JP4902819B1 - Phthalocyanine derivatives - Google Patents

Abstract

（式（１）中、Ｍは、金属等を表わし、Ｚ^１〜Ｚ^４は、それぞれ独立して、下記式（２）〜（５）であり、

式（２）〜（５）中、ｐ〜ｓは、０〜６の整数であり、Ｒ^１〜Ｒ^４は、下記式（６）、（６’）、（６’’）等で表される置換基（ア）またはハロゲン原子であり、

式（６）、（６’）、および（６’’）中、Ｒ^５は、アルコキシ基またはハロゲン原子であり、Ｒ^６は、アルキレン基であり、Ｒ^７は、アルキル基であり、ｔは、０〜４の整数であり、ｕは、０〜４の整数であり、ｔ’は、０〜６の整数である。
この際、Ｒ^１〜Ｒ^４として導入されるすべての基のうち、０．０５個以上３個未満は、水素原子であり、３〜６個は、置換基（ア）であり、かつ、残部はハロゲン原子である。）
【選択図】なしThe present invention provides a phthalocyanine derivative represented by the following formula (1) having high solubility in an ether solvent and improved heat resistance.

(In formula (1), M represents a metal or the ^like, Z 1 to Z ⁴ are each independently formula (2) to (5),

In formulas (2) to (5), p to s are integers of 0 to 6, and R ^{1 to} R ⁴ are represented by the following formulas (6), (6 ′), (6 ″) and the like. A substituent (a) or a halogen atom,

In formulas (6), (6 ′), and (6 ″), R ⁵ is an alkoxy group or a halogen atom, R ⁶ is an alkylene group, R ⁷ is an alkyl group, and t is , 0-4, u is an integer of 0-4, and t ′ is an integer of 0-6.
In this case, among all the groups introduced as R ^{1 to} R ⁴ , 0.05 or more and less than 3 are hydrogen atoms, 3 to 6 are substituents (a), and the balance Is a halogen atom. )
[Selection figure] None

Description

  The present invention relates to a phthalocyanine derivative and a flat panel display filter containing the compound.

  In recent years, phthalocyanine-based compounds are stable against light, heat, temperature, etc., and have excellent robustness, so that optical recording media such as compact discs, laser discs, optical memory discs, optical cards, etc. using semiconductor lasers as light sources It is used as a near-infrared absorbing dye used in In recent years, PDPs (Plasma Display Panels) that are thin and applicable to large screens have attracted attention. PDPs generate near-infrared light during plasma discharge, and these near-infrared rays are used for televisions for home appliances, coolers, and video decks. Inducing malfunctions of electrical devices such as these has become a problem.

  In order to solve these problems, the visible light transmittance is high, the near-infrared light cutting efficiency is high, the selective absorption ability in the near-infrared region is excellent, and the heat resistance, light resistance, and weather resistance are also good. Developments have been made on phthalocyanine compounds having excellent characteristics.

  As described above, various phthalocyanine compounds have been studied and developed. Conventional phthalocyanine compounds include methanol, alcohols such as ethanol and propanol, cellosolves such as ethyl cellosolve, glycols such as monoethylene glycol and diethylene glycol, acetone and methyl ethyl ketone. It is known that it is soluble in organic solvents such as ketones such as chloroform and toluene (for example, see Patent Document 1).

  However, conventional phthalocyanine compounds have not been sufficiently soluble in ether solvents. For this reason, there is a problem that even if the use of an ether solvent is appropriate, a sufficient amount of the phthalocyanine compound cannot be blended, and selection of the solvent to be used and the type of resin to be blended is limited. It was.

  In particular, color toner, inkjet ink, household inkjet ink, anti-counterfeit ink, especially anti-counterfeit bar code ink and anti-counterfeit offset ink, goggles lens and shielding plate, for sorting when recycling plastic Dyeing agents, optical recording media, photosensitive dyes for laser therapy, preheating aids during molding of PET bottles, photothermal exchange agents such as thermal transfer and thermal stencil, photothermal exchange agents for thermal rewritable recording, Anti-counterfeit prevention of ID cards, selection of solvents for use in laser heat transmission welding (LTW: Laser Transmission Welding), heat ray shielding agents, near-infrared absorption filters, etc. are limited There was a limit to the applications that can be applied. Therefore, there has been a high demand for phthalocyanine compounds that have high solubility in ether solvents and are useful for applications that cannot be applied conventionally. There was also a high demand for heat resistance.

JP-A-6-107663

  Accordingly, an object of the present invention is to provide a phthalocyanine derivative having high solubility in an ether solvent and improved heat resistance.

  As a result of intensive studies to solve the above problems, the present inventors have found that a phthalocyanine derivative having a specific structure has high heat resistance and high solubility in an ether solvent, and has found the present invention. It came to be completed.

  That is, the above object is achieved by the following formula (1):

In the above formula (1),
M represents metal-free, metal, metal oxide or metal halide;
Z ^{1 to} Z ⁴ are each independently the following formulas (2) to (5):

And
In the above formulas (2) to (5),
p is an integer of 0 to 4,
q is an integer of 0 to 3,
r is an integer from 0 to 2,
s is an integer from 0 to 6,
R ^{1 to} R ⁴ are each independently a nitro group, an amino group, a hydroxyl group, an alkyl group having 1 to 8 carbon atoms that may be substituted with a halogen atom, a substituent (a), a substituent (b),- A substituent (a) or a halogen atom selected from the group consisting of S- (R ⁹ O) _x R ¹⁰ , -S-L-A, and a substituent (c);
R ⁹ is an alkylene group having 1 to 3 carbon atoms, and R ¹⁰ may have a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, an acyl group having 1 to 8 carbon atoms, or a substituent. An alkylcarbamoyl group, x is an integer of 1 to 4,
L is an optionally substituted alkylene group having 1 to 3 carbon atoms, A is independently COOJ, OJ, CONJ ₂ or NJ ₂ , where J is each Independently, a hydrogen atom, an optionally substituted acyl group having 1 to 8 carbon atoms, an optionally substituted alkoxycarbonyl group, and an optionally substituted carbon number An alkyl group having 1 to 8 or — (R ¹¹ O) _y R ¹² , R ¹¹ is an alkylene group having 1 to 3 carbon atoms, and R ¹² is a hydrogen atom or an alkyl having 1 to 8 carbon atoms. A group, an acyl group having 1 to 8 carbon atoms, or an alkylcarbamoyl group which may have a substituent, and y is an integer of 1 to 4,
The substituent (a) is represented by the following formula (6), (6 ′) or (6 ″):

In the above formulas (6), (6 ′) and (6 ″), R ⁵ is an alkoxy group having 1 to 8 carbon atoms or a halogen atom, and R ⁶ is an alkylene group having 1 to 3 carbon atoms. , R ⁷ is an alkyl group having 1 to 8 carbon atoms, t is an integer of 0 to 4, u is an integer of 0 to 4, and t ′ is an integer of 0 to 6. I was
The substituent (b) is represented by the following formula (7):

In the above formula (7), X is an oxygen atom or a sulfur atom, Ar is an optionally substituted phenyl group or a naphthyl group R ^8, this time, R ⁸ are each independently cyano A group, a nitro group, COOY, OY, a halogen atom, an aryl group, or an alkyl group having 1 to 8 carbon atoms which may be substituted with a halogen atom, wherein Y is an alkyl group having 1 to 8 carbon atoms And represented by
The substituent (c) is represented by the following formula (8):

In the above formula (8), R ¹³ is independently COOJ ′, OJ ′, CON (J ′) ₂ , N (J ′) ₂ or a halogen atom, and J ′ is independently A hydrogen atom, an alkoxycarbamoyl group which may have a substituent, an alkoxycarbonyl group which may have a substituent, a phenyl group which may have a substituent, and a substituent. An optionally substituted alkyl group having 1 to 8 carbon atoms, an optionally substituted alkoxy group having 1 to 8 carbon atoms or — (R ¹⁴ O) _z R ¹⁵ , and w is 0 to 5 R ¹⁴ is an alkylene group having 1 to 3 carbon atoms, R ¹⁵ is a hydrogen atom or an alkyl group having 1 to 8 carbon atoms, and z is an integer of 1 to 4. Represented,
At this time, among all the groups introduced as R ^{1 to} R ⁴ , 0.05 or more and less than 3 are hydrogen atoms, 1 to 6 are substituents (a), and the balance Is achieved by a phthalocyanine derivative represented by

  According to the present invention, a phthalocyanine derivative having high solubility in an ether solvent and improved heat resistance can be provided.

