2 mmol), 3.14 g (9.8 mmol) of zinc iodide and 50 ml of benzonitrile, then kept at reflux for about 5 hours with stirring. Thereafter, the green solid obtained by cooling was filtered, washed with acetone, and washed with ZnPc.
7.90 g of (PhS) ₈ F ₈ (vs. 3,6-difluoro-
4,5-bisphenylthiophthalonitrile yield 77.2
Mol%).

Synthesis Example 2 Abbreviation: Synthesis of VOPc (PhS) ₈ F ₈ 3,6-difluoro- was added to a 100 ml four-necked flask.
4,5-bisphenylthiophthalonitrile 10 g (2
6.2 mmol), 0.6 g (4 mmol) of divanadium trioxide and 1.01 g (5.3 mmol) of p-toluenesulfonic acid.
Mmol) and 50 ml of benzonitrile, then kept at reflux for about 5 hours with stirring. After cooling, the resulting green solid was filtered, washed with acetone, and
7.86 g of c (PhS) ₈ F ₈ (based on 3,6-difluoro-4,5-bisphenylthiophthalonitrile, yield: 75.
7 mol%).

Synthesis Example 3 Abbreviation: Synthesis of CuPc (PhS) ₈ F _{8 In} a 200 ml four-necked flask, 3,6-difluoro-
4,5-bisphenylthiophthalonitrile 10 g (2
6.2 mmol), 0.95 g (9.1 mmol) of cuprous chloride and 100 ml of N-methyl-2-pyrrolidone and then kept at 140 DEG C. with stirring for about 5 hours. After cooling, the resulting green solid was filtered, washed with acetone, and 8.45 g of CuPc (PhS) ₈ F ₈ (vs. 3,6-
Difluoro-4,5-bisphenylthiophthalonitrile yield 85.2 mol%) was obtained.

Synthesis Example 4 Abbreviation: VOPc (PhO)₈F₈In a 100 ml four-necked flask, 3,6-difluoro-
9.12 g of 4,5-bisphenoxyphthalonitrile (2
6.2 mmol), 0.6 g of divanadium trioxide (4
0.19 g (1 mm) of p-toluenesulfonic acid
Mol) and 50 ml of benzonitrile
Maintained at reflux temperature with stirring for about 5 hours. Then cool down
The filtered green solid is washed with acetone and washed with VOPc
(PhO) ₈F₈6.95 g (vs. 3,6-difluoro-
4,5-bisphenoxyphthalonitrile yield 72.7 mol
%) Was obtained.

Synthesis Example 5 Abbreviation: Synthesis of VOPc (PhO) ₄ F _{12 In} a 100 ml four-necked flask, 7.18 g of 3,5,6-trifluoro-4-phenoxyphthalonitrile (2
6.2 mmol), 0.6 g (4 mmol) of divanadium trioxide, 0.19 g (1 mmol) of p-toluenesulfonic acid and 50 ml of benzonitrile and then kept under reflux for about 5 hours with stirring at reflux temperature. After cooling, the resulting green solid was filtered, washed with acetone, and VOPc
5.78 g of (PhO) ₄ F ₁₂ (yield: 7,5 mol% based on 2,5,6-trifluoro-4-phenoxyphthalonitrile) was obtained.

Synthesis Example 6 Abbreviation: Synthesis of VOPc (p-CNPhO) ₈ F ₈ 3,6-difluoro-
4,5-bis (p-cyanophenoxy) phthalonitrile 10 g (25.1 mmol), divanadium trioxide 0.1 g
6 g (4 mmol), p-toluenesulfonic acid 1.14
g (6 mmol) and 50 ml of benzonitrile were then charged and kept at reflux for about 8 hours with stirring. Thereafter, the cooled reaction solution was poured into 500 ml of toluene, and the obtained precipitate was filtered, washed with 200 ml of toluene until the filtrate became colorless, and vacuum-dried at 60 ° C. overnight to obtain VOPc (p-p). CNPhO) ₈ F ₈ 9.31
g (vs. 3,6-difluoro-4,5-bis (p-cyanophenoxy) phthalonitrile yield: 89.3 mol%).

Synthesis Example 7 Abbreviation: Synthesis of VOPc (2,5-Cl ₂ PhO) ₈ F ₈ 3,6-difluoro-
12.73 g (26.2 mmol) of 4,5-bis (2,5-dichlorophenoxy) phthalonitrile, 0.6 g (4 mmol) of divanadium trioxide, 0.76 g (4 mmol) of p-toluenesulfonic acid and Benzonitrile 5
0 ml was charged and then maintained at reflux temperature with stirring for about 5 hours. Thereafter, the cooled reaction solution was put into 500 ml of toluene, and the obtained solid substance was filtered.
and washed with VOPc (2,5-Cl ₂ PhO) ₈ F ₈
11.5 g (vs. 3,6-difluoro-4,5-bis (2,5-dichlorophenoxy) phthalonitrile yield 8
7.6 mol%).