  The phthalocyanine derivative of the present invention can be dissolved in an ether solvent. Therefore, even a resin that is relatively selectively dissolved in an ether solvent can be used. It can also be used for applications in which a phthalocyanine dye is applied to a plastic that may be dissolved when a solvent other than an ether solvent is used.

  In addition, the phthalocyanine derivative of the present invention has improved heat resistance. Therefore, adaptability to the external environment is significantly high, and it can be used for various purposes.

<First of the present invention>
The first of the present invention is the following formula (1):

In the above formula (1),
M represents metal-free, metal, metal oxide or metal halide;
Z ^{1 to} Z ⁴ are each independently the following formulas (2) to (5):

And
In the above formulas (2) to (5),
p is an integer of 0 to 4,
q is an integer of 0 to 3,
r is an integer from 0 to 2,
s is an integer from 0 to 6,
R ^{1 to} R ⁴ are each independently a nitro group, an amino group, a hydroxyl group, an alkyl group having 1 to 8 carbon atoms that may be substituted with a halogen atom, a substituent (a), a substituent (b),- A substituent (a) or a halogen atom selected from the group consisting of S- (R ⁹ O) _x R ¹⁰ , -S-L-A, and a substituent (c);
R ⁹ is an alkylene group having 1 to 3 carbon atoms, and R ¹⁰ may have a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, an acyl group having 1 to 8 carbon atoms, or a substituent. An alkylcarbamoyl group, x is an integer of 1 to 4,
L is an optionally substituted alkylene group having 1 to 3 carbon atoms, A is independently COOJ, OJ, CONJ ₂ or NJ ₂ , where J is each Independently, a hydrogen atom, an optionally substituted acyl group having 1 to 8 carbon atoms, an optionally substituted alkoxycarbonyl group, and an optionally substituted carbon number An alkyl group having 1 to 8 or — (R ¹¹ O) _y R ¹² , R ¹¹ is an alkylene group having 1 to 3 carbon atoms, and R ¹² is a hydrogen atom or an alkyl having 1 to 8 carbon atoms. A group, an acyl group having 1 to 8 carbon atoms, or an alkylcarbamoyl group which may have a substituent, and y is an integer of 1 to 4,
The substituent (a) is represented by the following formula (6), (6 ′) or (6 ″):

In the above formulas (6), (6 ′) and (6 ″), R ⁵ is an alkoxy group having 1 to 8 carbon atoms or a halogen atom, and R ⁶ is an alkylene group having 1 to 3 carbon atoms. , R ⁷ is an alkyl group having 1 to 8 carbon atoms, t is an integer of 0 to 4, u is an integer of 0 to 4, and t ′ is an integer of 0 to 6. I was
The substituent (b) is represented by the following formula (7):

In the above formula (7), X is an oxygen atom or a sulfur atom, Ar is an optionally substituted phenyl group or a naphthyl group R ^8, this time, R ⁸ are each independently cyano A group, a nitro group, COOY, OY, a halogen atom, an aryl group, or an alkyl group having 1 to 8 carbon atoms which may be substituted with a halogen atom, wherein Y is an alkyl group having 1 to 8 carbon atoms And represented by
The substituent (c) is represented by the following formula (8):

In the above formula (8), R ¹³ is independently COOJ ′, OJ ′, CON (J ′) ₂ , N (J ′) ₂ or a halogen atom, and J ′ is independently A hydrogen atom, an alkoxycarbamoyl group which may have a substituent, an alkoxycarbonyl group which may have a substituent, a phenyl group which may have a substituent, and a substituent. An optionally substituted alkyl group having 1 to 8 carbon atoms, an optionally substituted alkoxy group having 1 to 8 carbon atoms or — (R ¹⁴ O) _z R ¹⁵ , and w is 0 to 5 R ¹⁴ is an alkylene group having 1 to 3 carbon atoms, R ¹⁵ is a hydrogen atom or an alkyl group having 1 to 8 carbon atoms, and z is an integer of 1 to 4. Represented,
At this time, among all the groups introduced as R ^{1 to} R ⁴ , 0.05 or more and less than 3 are hydrogen atoms, 1 to 6 are substituents (a), and the balance Relates to a phthalocyanine derivative represented by

  Hereinafter, the phthalocyanine derivative represented by the above formula (1) is also simply referred to as “phthalocyanine derivative” or “phthalocyanine derivative of the present invention”. The reason why it can be a decimal number such as “0.1” is as follows. That is, in order to produce the “phthalocyanine derivative” of the present invention, the raw material (phthalonitrile derivative) for producing the “phthalocyanine derivative” is mixed in a desired ratio. At this time, the produced “phthalocyanine derivative” is in the form of a mixture having various structures. That is, the number of “hydrogen atoms” can be decimal, and the remaining halogen atoms can be decimal.

  Since the phthalocyanine derivative of the present invention has the above structure, it has the following advantages.

  (I) The solubility in an ether solvent can be improved.

  In the phthalocyanine derivative of the present invention, there are a specific number of hydrogen atoms into which substituent (a) and halogen atom are not introduced. Therefore, the structure of the phthalocyanine derivative is entirely irregular (random structure), and the crystallinity is deteriorated. If it does so, the solubility to an ether solvent can be improved. Also, thanks to its high solubility in ether solvents, it can be used in combination with resins and dyes that are highly soluble in ether solvents, and plastics that are soluble in solvents other than ether solvents can be used. Even if it is used, a pigment can be coated on the plastic.

  (Ii) It has a maximum absorption wavelength (λmax) in a wavelength region of 640 to 750 nm in the near infrared region. Thanks to the maximum absorption wavelength (λmax) in the short wavelength region, light in the useless near infrared region (700 to 750 nm) emitted by flat panel displays, particularly PDPs and LCDs, and the so-called impure red wavelength (640) (Up to 700 nm) can be cut, for example, to prevent malfunction of the optical communication system, and at the same time, the effect of reproducing a clear red color can be exhibited. In particular, since PDP exhibits excessively large light emission in the vicinity of 710 nm, a dye that absorbs light at 710 nm and has high visible light transmittance such as 520 nm is useful. In addition to the above, each phthalocyanine derivative has a low wavelength mobility and a spectrum having a relatively sharp peak at the maximum absorption wavelength. For this reason, even if the phthalocyanine derivative of this invention is a form of a mixture, it is easy to be settled in a desired wavelength. In the phthalocyanine derivative of the present invention, a substituent (—OE) containing an oxygen atom or a substituent (—SE) containing a sulfur atom is introduced into the phthalocyanine skeleton as the substituent (a) or (b). preferable. Here, the characteristics of the phthalocyanine derivative generally vary depending on the type of substituent, the introduction site, the number of introductions, and the like. For example, as the type of the substituent, the absorption wavelength of the phthalocyanine derivative is changed in the order of a substituent containing an oxygen atom (—OE), a substituent containing a sulfur atom (—SE), and a substituent containing a nitrogen atom (—NE). It can be shifted to the shorter wavelength side. In the phthalocyanine derivative of the present invention, when a substituent containing an oxygen atom (-OE) or a substituent containing a sulfur atom (-SE) is introduced, the selective absorption ability in the near infrared wavelength region of 640 to 750 nm is increased. . “E” means any substituent.

  (Iii) High heat resistance.

Of all the groups introduced as R ^{1 to} R ⁴ , the remainder other than the hydrogen atom and the substituent (a) is a halogen atom. Thus, heat resistance can be improved by arrange | positioning a halogen atom in remainder.

  Hereinafter, a preferred embodiment in the first aspect of the present invention will be described.

  In the first of the present invention, the following formula (1):

  In said formula (1), M represents a non-metal, a metal, a metal oxide, or a metal halide.

  In the above formula (1), M represents a metal-free, metal, metal oxide or 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 (II) chloride, tin (IV) chloride, and silicon chloride. Preferred are metals, metal oxides or metal halides, more preferred are copper, vanadyl and zinc, and even more preferred are zinc and copper. It is particularly preferable that the central metal is zinc or copper because of high heat resistance.