Synthesis Example 8 Abbreviation: Synthesis of ZnPc (2,5-Cl ₂ PhO) ₈ F ₈ 3,6-difluoro- was added to a 100 ml four-necked flask.
12.73 g (26.2 mmol) of 4,5-bis (2,5-dichlorophenoxy) phthalonitrile, 0.64 g (7.9 mmol) of zinc oxide, 0.095 g (0.5 mmol) of p-toluenesulfonic acid ) And 50 ml of benzonitrile and then kept at reflux for about 5 hours with stirring. Thereafter, the cooled reaction solution was poured into 500 ml of isopropyl alcohol (IPA), and the obtained solid was filtered, washed with 200 ml of IPA, and washed with ZnPc.
(2,5-Cl ₂ PhO) ₈ F ₈ 11.36 g (vs. 3,
6-Difluoro-4,5-bis (2,5-dichlorophenoxy) phthalonitrile yield was 86.3 mol%.

Example 1 Abbreviation: Synthesis of ZnPc (PhS) ₈ (PhNH) ₄ F ₄ The F obtained in Synthesis Example 1 was placed in a 100 ml four-necked flask.
₈ (PhS) ₈ ZnPc (2 g, 1.26 mmol), calcium carbonate, 1.0 g (10 mmol), and aniline (60 ml) were charged, and the mixture was kept at 150 ° C. with stirring for about 8 hours. Thereafter, the inorganic component was filtered and aniline was distilled off to obtain ZnPc (PhS) ₈ (PhNH) ₄ F ₄ 2.0
7 g was obtained (yield 87.6 mol%). Elemental analysis; C (%) H (%) N (%) S (%) F (%) Theoretical 66.46 3.43 8.94 13.65 4.04 Analytical 66.42 3.398 .99 13.61 4.09 Using a spectrophotometer (manufactured by Shimadzu Corporation: UV-3100), the phthalocyanine compound @ZnP obtained in this example was used.
The maximum absorption wavelength and extinction coefficient of c (PhS) ₈ (PhNH) ₄ F ₄ } in ethyl cellosolve were measured.

Further, this phthalocyanine compound was added in an amount of 1 cm.
Was diluted with chloroform until the minimum value of the light transmittance at 750 to 1,100 nm became 5 to 6% in a quartz cell, and the transmittance at that time was measured with a spectrophotometer. It was calculated according to the standard of R3106.

At room temperature (25 ° C.), each solution of toluene and methyl ethyl ketone (MEK) (both 10 m
While gradually dissolving the phthalocyanine compound in 1), the state was visually checked to determine the limit amount of the phthalocyanine compound finally dissolved, that is, the concentration (solubility) of the solute phthalocyanine compound in the saturated solution.

The results of these measurements are shown in Table 1 below. Table 1
The solubility was evaluated as ◎ when the solubility was 5% by weight or more, ○ when 1% by weight or more and less than 5% by weight, Δ when 0.1% by weight or more and less than 1% by weight, and X when less than 0.1% by weight. .

Example 2 Abbreviations: ZnPc (PhS) ₈ (PhCH ₂ NH) ₅ F ₃
The synthesis of ZnPc (P) was carried out in the same manner as in Example 1 except that benzylamine was replaced with 60 ml, the reaction temperature was changed to 50 ° C., and the reaction time was changed to 3 hours.
2.38 g of (hS) ₈ (PhCH ₂ NH) ₅ F ₃ were obtained (yield 93.4 mol%). Elemental analysis; C (%) H (%) N (%) S (%) F (%) Theoretical 68.28 3.99 9.00 12.68 2.82 Analytical 68.20 3.92 9 .06 12.61 2.86 In the same manner as in Example 1, the maximum absorption wavelength, extinction coefficient,
Visible light transmittance and solubility were measured. The results of these measurements are shown in Table 1 below.

Example 3 Abbreviation: Synthesis of ZnPc (PhS) ₈ (BuNH) ₅ F ₃ The procedure was carried out except that n-butylamine was 60 ml instead of aniline, the reaction temperature was changed to 50 ° C., and the reaction time was changed to 3 hours. By operating in the same manner as in Example 1, ZnPc (P
1.90 g of hS) ₈ (BuNH) ₅ F ₃ were obtained (yield: 8).
1.5 mol%). Elemental analysis; C (%) H (%) N (%) S (%) F (%) Theoretical 64.8 4.90 9.83 13.85 3.08 Analytical 64.1 4.869 .88 13.79 3.11 Further, in the same manner as in Example 1, the maximum absorption wavelength, extinction coefficient,
Visible light transmittance and solubility were measured. The results of these measurements are shown in Table 1 below.