In the above formula (1), Z ^{1 to} Z ⁴ are each independently the following formulas (2) to (5):

It is. In the present invention, when the above formula (2) is introduced into all of Z ^{1 to} Z ⁴ , it is a generally called “phthalocyanine compound”.

p is an integer of 0-4. There is no particular limitation on the site where R ¹ is introduced, and any of the 1-, 2-, 3-, and 4-positions may be used, but the 2-, 3-position is preferred. Of course, a plurality may be introduced. In the case of introducing a plurality, it is preferable that the first, second, second, third and first, third combinations are introduced.

q is an integer of 0-3. There are no particular restrictions on the site where R ² is introduced, and any of the 2nd, 3rd and 4th positions may be used, but the 2nd and 3rd positions are preferred. Of course, a plurality may be introduced. In the case of introducing a plurality, for example, it is preferable that they are introduced in a combination of 2nd, 3rd, 2nd, 4th.

r is an integer of 0-2. There is no particular limitation on the site where R ³ is introduced, and it may be in any of the 2nd and 3rd positions. Of course, a plurality may be introduced.

s is an integer of 0-6. In particular limitations on site R ⁴ is introduced instead, may be any position of the 1-6-position, preferably 3-position, 4-position. Of course, a plurality may be introduced. In the case of introducing a plurality, it is preferable to introduce them in a combination of, for example, 3, 4 positions, 1, 3 positions, or 1, 4 positions.

In addition, when p, q, r, and s are each 0, it means that R ^{1 to} R ⁴ are not introduced but a hydrogen atom is introduced.

In addition, when the above formulas (2) to (4) are introduced as Z ^{1 to} Z ⁴ , the 1-position and 4-position may be referred to as α-position (substituent at α-position), and the 2-position, 3-position May also be referred to as β-position (substituent at β-position).

R ^{1 to} R ⁴ are each independently a nitro group, an amino group, a hydroxyl group, an alkyl group having 1 to 8 carbon atoms that may be substituted with a halogen atom, a substituent (a), a substituent (b),- S— (R ⁹ O) _x R ¹⁰ , —S—L—A, and a substituent (a) selected from the group consisting of the substituent (c) or a halogen atom. Among these, in consideration of heat resistance and solvent solubility, it is preferable that at least one of the substituent (a) and the substituent (b) is introduced, and at least the substituent (a) is introduced. More preferably. In consideration of heat resistance such as heat resistance and solvent solubility, it is also preferable that at least a halogen atom is introduced.

(C1-C8 alkyl group which may be substituted with a halogen atom)
It does not restrict | limit especially as a C1-C8 alkyl group which may be substituted by a halogen atom, A C1-C8 linear, branched or cyclic alkyl group is mentioned. More specifically, examples of the alkyl group having 1 to 8 carbon atoms include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert-butyl group, n Examples include linear, branched or cyclic alkyl groups such as -pentyl group, isopentyl group, neopentyl group, n-hexyl group, cyclohexyl group, n-heptyl group, n-octyl group and 2-ethylhexyl group. Among these, in consideration of the above properties such as heat resistance and solvent solubility, particularly solvent solubility, a linear or branched alkyl group having 1 to 5 carbon atoms, particularly a linear or branched alkyl group having 1 to 3 carbon atoms. Group is preferable, and in particular, a tert-butyl group is preferable. When a bulky substituent such as a tert-butyl group is present, the structure of the resulting phthalocyanine derivative becomes entirely random (becomes a random structure) and crystallinity is deteriorated, so that the solubility in an ether solvent is improved. This is also preferable. In addition, as for the halogen atom, the explanation items disclosed in the present specification are equally applicable.

  Moreover, as a halogen atom, a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom are mentioned. Among these, a chlorine atom, a fluorine atom, and a bromine atom are preferable in consideration of heat resistance and solvent solubility.

(Substituent (a))
The substituent (a) is represented by the following formula (6), (6 ′) or (6 ″).

In the above formulas (6), (6 ′) and (6 ″), R ⁵ is an alkoxy group having 1 to 8 carbon atoms or a halogen atom, t is an integer of 0 to 4, and t ′ is , An integer from 0 to 6.

  Here, as the alkoxy group having 1 to 8 carbon atoms, methoxy group, ethoxy group, propoxy group, isopropoxy group, butoxy group, pentyloxy group, hexyloxy group, 2-ethylhexyloxy group, octyloxy group, etc. Examples include a chain, branched or cyclic alkoxy group. Among these, in consideration of the above properties such as heat resistance and solvent solubility, especially solvent solubility, a linear or branched alkoxy group having 1 to 5 carbon atoms, particularly a linear or branched alkoxy group having 1 to 3 carbon atoms. Groups are preferred.

  Further, as the halogen atom, the above specific examples are equally applicable, and among them, a chlorine atom or a bromine atom is preferable in consideration of heat resistance, solvent solubility, and the like.

Further, in the above formula, t and t ′ represent the number of alkoxy groups or halogen atoms (R ⁵ ) bonded to the phenoxy group, t is an integer of 0 to 4, and t ′ is 0 to 6 It is an integer. t is preferably an integer of 0 to 3 from the viewpoint of molecular weight. Further, t ′ is preferably an integer of 0 to 3 from the viewpoint of molecular weight.

As is clear from the above formula, the substituent (a) includes one substituent “—COO (R ⁶ O) _u R ⁷ ” and, if necessary, one or more C 1-8 alkoxy groups. Or it is a phenoxy group (Formula (6)) which has a halogen atom (-R < ⁵ >). Alternatively, the substituent (a) includes one substituent “—COO (R ⁶ O) _u R ⁷ ” and, if necessary, one or more alkoxy groups having 1 to 8 carbon atoms or a halogen atom (—R ⁵ ). A naphthoxy group having the formula (formula (6 ′)). Alternatively, the substituent (a) includes one substituent “—SO ₃ (R ⁶ O) _u R ⁷ ” and, if necessary, one or more alkoxy groups having 1 to 8 carbon atoms or a halogen atom (—R ⁵ ) Having a phenoxy group (formula (6 ″)).

In the above formula (6 ′), —R ⁵ , oxygen atom (—O—) and substituent “—COO (R ⁶ O) _u R ⁷ ” may be replaced with any hydrogen atom of the naphthalene ring. Good. That is, in the above formula (6 ′), the substituent “—COO (R ⁶ O) _u R ⁷ ” is present in the benzene ring on the side where the oxygen atom is present, of the two benzene rings. This substituent is not meant to be present at that position, but may be present on the other benzene ring. That is, the substituent (a) of the above formula (6 ′) includes both the following substituents (a ₁ ) and (a ₂ ). Similarly, -R ⁵ may be present in any benzene ring (however, it is not represented in the following substituents (a ₁ ) and (a ₂ )).

In the above formulas (6), (6 ′) and (6 ″), R ⁶ is an alkylene group having 1 to 3 carbon atoms, and u is an integer of 0 to 4.

Here, examples of the alkylene group having 1 to 3 carbon atoms include a methylene group, an ethylene group, a tetramethylene group, and a propylene group. Among these, considering the above characteristics such as heat resistance and solvent solubility, particularly solvent solubility, R ⁶ is preferably an ethylene group or a propylene group, and more preferably an ethylene group.

Further, in the above formula, u represents the number of repeating units of oxyalkylene groups ^(R 6 O), it is an integer of 0-4. In consideration of the above characteristics such as heat resistance and solvent solubility, particularly solvent solubility, u is preferably 0 to 3, particularly preferably 0 to 2.

In the above formulas (6), (6 ′) and (6 ″), R ⁷ is an alkyl group having 1 to 8 carbon atoms.

  Here, the alkyl group having 1 to 8 carbon atoms is not particularly limited, and examples thereof include the same ones as described above. Among these, in consideration of the above properties such as heat resistance and solvent solubility, particularly solvent solubility, a linear or branched alkyl group having 1 to 5 carbon atoms, particularly a linear or branched alkyl group having 1 to 3 carbon atoms. Group is preferable, and a methyl group is particularly preferable.

In the substituent (a) of the above formula (6), the bonding position of the substituent —COO (R ⁶ O) R ^{7 to} the benzene ring is not particularly limited. For example, when t is 0, the substituent (a) has a structure in which one substituent “—COO (R ⁶ O) _u R ⁷ ” is bonded to a phenoxy group. Here, the substituent “—COO (R ⁶ O) _u R ⁷ ” is arranged at any position of the phenoxy group in the ortho position (second position), the meta position (third position), or the para position (fourth position). Is done. Of these, the 2nd and 4th positions are preferred, and the 4th position is particularly preferred. When the relatively bulky substituent —COO (R ⁶ O) _u R ⁷ is placed in the 4-position, the resulting phthalocyanine derivative absorbs light at 710 nm and has a high transmittance for visible light such as 520 nm, The absorbance ratio [= absorbance at 710 nm / absorbance at 520 nm; also referred to as “Abs (λ710 nm) / Abs (λ520 nm)”] can be increased. Moreover, when the relatively bulky substituent —COO (R ⁶ O) _u R ⁷ is arranged at the 4-position, the resulting phthalocyanine derivative can improve the solvent solubility.

In the above formula (6), when t is 1, the substituent (a) has one substituent “—COO (R ⁶ O) _u R ⁷ ” and one carbon number 1 to 1 8 has a structure in which an alkoxy group or a halogen atom (—R ⁵ ) is bonded to a phenoxy group. Here, each of the substituents “—COO (R ⁶ O) _u R ⁷ ” and “R ⁵ ” may be introduced at any position of the phenoxy group. At this time, considering the above-mentioned characteristics such as heat resistance, absorbance ratio and solvent solubility, especially solvent solubility, considering solvent solubility and absorbance ratio, 2, 4th, 2, 5th, 2, 6th, The 3rd and 4th positions are preferable, and the 2nd, 4th and 2nd and 6th positions are more preferable.

In the above formula (6), when t is 2, the substituent (a) has one substituent “—COO (R ⁶ O) _u R ⁷ ” and two carbon atoms 1 to 8 has a structure in which an alkoxy group or a halogen atom (—R ⁵ ) is bonded to a phenoxy group. Here, each of the substituents “—COO (R ⁶ O) _u R ⁷ ” and “R ⁵ ” may be introduced at any position of the phenoxy group. At this time, considering the above characteristics such as heat resistance, absorbance ratio and solvent solubility, especially solvent solubility, considering solvent solubility and absorbance ratio, 2, 4, 5 position, 2, 4, 6 position, 3 , 4, 5 and the like, and 2, 4, 6 and 3,4, 5 are more preferable.

In addition, in the substituent (a) of the above formula (6 ′), the bonding position of the oxygen atom (—O—) to the naphthalene ring is not particularly limited, and may be derived from 1-naphthol or 2-naphthol. Preferably, the substituent (a) is derived from 1-naphthol. Similarly, the bonding position of the substituent —COO (R ⁶ O) _u R ^{7 to} the naphthalene ring is not particularly limited. For example, when t ′ is 0, the substituent (a) has a structure in which one substituent “—COO (R ⁶ O) _u R ⁷ ” is bonded to a naphthoxy group. When t ′ is 1, the substituent (a) includes one substituent “—COO (R ⁶ O) _u R ⁷ ” and one alkoxy group having 1 to 8 carbon atoms or a halogen atom ( -R ⁵⁾ has a structure bonded to a naphthoxy group. Therefore, when the substituent (a) is derived from 1-naphthol, the bonding position of the substituent: —COO (R ⁶ O) R ^{7 to} the naphthalene ring is the 2-position, 3-position, 4-position, 5 However, in consideration of the absorbance ratio, solvent solubility, etc., the 2nd, 3rd and 4th positions are preferable, and the 2nd position is more preferable. In addition, when the substituent (a) is derived from 2-naphthol, the bonding position of the substituent: —COO (R ⁶ O) R ^{7 to} the naphthalene ring is 1, 3, 4, 5, , 6-position, 7-position, or 8-position may be used, but 3-position and 6-position are preferable in consideration of the absorbance ratio and solvent solubility.

In the substituent (a) of the above formula (6 ″), the bonding position of the substituent —SO ₃ (R ⁶ O) R ^{7 to} the benzene ring is not particularly limited. For example, when t is 0, the substituent (a) has a structure in which one substituent “—SO ₃ (R ⁶ O) _u R ⁷ ” is bonded to a phenoxy group. Here, the substituent “—SO ₃ (R ⁶ O) _u R ⁷ ” is located at any position of the phenoxy group in the ortho position (the 2-position), the meta position (the 3-position), or the para-position (the 4-position). Be placed. Of these, the 2nd and 4th positions are preferred, and the 4th position is particularly preferred. When the relatively bulky substituent —SO ₃ (R ⁶ O) _u R ⁷ is placed in the 4-position, the resulting phthalocyanine derivative absorbs light at 710 nm and has a high transmittance for visible light such as 520 nm, ie The absorbance ratio [= absorbance at 710 nm / absorbance at 520 nm; also referred to as “Abs (λ710 nm) / Abs (λ520 nm)”] can be increased. Moreover, when the relatively bulky substituent —SO ₃ (R ⁶ O) _u R ⁷ is arranged at the 4-position, the resulting phthalocyanine derivative can improve solvent solubility.

In the above formula (6 ″), when t is 1, the substituent (a) includes one substituent “—SO ₃ (R ⁶ O) _u R ⁷ ” and one carbon. It has a structure in which an alkoxy group of formula 1 to 8 or a halogen atom (—R ⁵ ) is bonded to a phenoxy group. Here, the substituents “—SO ₃ (R ⁶ O) _u R ⁷ ” and “R ⁵ ” may each be introduced at any position of the phenoxy group. At this time, considering the above-mentioned characteristics such as heat resistance, absorbance ratio and solvent solubility, especially solvent solubility, considering solvent solubility and absorbance ratio, 2, 4th, 2, 5th, 2, 6th, The 3rd and 4th positions are preferable, and the 2nd, 4th and 2nd and 6th positions are more preferable.

  That is, the substituent (a) is particularly preferably one having the following structure.

In view of the intended purpose of the present invention, R ⁵ is preferably a methoxy group or a halogen atom, R ⁶ is preferably a methylene group or an ethylene group, and u is It is preferably 0, 1 or 2, and R ⁷ is preferably a methyl group or an ethyl group. In particular, R ⁶ is preferably an ethylene group, u is preferably 0 or 1, and R ⁷ is preferably a methyl group.

(Substituent (b))
The substituent (b) is represented by the following formula (7).

In the above formula (7), X is an oxygen atom (-O-) or a sulfur atom (-S-), Ar is an optionally substituted phenyl group or a naphthyl group ^{R 8.}

In the formula (7), each R ⁸ may be independently substituted with a cyano group (—CN), a nitro group (—NO ₂ ), COOY, OY, a halogen atom, an aryl group, or a halogen atom. A good alkyl group having 1 to 8 carbon atoms, wherein Y is an alkyl group having 1 to 8 carbon atoms. When a plurality of R ⁸ are present (that is, 2 to 7 R ⁸ are present), the plurality of R ⁸ may be the same or different.

When R ⁸ is COOY or OY, Y is an alkyl group having 1 to 8 carbon atoms. Here, the alkyl group having 1 to 8 carbon atoms is not particularly limited, and examples thereof are the same as those described above. Specifically, an alkyl group having 1 to 4 carbon atoms is preferable, and An alkyl group is preferable, and an ethyl group or a methyl group is more preferable. Of these, halogen atoms, COOY, and OY are preferable in consideration of the above properties such as heat resistance, solvent solubility, and absorbance ratio, particularly solvent solubility, and substitution with a cyano group, nitro group, or halogen atom in consideration of heat resistance. An alkyl group having 1 to 8 carbon atoms which may be used is preferable, and an aryl group is preferable in consideration of an absorbance ratio. Note that when R ⁸ is COOY, there may overlap with a substituent (a), if so, shall prevail substituents (a). That is, in the “substituent (b)”, a portion overlapping with the “substituent (a)” is excluded.