Example 4 Abbreviations: ZnPc (PhS) ₈ (HOEtOEtNH) ₆
Instead of the synthetic aniline F ₂ 2- and (2-aminoethoxy) ethanol 60 ml, further the reaction temperature 50 ° C., except for changing the reaction time to 3 hours, ZnPc by the procedure of Example 1 ( PhS) ₈ (HOEtOEtNH)
2.46 g of ₆ F ₂ was obtained (yield 93.0 mol%). Elemental analysis; C (%) H (%) N (%) S (%) F (%) Theoretical 59.54 4.80 9.35 12.23 1.81 Analytical 59.49 4.789 .38 12.18 1.87 In the same manner as in Example 1, the maximum absorption wavelength, extinction coefficient,
Visible light transmittance and solubility were measured. The results of these measurements are shown in Table 1 below.

Example 5 Abbreviation: ZnPc (PhS) ₈ {(Ph) ₂ CHNH} ₄
Synthesis of F ₄ ZnP was prepared in the same manner as in Example 1 except that aminodiphenylmethane was replaced by 15 ml instead of aniline, the reaction temperature was changed to 50 ° C., and the reaction time was changed to 3 hours.
c (PhS) ₈ {(Ph) ₂ CHNH} ₄ F ₄ 2.62
g was obtained (yield 92.8 mol%). Elemental analysis; C (%) H (%) N (%) S (%) F (%) Theoretical 70.77 3.96 7.50 11.45 3.39 Analytical 70.72 3.95 7 .51 11.49 3.41 Further, in the same manner as in Example 1, the maximum absorption wavelength, extinction coefficient,
Visible light transmittance and solubility were measured. The results of these measurements are shown in Table 1 below.

Example 6 Abbreviations: VOPc (PhS) ₈ (PhCH ₂ NH) ₆ F ₂
Synthesis of F obtained in Synthesis Example 2 in a 100 ml four-necked flask
₈ (PhS) ₈ VOPc 2 g (1.26 mmol), calcium carbonate 1.0 g (10 mmol) and benzylamine 60 ml were charged, and the mixture was kept at 60 ° C. for about 3 hours with stirring. Thereafter, the inorganic component was filtered, and benzylamine was distilled off to obtain VOPc (PhS) ₈ (PhCH ₂ N).
H) ₆ F ₂ 2.17 g was obtained (yield 81.6 mol%). Elemental analysis: C (%) H (%) N (%) S (%) F (%) Theoretical 69.39 4.20 9.29 12.15 1.80 Analytical 69.43 4.19 .33 12.10 1.85 In the same manner as in Example 1, the maximum absorption wavelength, extinction coefficient,
Visible light transmittance and solubility were measured. The results of these measurements are shown in Table 1 below.

Example 7 Abbreviation: Synthesis of VOPc (PhS) ₈ (n-BuNH) ₇ F The procedure of Example 6 was repeated except that 60 ml of n-butylamine was used instead of benzylamine.
1.86 g of Pc (PhS) ₈ (n-BuNH) ₇ F was obtained (yield 75.2 mol%). Elemental analysis: C (%) H (%) N (%) S (%) F (%) Theoretical 66.16 5.65 10.72 13.08 0.97 Analytical 66.12 5.61 10 0.74 13.02 0.99 In the same manner as in Example 1, the maximum absorption wavelength, extinction coefficient,
Visible light transmittance and solubility were measured. The results of these measurements are shown in Table 1 below.

Example 8 Abbreviation: CuPc (PhS)₈(PhCH_TwoNH)₆F_Two
Synthesis of ZnPc (PhS)₈F₈Instead of the one obtained in Synthesis Example 3.
CuPc (PhS) ₈F₈2 g (1.26 mmol)
Other than that described above, the same operation as in Example 2 was performed to obtain C
uPc (PhS)₈(PhCH_TwoNH)₆F_Two2.04
g was obtained (yield 76.8 mol%). Elemental analysis: C (%) H (%) N (%) S (%) F (%) Theoretical 69.51 4.21 9.30 12.17 1.80 Analysis 69.48 4.189 .35 12.11 1.83 In the same manner as in Example 1, the maximum absorption wavelength, extinction coefficient,
Visible light transmittance and solubility were measured. These measurement results
It is shown in Table 1 below.

Example 9 Abbreviation: VOPc (PhO)₈(PhCH_TwoNH)₆F_Two
Synthesis of ZnPc (PhS)₈F₈Instead of that obtained in Synthesis Example 4.
VOPc (PhO) ₈F₈2 g (1.37 mmol)
The same operation as in Example 2 was performed except that
OPc (PhO)₈(PhCH_TwoNH)₆F_Two2.05
g was obtained (yield 75.5 mol%). Elemental analysis value; C (%) H (%) N (%) F (%) Theoretical value 73.89 4.47 9.89 1.92 Analysis value 73.80 4.42 9.92 1.99 Maximum absorption wavelength, extinction coefficient,
Visible light transmittance and solubility were measured. These measurement results
It is shown in Table 1 below.

Example 10 Abbreviation: VOPc (PhO)_FourF_Four(PhCH_TwoNH)₆
F_TwoSynthesis of ZnPc (PhS)₈F₈Instead of the one obtained in Synthesis Example 5.
VOPc (PhO) _FourF₁₂2 g (1.72 mmol)
The same operation as in Example 2 was performed except that
OPc (PhO)_FourF_Four(PhCH_TwoNH)₆F_Two1.
89 g were obtained (yield: 65.2 mol%). Elemental analysis: C (%) H (%) N (%) F (%) Theoretical 69.79 4.06 11.63 6.76 Analytical 69.72 4.02 11.68 6.77 Maximum absorption wavelength, extinction coefficient,
Visible light transmittance and solubility were measured. These measurement results
It is shown in Table 1 below.

Example 11 Abbreviations: VOPc (PhS) ₈ ｛Ph (CH ₃ ) CHN
Four-necked flask H} ₇ F Synthesis 50 ml, VO prepared in Synthesis Example 1
Pc (PhS) were charged ₈ F ₈ 5g (3.15 mmol) and DL-1-phenylethylamine 25 ml, then kept under stirring for about 10 hours at 120 ° C.. After filtration, the filtrate was dropped into 250 ml of isopropyl alcohol with stirring, and the precipitated solid was removed by filtration.
VOPc (PhS) by vacuum drying overnight at
6.81 g of ₈ {Ph (CH ₃ ) CHNH} ₇ F was obtained (based on VOPc (PhS) ₈ F _8, yield: 94.2 mol%).

Elemental analysis value C (%) H (%) N (%) S (%) F (%) Theoretical value 71.12 4.83 9.15 11.17 0.83 Analytical value 71.18 4.85 9.13 11.13 0.85 The maximum absorption wavelength in the same manner as in Example 1. , Extinction coefficient, visible light transmittance, and solubility were measured. Table 1 shows the results.

Example 12 Abbreviation: CuPc (PhS)₈(PhCH_TwoCH_TwoNH)
₇Synthesis of F VOPc (PhS)₈F₈Instead of
CuPc (PhS) ₈F₈, DL-1-phenylethyl
2-phenylethylamine 25m instead of ruamine
1, the reaction temperature is 125 ° C and the reaction time is 12 hours.
By operating in the same manner as in Example 11 except that
uPc (PhS)₈(PhCH_TwoCH_TwoNH)₇F5.
95g (vs. CuPc (PhS)₈F₈82.3 mol yield
%).

Elemental analysis value C (%) H (%) N (%) S (%) F (%) Theoretical value 71.22 4.83 9.16 11.18 0.83 Analytical value 71.26 4.85 9.12 11.14 0.86 In the same manner as in Example 1, the maximum value was obtained. Absorption wavelength, extinction coefficient,
Visible light transmittance and solubility were measured. Table 1 shows the results.

Example 13 Abbreviation: VOPc (p-CNPhO) ₈ (PhCH ₂ N
H) Synthesis of ₇ F The VO prepared in Synthesis Example 6 was placed in a 50 ml four-necked flask.
_{Pc (p-CNPhO) 8 F} 8 5g (3.01 mmol) and benzylamine 5.16 g (48.2 mmol)
And 1.5 g (15 mmol) of calcium carbonate and 28.2 g of benzonitrile, and then kept at 150 ° C. with stirring for about 8 hours. After filtration, the filtrate was added dropwise to a mixed solution of 125 ml of isopropyl alcohol and 125 ml of hexane with stirring, and the precipitated solid was removed by filtration and vacuum-dried at 60 ° C. overnight to obtain VOPc.
_{(P-CNPhO) 8 (PhCH} 2 NH) 7 F5.98
g (vs. VOPc (p-CNPhO) ₈ F ₈ yield 8)
7.5 mol%).

Elemental analysis value C (%) H (%) N (%) F (%) Theoretical value 72.48 3.91 14.19 0.84 Analytical value 72.52 3.89 14.12 0.86 In addition, except that the maximum absorption wavelength and the absorption coefficient were measured in MEK. The maximum absorption wavelength, extinction coefficient, visible light transmittance, and solubility were measured in the same manner as in Example 1. Table 1 shows the results.
Shown in

Example 14 Abbreviation: VOPc (p-CNPhO) ₈ ｛(Ph) ₂ CH
Synthesis of NH @ ₇ F Benzhydrylamine 8.8 instead of benzylamine
3 g (48.2 mmol), benzonitrile in 24.5
g, the reaction temperature was changed to 150 ° C., and the reaction time was changed to 8 hours.
Pc (p-CNPhO) ₈ {(Ph) ₂ CHNH} ₇ F
8.16 g was obtained (vs. VOPc (p-CNPhO) ₈ F
₈ yield 86.3 mol%).