When R ⁸ is a halogen atom, examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. Among these, considering heat resistance and solvent solubility, a chlorine atom and a fluorine atom are preferable, and a chlorine atom is particularly preferable. In addition, when R ⁸ is a chlorine atom, a fluorine atom, particularly a fluorine atom, the molecular weight of the dye is decreased, and the absorbance per gram can be increased.

In addition, when R ⁸ is an aryl group, examples of the aryl group include aryl groups such as a phenyl group, a p-methoxyphenyl group, a pt-butylphenyl group, and a p-chlorophenyl group. Among them, a phenyl group is preferable because the molecular weight of the dye is reduced and the absorbance per gram is increased.

In addition, when R ⁸ is an alkyl group having 1 to 8 carbon atoms which may be substituted with a halogen atom, the alkyl group having 1 to 8 carbon atoms which may be substituted is not particularly limited, Specific examples described above can be given. Among these, in consideration of the above properties such as heat resistance and solvent solubility, particularly solvent solubility, a linear or branched alkyl group having 1 to 5 carbon atoms is preferable. Examples of the halogen atom that is a substituent of the alkyl group that may be present include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. Among these, a fluorine atom or a chlorine atom is preferable, and a fluorine atom is more preferable. There may be a plurality of halogen atoms as substituents for the alkyl group, and when there are a plurality of halogen atoms, they may be the same or different. The number of substituents on the alkyl group is not particularly limited, but is preferably 1 to 3. For example, when a plurality of halogen atoms are substituted such as two or three, the effect of improving heat resistance is achieved. R ⁸ is not particularly limited as long as it is in the range of 0 to 7, but from the viewpoint of molecular weight reduction, 0 to 5 is preferable, 0 to 3 is more preferable, and 0 to 2 is particularly preferable.

In the substituent (b) of the above formula (7), the bonding position of the substituent R ^{8 to} the benzene ring is not particularly limited. Preferably, any of ortho position (2nd position), meta position (3rd position) or para position (4th position) may be used.

When the substituent R ⁸ is arranged in these, the obtained phthalocyanine derivative absorbs light at 710 nm and has high transmittance of visible light such as 520 nm, that is, an absorbance ratio [= absorbance at 710 nm / absorbance at 520 nm. “Abs (λ710 nm) / Abs (λ520 nm)”] can be increased. Further, when the substituent R ⁸ is arranged at the 2-position, the 3-position or the 4-position, the resulting phthalocyanine derivative can improve the solvent solubility.

Further, when R ⁸ is 2 may be introduced at any position in the benzene ring. At this time, considering the above-mentioned characteristics such as heat resistance, absorbance ratio and solvent solubility, especially solvent solubility, considering solvent solubility and absorbance ratio, 2, 4th, 2, 5th, 2, 6th, The 3rd and 4th positions are preferred, the 2nd, 4th, 2,5th and 2nd and 6th positions are more preferred, and the 2nd and 6th positions are even more preferred.

When R ⁸ is 3, it may be introduced at any position of the benzene ring. In this case, considering the above-mentioned characteristics such as heat resistance, absorbance ratio and solvent solubility, especially solvent solubility, the 2,4,6 position, 2,5,6 position and the like are considered when considering the solvent solubility and absorbance ratio. Preferably, the 2, 4, and 6 positions are more preferable.

Among the above, considering the intended purpose of the present invention, X is an oxygen atom (—O—) or a sulfur atom (—S—), and R ⁸ is a halogen atom (especially a chlorine atom or a bromine atom). , An alkyl group having 1 to 8 carbon atoms which may be substituted with a halogen atom (particularly an alkyl group having 1 to 4 carbon atoms which may be substituted with a halogen atom), an aryl group (particularly a phenyl group or a naphthyl group) Are preferably COOY (Y is particularly an alkyl group having 1 to 3 carbon atoms), OY (Y is particularly an alkyl group having 1 to 3 carbon atoms), R ⁸ is 0 to 2, and R ⁸ is for one, the 2-position, a 3-position or 4-position, when R ⁸ is a 2, preferably a position of the 2,6 position.

Also, in the substituents of the above formula (7) (b), Ar is when it is a naphthyl group which may be substituted with ^{R 8,} substitution number of ^{R 8} in Ar also substituted for ^{R 8} in Ar The number is not particularly limited and can be appropriately selected depending on the desired effect (gram absorption coefficient, solvent solubility, heat resistance, light absorption at 710 nm, visible light transmittance at 520 nm, etc.). For example, when Ar is a naphthyl group optionally substituted by ^{R 8,} substitution number of ^{R 8} in Ar is 0-5, preferably 0-3, more preferably 0-2 And particularly preferably 0 or 1. Further, the bonding position of the substituent R ^{8 to} the naphthalene ring is not particularly limited, and depends on the desired effect (gram absorption coefficient, solvent solubility, heat resistance, 710 nm light absorption, 520 nm visible light transmission, etc.). It can be selected as appropriate. For example, when R ⁸ is 1 and Ar is a 1-naphthyl group, the bonding position of R ^{8 to} the naphthalene ring is 2, 3, 4, 5, 6, 7 or Any of the 8-positions may be used, but in consideration of heat resistance, solvent solubility, etc., the 2-position, 3-position, and 4-position are preferred, and the 2-position is more preferred. When the substituent (a) is derived from 2-naphthol, the bonding position of the substituent (b) to the naphthalene ring is the 1st, 3rd, 4th, 5th, 6th, 7th or Any of the 8th positions may be used, but the 1st, 3rd and 6th positions are preferable, and the 3rd and 6th positions are more preferable in consideration of heat resistance and solvent solubility.

_{^{(-S- (R 9 O) x}} R 10)
R ^{1 to} R ⁴ are each independently preferably —S— (R ⁹ O) _x R ¹⁰ .

R ⁹ is an alkylene group having 1 to 3 carbon atoms. Such an alkylene group may be linear or branched. Here, examples of the alkylene group having 1 to 3 carbon atoms include a methylene group, an ethylene group, a tetramethylene group, a propylene group, and an isopropylene group. Here, an ethylene group and an isopropylene group are preferable from the viewpoint of solvent solubility.

R ¹⁰ is a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, an acyl group having 1 to 8 carbon atoms, or an alkylcarbamoyl group which may have a substituent.

  Examples of the alkyl group having 1 to 8 carbon atoms are the same as those described above. A methyl group, an ethyl group, an isopropyl group, and a 2-ethylhexyl group are preferable.

Acyl group having 1 to 8 carbon atoms are those represented by ^{-COR 16, wherein,} as the ^{R 16,} an alkyl group having 1 to 8 carbon atoms which may have a hydrogen atom or a substituent. Examples of the alkyl group having 1 to 8 carbon atoms are the same as those described above. Therefore, from the viewpoint of solvent solubility, R ¹⁶ is preferably a methyl group, an ethyl group, a tert-butyl group, an n-butyl group, or the like.

The alkylcarbamoyl group which may have a substituent is represented by —CON (R ¹⁷ ) ₂ , where R ¹⁷ independently has a hydrogen atom or a substituent. Examples thereof include an alkyl group having 1 to 8 carbon atoms. As such a substituent, a methoxy group and the like are preferable. The alkyl group having 1 to 8 carbon atoms is preferably an ethyl group or an isopropyl group from the viewpoint of solvent solubility. Accordingly, R ¹⁷ is preferably independently an ethyl group, an isopropyl group, a methoxyethyl group, or the like.

  Moreover, x is an integer of 1-4, Preferably it is an integer of 1-3.

When “—S— (R ⁹ O) _x R ¹⁰ ” is summarized, the following specific examples are preferred.

(-S-L-A)
R ^{1 to} R ⁴ are preferably each independently -SLA.

  Of “—S—L—A”, S is a sulfur atom.

  Among “—S—L—A”, L is an alkylene group having 1 to 3 carbon atoms which may have a substituent. Here, the number of substituents is not particularly limited, and is one or two, for example. Examples of the alkylene group having 1 to 3 carbon atoms include a methylene group, an ethylene group, and a propylene group. Among these, in consideration of the above properties such as heat resistance and solvent solubility, particularly solvent solubility, a methylene group or an ethylene group is particularly preferable.

  Here, examples of the substituent include an alkoxycarbonyl group having 1 to 4 carbon atoms, an alkylcarbamoyl group which may have a substituent, an alkyl group having 1 to 12 carbon atoms, and an acyl group having 1 to 8 carbon atoms. It is done.