Elemental analysis value C (%) H (%) N (%) F (%) Theoretical value 79.20 3.72 10.26 0.61 Analytical value 79.25 3.75 10.24 0.66 In the same manner as in Example 1, the maximum absorption wavelength, absorption coefficient,
Visible light transmittance and solubility were measured. Table 1 shows the results.

Example 15 Abbreviations: ZnPc (PhS) ₈ ｛Ph (CH ₃ ) CHN
Four-necked flask 50ml of H} ₄ F _4, Zn obtained in Synthesis Example 1
2 g (1.26 mmol) of Pc (PhS) ₈ F ₈ ,
1.222 g of L-1-phenylethylamine (10.0
8 mmol), 0.555 g (5.54 g) of calcium carbonate
Mmol) and 17 ml of benzonitrile, then kept at 110 ° C. with stirring for about 5 hours. Thereafter, the inorganic component was filtered, and 280 ml of isopropyl alcohol (IPA) was added.
It was allowed to crystallize dropwise. The solid content is filtered by suction, and IPA10
Washing with stirring was performed in 0 ml for 1 hour. The solid content is filtered by suction and dried in a vacuum at 60 ° C. overnight to obtain ZnPc.
(PhS) ₈ {Ph (CH ₃ ) CHNH} ₄ F ₄ 2.9
3 g were obtained. (Yield 92.4 mol%) Elemental analysis C (%) H (%) N (%) S (%) F (%) Theoretical 67.54 4.05 8.44 12.88 3.82 Analytical 67.52 4.04 8.42 12.85 3.80 Maximum absorption wavelength, extinction coefficient,
Visible light transmittance and solubility were measured. Table 1 shows the results.

Example 16 Abbreviation: ZnPc (PhS)₈｛(CH_Three)_ThreeCCH_TwoC
(CH_Three)_TwoNH｝_FourF _FourSynthesis of D, L-1-phenylethylamine,
2.606 g of 1,3,3-tetramethylbutylamine
(20.16 mmol), the reaction temperature was changed to 150 ° C.
Other than that described above, ZnPc
(PhS)₈｛(CH_Three)_ThreeCCH_TwoC (CH_Three)_TwoN
H｝_FourF_Four2.11 g were obtained. (Yield 82.5 mol%) Elemental analysis value C (%) H (%) N (%) S (%) F (%) Theoretical value 66.46 5.58 8.30 12.67 3.75 Analytical value 66.46 5.60 8.31 12.65 3.74 Maximum absorption wavelength, extinction coefficient,
Visible light transmittance and solubility were measured. The results are shown in Table 1.
You.

Example 17 Abbreviation: VOPc (2,5-Cl ₂ PhO) ₈ ｛Ph (C
Synthesis of H ₃ ) CHNH｝ ₆ F ₂ The F ₈ obtained in Synthesis Example 7 was placed in a 50 ml four-necked flask.
(2,5-Cl ₂ PhO) ₈ VOPc ₂ g (0.99 mmol), D, L-1-phenylethylamine 1.92
8 g (15.84 mmol) and benzonitrile 10
Then, the mixture was kept at 120 ° C. with stirring for about 5 hours. Thereafter, the inorganic content was filtered, and the filtrate was concentrated to 8 ml, and crystallized dropwise in 80 ml of IPA. The solid content was filtered by suction, and washed with stirring in 50 ml of IPA for 1 hour. The solid content was filtered by suction and dried in a vacuum at 60 ° C. overnight to obtain VOPc (2,5-Cl ₂ PhO) ₈ @Ph.
2.03 g of (CH ₃ ) CHNH｝ ₆ F ₂ was obtained. (Yield: 78.0 mol%) Elemental analysis value C (%) H (%) N (%) F (%) Theoretical value 58.72 3.23 7.49 1.45 Analytical value 58.75 3.25 7.50 1.43 Absorption wavelength, extinction coefficient,
Visible light transmittance and solubility were measured. Table 1 shows the results.

Example 18 Abbreviation: VOPc (2,5-Cl ₂ PhO) ₈ (PhCH
Synthesis of ₂ NH) ₈ The F ₈ obtained in Synthesis Example 7 was placed in a 50 ml four-necked flask.
(2,5-Cl ₂ PhO) ₈ VOPc ( ₂ g, 0.99 mmol) and benzylamine (12 ml) were charged.
It was kept under stirring at 5 ° C. for about 12 hours. Thereafter, the inorganic content was filtered, and the filtrate was concentrated to 8 ml, and crystallized dropwise in 80 ml of IPA. The solid content was filtered by suction, and washed with stirring in 50 ml of IPA for 1 hour. The solid content is filtered by suction.
VOPc (2,5-
2.06 g of Cl ₂ PhO) ₈ (PhCH ₂ NH) ₈ were obtained. (Yield: 76.6 mol%) Elemental analysis value C (%) H (%) N (%) F (%) Theoretical value 60.31 3.27 8.27 0.00 Analytical value 60.29 3.30 8.30 0.00 Absorption wavelength, extinction coefficient,
Visible light transmittance and solubility were measured. Table 1 shows the results.

Example 19 Abbreviation: Synthesis of VOPc (PhS) ₈ (PhCH ₂ NH) ₈ VOPc (PhS) ₈ (PhCH ₂ N) was prepared in the same manner as in Example 6 except that the reaction temperature was changed to 80 ° C.
H) ₈ 3.03 g were obtained. (Yield 89.0 mol%) Elemental analysis value C (%) H (%) N (%) S (%) F (%) Theoretical value 71.46 4.59 9.80 11.22 0.00 Analytical value 71.44 4.57 9.83 11.20 0.00 Maximum absorption wavelength, extinction coefficient,
Visible light transmittance and solubility were measured. Table 1 shows the results.

Example 20 Abbreviations: ZnPc (2,5-Cl ₂ PhO) ₈ ｛Ph (C
Synthesis of H ₃ ) CHNH｝ ₅ F ₃ The F ₈ obtained in Synthesis Example 8 was placed in a 50 ml four-necked flask.
(2,5-Cl ₂ PhO) ₈ ZnPc ₂ g (1.00 mmol), D, L-1-phenylethylamine 18 ml
And kept at 80 ° C. for about 2 hours with stirring. Thereafter, the inorganic component was filtered, and crystallized dropwise in a mixture of 100 ml of IPA and 100 ml of water. The solid content is filtered by suction, and IP
Washing with stirring was performed in 100 ml of A for 1 hour. The solid content is filtered by suction and dried in a vacuum at 60 ° C. overnight to obtain Zn.
Pc (2,5-Cl ₂ PhO) ₈ ｛Ph (CH ₃ ) CH
NH} to obtain a ₅ F ₃ 1.80 g. (Yield 72.0 mol%) Elemental analysis value C (%) H (%) N (%) F (%) Theoretical value 57.29 2.96 7.24 2.27 Analytical value 57.25 2.99 7.26 2.24 In the same manner as in Example 1, the maximum value was obtained. Absorption wavelength, extinction coefficient,
Visible light transmittance and solubility were measured. Table 1 shows the results.

Comparative Example 1 A phthalocyanine compound described in Example 10 of Japanese Patent Application Laid-Open No. Hei 6-264050 (abbreviation: VOP)
Using c (BuNH) ₈ (BuS) ₈ }, solubility and visible light transmittance were measured in the same manner as in Example 1. The measurement results are shown in Table 1 below.

Comparative Example 2 A phthalocyanine compound described in Example 16 of JP-A-6-264050, which is a patent application of the present invention (abbreviation: VOP)
Using c (PhNH) ₈ F ₈ }, the solubility and visible light transmittance were measured in the same manner as in Example 1. The measurement results are shown in Table 1 below.

Comparative Example 3 Penta (4) described in Example 3 of JP-A-7-70129
Using -methoxyphenylamino) deca (4-methylphenylthio) copper phthalocyanine, the solubility and the visible light transmittance were measured in the same manner as in Example 1. The measurement results are shown in Table 1 below.

Comparative Example 4 The following compound described in Example 1 of JP-A-9-230134

[0152]

Embedded image

The solubility and the visible light transmittance were measured in the same manner as in Example 1 using The measurement results are shown in Table 1 below.
Shown in

[0154]

【table 1】

Example 21 A molten polycarbonate resin (manufactured by Teijin Chemicals Limited,
Example 1 with 100 parts by weight of Panlite 1285 (trade name)
Phthalocyanine compound obtained by the above {ZnPc (PhS)
₈ (PhNH) ₄ F ₄ ＮＨ is added by 0.0053 parts by weight,
A sheet having a thickness of 2.5 mm was formed at 280 ° C. using a T-die extruder to obtain a filter.

750 to 1,100 of the obtained filter
The minimum value of the light transmittance in nm was 5.6%, and the visible light transmittance was 74%.

The filter was actually mounted on the front surface of the plasma display, and an electronic device for controlling the operation by a remote controller was placed at a position 2.5 m from the display. It was confirmed that no malfunction was induced. In this case, a malfunction was induced. However, when the filter was attached, no malfunction was induced.

Example 22 The procedure of Example 21 was repeated except that the phthalocyanine compound was used in Example 8.
Phthalocyanine compound obtained by the above [CuPc (PhS)]
_A filter was obtained in the same manner as in Example 21, except that ₈ (PhCH ₂ NH) ₆ F ₂ was changed to 0.0084 parts by weight. The minimum value of the light transmittance at 750 to 1,100 nm of the obtained filter was 5.4%, and the visible light transmittance was 71%.

Further, it was confirmed whether or not an erroneous operation was induced in the same manner as in Example 21. When the filter was attached, no erroneous operation was induced.