The alkoxycarbonyl group has a structure of —COOR ¹⁸ , where R ¹⁸ is an optionally substituted alkyl group having 1 to 8 carbon atoms, and an alkyl group having 1 to 8 carbon atoms. Specific examples similar to those described above are appropriate for the group, and specific examples similar to those described above are also applicable to the substituent. Specific examples of R ¹⁸ are preferably an ethyl group, a methoxyethyl group, and the like.

The alkylcarbamoyl group which may have a substituent is represented by —CON (R ¹⁷ ) ₂ , where R ¹⁷ independently has a hydrogen atom or a substituent. Examples thereof include an alkyl group having 1 to 8 carbon atoms. Examples of the alkyl group having 1 to 8 carbon atoms include the same ones as described above, and specific examples of the substituents are the same as above. Specifically, R ¹⁷ is independently a hydrogen atom. And a methoxypropyl group are preferred.

  Further, the alkyl group having 1 to 12 carbon atoms is not particularly limited, but is methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert-butyl group, pentyl group. , Isopentyl group, neopentyl group, n-hexyl group, heptyl group, octyl group, nonyl group, n-decyl group, undecyl group, dodecyl group and 2-ethylhexyl group.

Moreover, the acyl group having 1 to 8 carbon atoms are those represented by ^{-COR 16, wherein,} as the ^{R 16,} an alkyl group having 1 to 8 carbon atoms which may have a substituent group, a substituted Examples of the alkyl group having 1 to 8 carbon atoms which may have a group include the same groups as those described above, and a tert-butyl group, a methyl group, and the like are preferable from the viewpoint of solvent solubility.

  Therefore, specific examples of the alkylene having 1 to 3 carbon atoms having a substituent include methylmethylene group, dimethylmethylene group, ethoxycarbonylethylene group, methoxyethoxycarbonylethylene group, methoxypropylcarbamoylmethylene group, methyl group and acetyl group. Methylene group substituted with a group, t-butylcarbonylmethylene group, methylene group substituted with ethoxycarbonyl group and methyl group, n-hexylmethylene group, n-butylmethylene group, n-decylmethylene group, A methylethylene group or the like is preferable.

In “—S-L-A”, each A is independently COOJ, OJ, CONJ ₂ or NJ ₂ . Among these, COOJ is preferable from the viewpoint of solvent solubility.

J each independently has a hydrogen atom, an optionally substituted acyl group having 1 to 8 carbon atoms, an optionally substituted alkoxycarbonyl group, or a substituent. Or an alkyl group having 1 to 8 carbon atoms or — (R ¹¹ O) _y R ¹² . R ¹¹ is an alkylene group having 1 to 3 carbon atoms. R ¹² is a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, an acyl group having 1 to 8 carbon atoms, or an alkylcarbamoyl group which may have a substituent. y is an integer of 1-4.

Among these, J is a hydrogen atom, an optionally substituted alkyl group having 1 to 8 carbon atoms, an optionally substituted acyl group having 1 to 8 carbon atoms, from the viewpoint of solvent solubility. _{^{- (R 11 O) y R}} 12 , more preferably an alkyl group having 1 to 8 carbon atoms which may have a substituent.

  Here, examples of the alkyl group having 1 to 8 carbon atoms include the same ones as described above, specifically, an ethyl group, an n-propyl group, an n-butyl group, a 2-ethylhexyl group, an isopropyl group, a methyl group, An n-hexyl group and the like are preferable, and an n-butyl group is particularly preferable from the viewpoint of solvent solubility. The substituent is not particularly limited, but is preferably an alkyl group having 1 to 8 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, an alkoxycarbonyl group having 1 to 8 carbon atoms, and specifically, methoxy Group, methoxycarbonyl group, methoxyethoxy group, ethoxy group and the like are preferable.

  More specifically, methoxy n-butyl group, 2-methoxybutyl group, 3-methoxybutyl group, ethyl group, n-propyl group, methoxyethyl group, ethoxyethyl group, 2-ethylhexyl group, isopropyl group, methoxyisopropyl Group, isopropoxycarbonylmethyl group, ethoxycarbonylmethyl group, methoxyethoxyethyl group, methoxy n-propyl group, n-hexyl group and the like are preferable.

Moreover, the acyl group having 1 to 8 carbon atoms in the acyl group having 1 to 8 carbon atoms which may have a substituent are those represented by ^{-COR 16, wherein,} as the ^{R 16,} the substituents From the viewpoint of solvent solubility, examples of the alkyl group having 1 to 8 carbon atoms that may have a substituent include the same as those described above. R ¹⁶ is preferably an ethylpentyl group, an ethyl group, an ethylmethyl group having a methoxycarbonyl group, or the like.

R ¹¹ is an alkylene group having 1 to 3 carbon atoms. Although it does not restrict | limit especially as a C1-C3 alkylene group, The same thing as the above is mentioned, Especially an ethylene group etc. are preferable.

R ¹² is a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, an acyl group having 1 to 8 carbon atoms, or an alkylcarbamoyl group which may have a substituent. Specific examples of these are the same as described above. Of these, a hydrogen atom and an ethyl group are preferable.

  y is an integer of 1-4, Preferably it is 2-3.

  The following specific examples are preferable when “-S-L-A” is put together.

(Substituent (c))
The substituent (c) is represented by the following formula (8):

Indicated by

In the above formula (8), each R ¹³ is independently COOJ ′, OJ ′, CON (J ′) ₂ , N (J ′) ₂ or a halogen atom. In addition, instead of “—S—” in formula (8), a form of “—SO ₂ —” may be used.

J ′ each independently represents a hydrogen atom, an optionally substituted alkoxycarbamoyl group, an optionally substituted alkoxycarbonyl group, or an optionally substituted phenyl; A C 1-8 alkyl group which may have a substituent, a C 1-8 alkoxy group which may have a substituent, or — (R ¹⁴ O) _z R ¹⁵ .

  Here, the substituent in the case where it may have a substituent is not particularly limited, and examples thereof include an alkyl group having 1 to 3 carbon atoms and an alkoxy group having 1 to 3 carbon atoms. The same applies, and specific examples include an ethoxy group, a methoxy group, and a methyl group. Moreover, there is no restriction | limiting in particular also in the number of substituents, the integer of 1-5 is preferable and the integer of 1-3 is preferable.

Here, the alkoxycarbamoyl group which may have a substituent has a structure such as —CON (R ¹⁹ ) ₂ . Here, as R ¹⁹ , each independently an optionally substituted alkyl group having 1 to 8 carbon atoms or a hydrogen atom is preferable, and the alkyl group having 1 to 8 carbon atoms is the same as described above. Specific examples are appropriate, and specifically, for example, an ethyl group is preferable. Therefore, each R ¹⁹ is preferably independently a methoxyethyl group or hydrogen.

Moreover, the alkoxycarbonyl group which may have a substituent has a structure of —COOR ¹⁸ , where R ¹⁸ is an alkyl having 1 to 8 carbons which may have a substituent. Specific examples of the alkyl group having 1 to 8 carbon atoms are the same as those described above, and specifically, for example, an isopropyl group is preferable. In addition, the substituent in this case is not particularly limited, but an alkoxy group having 1 to 3 carbon atoms is preferable, and for this specific example, the above-mentioned contents are similarly valid, and specifically, a methoxy group is preferable. . Therefore, R ¹⁸ is preferably a methoxyisopropyl group or the like.

  Moreover, as a phenyl group which may have a substituent, a trimethylphenyl group etc. are mentioned, for example.

  Moreover, what was described above is applicable similarly as a C1-C8 alkyl group which may have a substituent. These specific examples are not particularly limited, but for example, ethoxyethyl group, methoxyethyl group, methyl group, methoxyisopropyl group, and ethyl group are preferable.

  Moreover, what was described above is applicable similarly as a C1-C8 alkoxy group which may have a substituent. Although these specific examples do not have a restriction | limiting in particular, For example, they are a methoxy group, an ethoxy group, and a methoxypropoxy group.

R ¹⁴ is an alkylene group having 1 to 3 carbon atoms. The explanation given above also applies to an alkylene group having 1 to 3 carbon atoms, and specific examples include an ethylene group, a methylene group, and a propylene group.