Example 23 The phthalocyanine compound obtained in Example 2 {ZnPc} was added to 100 parts by weight of a molten polyethylene terephthalate resin.
(PhS) ₈ (PhCH ₂ NH) ₅ F ₃ } is 0.133
A part by weight was added, and a 0.1 mm filter film was obtained at a molding temperature of 280 ° C. using an extruder and a film manufacturing apparatus. 800 to 950 of the obtained filter film
The average light transmittance in nm is 5.2% and the visible light transmittance is 70%.
%Met.

Further, the filter film was actually attached to the front surface of the plasma display, and it was confirmed whether or not an erroneous operation was induced in the same manner as in Example 21. When the filter film was attached, an erroneous operation was induced. I didn't see it at all.

Embodiments 24 and 25 As shown in FIG. 1, a column 3 is provided in a direction perpendicular to the support base 2 adjusted so as to be substantially perpendicular to the direct sunlight 1 (the incident direction of the direct sunlight). A temperature measuring device 6 having a filter 4 for measurement installed at the tip of the column 3 and a sample support plate 5 that can be adjusted in the vertical direction near the lower portion of the column 3 (because the wind blows through the measurement panel). A black panel 7 was set on the sample supporting plate 5, and the distance between the surface of the black panel 7 and the lower surface of the measurement filter 4 was set to 200 mm. The temperature sensor 8 was brought into contact with the surface of the panel 7. The temperature sensor 8 is connected to a measuring device (not shown) via a conductor 9. Using this temperature measuring device 6, Examples 21 and 22 were obtained under direct sunlight.
The temperature of the part where light passed through the filter was applied was measured. Further, a light resistance test was performed at a humidity of 50%, a black panel temperature of 63 ° C., and an ultraviolet intensity of 90 mW / cm ² for 100 hours. The results are shown in Table 2 below.

Comparative Example 5 A molten polycarbonate resin (manufactured by Teijin Chemicals Limited,
Panlight 1285, trade name) with a T-die extruder for 280
C. to obtain a polycarbonate sheet having a thickness of 2.5 mm. Using the obtained sheets, the temperature and light resistance were measured in the same manner as in Examples 24 and 15. The results are shown in Table 2 below.

Comparative Examples 6 and 7 A molten polycarbonate resin (manufactured by Teijin Chemicals Limited,
Panlite 1285, trade name) 100 parts by weight of phthalocyanine compound shown in Table 2 {abbreviation: VOPc (BuNH)
₈ (BuS) ₈ and VOPc (PhNH) ₈ F ₈ } were also added in the amounts shown in Table 2, and a thickness of 2.5
mm sheet was molded at 280 ° C. to obtain a filter. The visible light transmittance of the obtained filter is shown in Table 2 below.

The temperature and light resistance were measured in the same manner as in Examples 24 and 25 using the obtained filter. The results are shown in Table 2 below.

[0166]

[Table 2]

As can be seen by comparing the results of the visible light transmittance obtained in each of the above Examples of the present invention with the visible light transmittances of Comparative Examples 1 to 3, in this Example, Comparative Examples 1 to 3 were used. 750 to 1,10 without further reducing the visible light transmittance
It absorbs near-infrared light and heat ray light of 0 nm. In other words, it can be seen that, while having near infrared light and heat ray light absorption capabilities equal to or greater than Comparative Examples 1 to 3, the transparency is further excellent.

Further, when comparing the solubility obtained in this example with the solubility of Comparative Example 4, a large difference is observed in the solubility. In other words, it can be seen that the phthalocyanine compound of the present invention has a very high solubility, and therefore has a feature that it is very easily compatible with a resin.

As is clear from comparison with Comparative Examples 6 and 7, this example can suppress the rise in temperature and has a high visible light transmittance, that is, it can reduce the transmission of visible light. It can be seen that heat rays can be efficiently absorbed and blocked without hindrance. That is, it is excellent in transparency and heat ray shielding effect.

Further, it can be seen that the change in color difference after the light fastness test is small, the weather fastness is excellent, and it can be sufficiently used practically.

[Brief description of the drawings]

FIG. 1 is a schematic view of a temperature measuring device having a structure in which heat does not accumulate because wind blows through the panels for measurement used in Examples 24 and 25 and Comparative Examples 5 to 7.

[Description of Signs] 1 ... direct sunlight, 2 ... support, 3 ... support, 4 ... measurement filter 5 ... sample support plate, 6 ... temperature measurement device, 7 ... black panel, 8 ... temperature sensor, 9 ... lead wire.

──────────────────────────────────────────────────続 き Continuation of the front page (51) Int.Cl. ⁷ Identification symbol FI G03G 9/09 G03G 9/08 361 (56) References JP-A-6-264050 (JP, A) JP-A-5-345661 ( JP, A) JP-A-6-25548 (JP, A) JP-A-64-45474 (JP, A) JP-A-2-283769 (JP, A) JP-A-7-70129 (JP, A) JP Sho-64-31692 (JP, A) (58) Fields investigated (Int. Cl. ⁷ , DB name) C09B 47/22 B41M 5/00 C09K 3/00 105 CAPLUS (STN) REGISTRY (STN) WPIDS (STN)

Claims (13)

(57) [Claims] (1) The following general formula (1) (Wherein, Z ₂ , Z ₃ , Z ₆ , Z ₇ , Z ₁₀ , Z ₁₁ , Z ₁₄ ,
Z ₁₅ independently represents SR ¹ , OR ² or a fluorine atom, and at least one represents SR ¹ or OR ² , and Z ₁ , Z ₄ , Z ₅ , Z ₈ , Z ₉ , Z ₁₂ , Z ₁₃ , Z ₁₆
Independently represents NHR ³ , SR ¹ , OR ² or a fluorine atom, and at least one represents NHR ³ , and at least one of Z _{1 to} Z ₁₆ represents a fluorine atom or OR ²
And R ¹ , R ² , and R ^{3 each} independently may have a phenyl group which may have a substituent, an aralkyl group which may have a substituent or a substituent. Represents an alkyl group having 1 to 20 carbon atoms, and M represents a metal-free, metal, metal oxide or metal halide. The phthalocyanine compound represented by). 2. In the general formula (1), Z ₂ ,
_{Z 3, Z 6, Z 7} , Z 10, Z 11, Z 14, 4 or 8 all of Z ₁₅ is a phthalocyanine compound according to claim 1, characterized in that the SR ¹ or OR ² . 3. The phthalocyanine compound according to claim ¹ , wherein R ¹ , R ² and R ³ are each independently an alkyl group having 1 to 8 carbon atoms. 4. The method according to claim 1, wherein the remaining 5 to 1 substituents having ³ to 7 NHR ³ as substituents for substitution at 8 α-positions of the phthalocyanine nucleus are all fluorine atoms. The phthalocyanine compound according to one of the above. 5. The phthalocyanine compound according to claim 4, wherein 4 to 8 substituents which substitute at eight β-positions of the phthalocyanine nucleus are all SR ¹ or OR ² . 6. The method according to claim 6, wherein the transmission spectrum is measured at 750.
The visible light transmittance is 65% or more in a solution in which the concentration of the phthalocyanine compound is adjusted so that the minimum value of the transmittance at 〜1,100 nm is 5 to 6%.
A near-infrared absorbing dye comprising the phthalocyanine compound according to any one of the above. 7. A compound of the general formula (2) (Wherein Y represents SR ¹ or OR ² , and R ¹ ,
R ² is independently a phenyl group which may have a substituent, an aralkyl group which may have a substituent or an alkyl group having 1 to 20 carbon atoms which may have a substituent. And ad is independently an integer of 0 to 2,
And a sum of ad is an integer of 1 to 8, and M represents a metal-free, metal, metal oxide or metal halide) and NH ₂ R
³ (here, R ³ represents a phenyl group which may have a substituent, an aralkyl group which may have a substituent, or a C 1 to C 20 atom which may have a substituent. (Representing an alkyl group)) with an amino compound represented by the following general formula (3): (Wherein, Z ₂ , Z ₃ , Z ₆ , Z ₇ , Z ₁₀ , Z ₁₁ , Z ₁₄ ,
Z ₁₅ independently represents SR ¹ , OR ² or a fluorine atom, and at least one represents SR ¹ or OR ² , and Z ₁ , Z ₄ , Z ₅ , Z ₈ , Z ₉ , Z ₁₂ , Z ₁₃ , Z ₁₆
Independently represents NHR ³ , SR ¹ , OR ² or a fluorine atom, and at least one represents NHR ³ , and R ¹ , R ² , and R ³ independently represent a substituent. A good phenyl group, an optionally substituted aralkyl group or an optionally substituted 1 to 20 carbon atom (s)
M represents a metal-free, metal, metal oxide or metal halide. )). 8. The method according to claim 7, wherein the reaction is performed in an inert organic solvent. 9. A phthalocyanine compound or a near-infrared absorbing dye according to any one of claims 1 to 5 or a phthalocyanine compound represented by the formula (3) based on 100 parts of a resin. A heat ray shielding material comprising a resin containing 0.0005 to 20 parts by weight. 10. The resin according to claim 9, wherein said resin is a transparent resin.
The heat ray shielding material according to 1. 11. The transparent resin is a polycarbonate resin, a poly (meth) acrylic resin, a polyethylene resin,
The heat ray shielding material according to claim 9 or 10, wherein the heat ray shielding material is at least one selected from the group consisting of a polyester resin, a polystyrene resin, and a vinyl chloride resin. 12. A plasma display filter comprising the phthalocyanine compound or near-infrared absorbing dye according to any one of claims 1 to 5 or the phthalocyanine compound represented by the general formula (3). . 13. An amount of 0.1 to 100 parts by weight of the transparent resin.
The filter according to claim 12, comprising 0005 to 20 parts by weight of a phthalocyanine compound or a near-infrared absorbing dye.