R ¹⁵ is a hydrogen atom or an alkyl group having 1 to 8 carbon atoms. As the alkyl group having 1 to 8 carbon atoms, the explanation given above is similarly valid, and specific examples include a methyl group and an ethyl group.

  z is an integer of 1 to 4, preferably an integer of 1 to 3.

  w is an integer of 0 to 5, preferably an integer of 1 to 3.

  Therefore, the following specific examples are preferable when the “substituent (c)” is summarized. It should be noted that, in the “substituent (c)”, the “substituent (b)” is given priority in the portion overlapping with “substituent (b)”. That is, in the “substituent (c)”, a portion overlapping with the “substituent (b)” is excluded.

R ¹ is a nitro group, an amino group, a hydroxyl group, an alkyl group having 1 to 8 carbon atoms (particularly, a t-Bu group), -S- (R ⁹ O, considering the above properties such as heat resistance and solvent solubility. ^{_{) x R 10, -S-L}} -a, substituent (a), is preferably a substituent (a) or a halogen atom selected from the group consisting of substituents (b) and substituents (c). At least one of R ^{1 to} R ⁴ is preferably introduced with a skeleton represented by R ¹ because of the effect of improving the solubility in ether solvents.

In R ² , in consideration of the above characteristics such as heat resistance and solvent solubility, a skeleton (that is, a pyridine skeleton) in which q is more preferably 0 is preferably introduced.

In R ³ , in consideration of the above characteristics such as heat resistance and solvent solubility, a skeleton (that is, a pyrazine skeleton) in which q is more preferably 0 is preferably introduced.

In R ⁴ , in consideration of the above characteristics such as heat resistance and solvent solubility, it is preferable that a skeleton (that is, a naphthalene skeleton) in which s is more preferably 0 is introduced. Further, s is more preferably 2, and a skeleton that is a halogen atom (that is, a dihalonaphthalene skeleton) is preferably introduced. In this case, the halogen atom is particularly preferably a bromine atom.

In summary, in the above formula (1), preferred specific examples of Z ^{1 to} Z ⁴ are each independently

It is.

  In the above formula, p may be an integer of 1 to 4. s may be an integer from 1 to 6. In the above formula, v may be an integer of 0 to 5. In the above formula, a is preferably 0.25 or more and less than 4. b is preferably 0 or more and less than 3.75. Also:

When b is a group containing an ester group, b is preferably 0.2 or more and less than 4. However, the number of halogen atoms introduced (that is, for example, chlorine atoms and bromine atoms) (“4-a-b” or “4-a”) is more than 0, and more preferably 2 or more.

At this time, as described above, in the phthalocyanine derivative of the present invention, among all the groups introduced as R ^{1 to} R ⁴ , 0.05 to less than 3 are hydrogen atoms, and 1 to 6 Is a substituent (a) and Z ^{1 to} Z ⁴ are selected so that the remainder is a halogen atom.

  Thus, the presence of various substituents as specified in the present invention balances solubility in various solvents, wavelength control, durability (light resistance, heat resistance), and Gram extinction coefficient. This is preferable. Although the mechanism by which the intended purpose of the present invention is achieved is unclear, the presence of an appropriate number of substituents (a) improves the solubility in ether solvents, and the halogen atom is appropriate. The presence of a large number makes it possible to increase the absorption wavelength, improve durability (light resistance, heat resistance), and the presence of an appropriate number of hydrogen atoms improves the gram extinction coefficient, resulting in a poor overall skeleton. It becomes uniform, crystallinity deteriorates, and solvent solubility improves.

Of all the groups introduced as R ^{1 to} R ⁴ , the number of hydrogen atoms is 0.1 or more and less than 3, preferably 0.05 to 2, and more preferably 0.05 to 1. . This range is particularly preferable from the viewpoints of solvent solubility and heat resistance. Thus, when the phthalocyanine derivative of the present invention has an appropriate number of hydrogen atoms, the absorbance per gram is higher than that of a compound composed of only the substituent (a) and the halogen atom. For this reason, the effect of a phthalocyanine derivative can be exhibited with a small amount of blending. Further, in the phthalocyanine derivative of the present invention, when a suitable number of hydrogen atoms other than the substituent (a) and the halogen atom are present, the structure as the phthalocyanine derivative becomes nonuniform (random) and the crystallinity is deteriorated. This improves the solubility in various solvents. That is, if the number is less than 0.1, the absorbance per gram increases.

Of all the groups introduced as R ^{1 to} R ⁴ , 1 to 6 are substituents (a), and from the viewpoint of improving solvent solubility, it is particularly preferably 1.05 to 5.8. From the viewpoint of improving the gram extinction coefficient, the number is particularly preferably 1.1 to 5.6. Here, it is not preferable that the number of substituents (a) is less than one because the solvent solubility is lowered. When the number of substituents (a) exceeds 6, the molecular weight increases and the gram extinction coefficient decreases.

In addition, as described above, among all the groups introduced as R ^{1 to} R ⁴ , at least one is preferably the substituent (a) or the substituent (b), and more preferably at least one is substituted. The group (a) is preferred. The number of substituents in that case is not particularly limited as long as it is within the predetermined range of the present invention, but the number of substituents (a) is preferably 1 to 6, more preferably 1 to 5. Yes, and more preferably 1-4. When the number of the substituents (a) is within such a range, the intended purpose having both heat resistance, solvent solubility, and high permeability at 520 nm is achieved.

Of all the groups introduced as R ^{1 to} R ⁴ , the remainder other than the hydrogen atom and the substituent (a) is a halogen atom. Thus, heat resistance can be improved by arrange | positioning a halogen atom in remainder. As described above, among all groups introduced as R ^{1 to} R ⁴ , it is also preferable that at least a halogen atom is introduced in consideration of heat resistance such as heat resistance and solvent solubility. In this case, the number of halogen atoms is not particularly limited as long as it is within the predetermined range of the present invention, but is preferably 9 to 15, more preferably 9 to 14. Within this range, the solubility is maintained by preventing excessive stacking between molecules, so that the intended purpose of having both high solubility and heat resistance is achieved. However, it is needless to say that such a mechanism is only a guess of the present inventors and does not limit the technical scope of the present invention.

  The absorption wavelength of the phthalocyanine derivative of the present invention preferably has a maximum absorption wavelength (λmax) in the wavelength region of 640 to 750 nm in the near infrared region. In addition, in this specification, the value measured by the measuring method in the following Example is employ | adopted for the maximum absorption wavelength. Since the phthalocyanine derivative of the present invention exhibits a maximum absorption wavelength in the vicinity of 640 to 750 nm, light in useless near infrared region (700 to 750 nm) emitted by flat panel displays, particularly PDPs and LCDs, and an impure red color called so-called crimson. The light of the wavelength (640-700 nm) is cut, for example, the malfunction induction of an optical communication system is prevented, and the effect of reproducing a clear red color can be exhibited at the same time. Further, the phthalocyanine derivative of the present invention absorbs light at 710 nm and has high transmittance for visible light such as 520 nm, that is, has a high absorbance ratio. In particular, since PDP shows excessively large light emission in the vicinity of 710 nm, the phthalocyanine derivative of the present invention absorbs light at 710 nm and has a high visible light transmittance such as 520 nm as a pigment for PDP, particularly for flat panel displays. Useful as a filter.

  As described above, the phthalocyanine derivative of the present invention has particularly high solubility in an ether solvent. When the phthalocyanine derivative is applied, the solubility of the phthalocyanine derivative in the solvent is important because the substrate used in the device is not dissolved by the solvent and the solubility in the resin is also required. And the phthalocyanine derivative of various absorption wavelengths can be obtained by selection of the kind, number, and central metal of a substituent. As the ether solvent, branched or linear ethers and cyclic ethers are effectively used. Specifically, tetrahydrofuran, 1,4-dioxane, 1,3-dioxolane, diethyl ether, diisopropyl ether, 1,2-dimethoxyethane, cyclopentyl methyl ether, propylene glycol monomethyl ether acetate (PGMEA), ethylene glycol monoethyl ether Examples include acetate, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, and the like. PGMEA is often used in flat panel display applications. The solubility of the phthalocyanine derivative of the present invention in PGMEA, which is an ether solvent, is preferably 10% by mass or more, and more preferably 20% by mass or more. The upper limit of solubility is not particularly limited, but is usually about 50% by mass or less.

  The method for producing the phthalocyanine derivative of the present invention is not particularly limited, and a conventionally known method can be appropriately used. Preferably, the phthalonitrile derivative and the metal salt are used in a molten state or in an organic solvent. A method of cyclization reaction is particularly preferably used. Hereinafter, particularly preferred embodiments of the production method of the phthalocyanine derivative of the present invention will be described. However, the present invention is not limited to the following preferred embodiments.

  That is, the following formula (2 '):

A phthalonitrile derivative (1) represented by the following formula (3 '):

A phthalonitrile derivative (6) represented by the following formula (4 '):

And a phthalonitrile derivative (3) represented by the following formula (5 '):

And at least one selected from the group consisting of phthalonitrile derivatives (4) represented by the following: metal, metal oxide, metal carbonyl, metal halide, and organic acid metal (in this specification, “metal compound” The phthalocyanine derivative of the present invention can be produced by a cyclization reaction with one selected from the group consisting of Among these, from the viewpoint of achieving the intended purpose, it is also preferable to cyclize only the phthalonitrile derivative (1) with the metal compound. It is also preferable to cyclize the phthalonitrile derivative (1) and the phthalonitrile derivative (2) with a metal compound. It is also preferable to cyclize the phthalonitrile derivative (1) and the phthalonitrile derivative (3) with a metal compound. It is also preferable to cyclize the phthalonitrile derivative (1) and the phthalonitrile derivative (4) with a metal compound. It is also preferable to cyclize the phthalonitrile derivative (1), the phthalonitrile derivative (2) and the phthalonitrile derivative (4) with a metal compound.

In the above reaction, phthalonitrile derivatives (1) to (4) have been described in accordance with the structure of the phthalocyanine derivative of formula (1), but depending on the structure of the target phthalocyanine derivative, 1 to 4 types of phthalonitrile derivatives may be used. Sometimes it becomes. For example, the phthalocyanine derivative of the present invention can be produced by cyclization reaction of only the phthalonitrile derivative (1) with a metal compound as described above. In this case, the structure represented by the phthalonitrile derivative (1) is R ¹ or Various structures can be adopted depending on the number of p. Therefore, 0.05 or more and less than 3 are hydrogen atoms, 1 to 6 are substituents (a), and the remainder is a halogen atom, and the desired phthalocyanine A cyclization reaction may be performed by appropriately combining conventionally known knowledge so as to obtain a derivative structure.

In the present invention, “at this time, among all the groups introduced as R ^{1 to} R ⁴ , 0.05 or more and less than 3 are hydrogen atoms, and 1 to 6 are substituents (a) One of the characteristics is that the inventors have come up with the technical idea that “the remainder is a halogen atom”. Therefore, if it is determined, the target phthalocyanine derivative can be produced by referring to conventionally known knowledge as appropriate, referring to the examples, or combining them.

In addition, said Formula (2 ')-(5') is prescribed | regulated by the structure of a desired phthalocyanine derivative. Specifically, in the above formulas (2 ′) to (5 ′), the definitions are the same as the definitions of R ^{1 to} R ^{4 in} the above formulas (2) to (5). .

  In the above embodiment, the phthalonitrile derivatives (phthalonitrile derivatives (1) to (4)) of the formulas (2 ′) to (5 ′) which are starting materials can be synthesized by a conventionally known method, and commercially available products are used. You can also.

  Hereinafter, in particular, a method for synthesizing the phthalonitrile derivative (1) represented by the formula (2 ') into which the substituent (a) and / or the substituent (b) is introduced will be described.

  For example, the following formula (V):

A phthalonitrile derivative (V) represented by the following formula (6a), (6′a) or (6 ″ a):

A substituent (a) -containing precursor represented by the formula (herein also simply referred to as “substituent (a) -containing precursor”), and / or the following formula (7a):

It is obtained by reacting with a substituent (b) -containing precursor represented by the formula (herein also simply referred to as “substituent (b) -containing precursor”). In the following, the substituent (a) -containing precursor and the substituent (b) -containing precursor are collectively referred to as “precursor”.

In the above formulas (6a), (6′a) and (6 ″ a), R ⁵ , R ⁶ and R ⁷ , and t, t ′ and u are respectively represented by the above formulas (6), (6 Since the definitions of R ⁵ , R ⁶ and R ⁷ , and t, t ′ and u in ′) and (6 ″ a) are the same, the description thereof is omitted here. Similarly, in the above formula (7a), X and Ar are the same as the definitions of X and Ar in the above formula (7), respectively, and thus description thereof is omitted here.

In the above reaction, the phthalonitrile derivative (V) is used as a starting material. In the above formula (V), X ₁ , X ₂ , X ₃ and X ₄ each independently represent a hydrogen atom, a halogen atom or a nitro group. Here, X ₁ , X ₂ , X ₃ and X ₄ may be the same or different. Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. Of these, it is preferable to represent a fluorine atom or a chlorine atom. In particular, when tetrachlorophthalonitrile (TCPN) or tetrafluorophthalonitrile (TFPN) is used as a starting material, the substituent (a) -containing precursor or the substituent (b) -containing precursor is the tetrachlorophthalonitrile. Or it reacts with the 3-6 position chlorine atom or fluorine atom of tetrafluorophthalonitrile at random. For this reason, by using tetrachlorophthalonitrile or tetrafluorophthalonitrile as a starting material, substituents (a) and (b) can be randomly introduced into the α-position and β-position of the phthalocyanine skeleton. Therefore, when tetrachlorophthalonitrile or tetrafluorophthalonitrile is used as the phthalonitrile derivative, the phthalonitrile derivative has four chlorine atoms of tetrachlorophthalonitrile or four fluorine atoms of tetrafluorophthalonitrile. It is obtained in the form of a mixture optionally substituted with precursors. It is also preferable to use 3-nitrophthalonitrile or 4-nitrophthalonitrile as a starting material.

  In the reaction of the phthalonitrile derivative with the substituent (a) -containing precursor / substituent (b) -containing precursor, the ratio of the precursor is appropriately selected depending on the structure of the target phthalonitrile derivative. For example, the amount used when only the substituent (a) -containing precursor is introduced is not particularly limited as long as these reactions can proceed to produce a desired phthalonitrile derivative. Preferably, the amount is such that 0.25 to 3, more preferably 0.5 to 2 substituent (a) -containing precursors are introduced into the phthalonitrile derivative. In consideration of such points, the amount of the substituent (a) -containing precursor used is usually 0.25 to 3 mol, more preferably 0.25 to 2 mol, particularly 1 mol to 1 mol of the phthalonitrile derivative. Preferably it is 0.5-2 mol. It goes without saying that the amount used can be appropriately changed according to what is desired to be synthesized (the description of other amounts used is the same).

  In addition, when the substituent (a) -containing precursor and the substituent (b) -containing precursor are introduced, the total amount used is particularly an amount that can produce a desired phthalonitrile derivative by proceeding with these reactions. Not limited. Preferably, in an amount such that 0.25 to 3, more preferably 0.5 to 2 substituent (a) containing precursor / substituent (b) containing precursor is introduced into the phthalonitrile derivative. Preferably there is. In consideration of such points, the total amount of the substituent (a) -containing precursor / substituent (b) -containing precursor is usually 0.25 to 3 mol per 1 mol of the phthalonitrile derivative. More preferably, it is 0.25-2 mol, Most preferably, it is 0.5-2 mol. The reaction between the phthalonitrile derivative and the precursor may be performed in the absence of a solvent or in an organic solvent, but is preferably performed in an organic solvent. Examples of the organic solvent that can be used in this case include nitriles such as acetonitrile and benzonitrile; polar solvents such as acetone and 2-butanone. Of these, acetonitrile, benzonitrile and acetone are preferred. The amount of the organic solvent used when the solvent is used is such an amount that the concentration of the phthalonitrile derivative is usually 2 to 40% by mass, preferably 5 to 30% by mass.

  Further, in the reaction of the phthalonitrile derivative and the precursor, it is preferable to use these trapping agents in order to remove hydrogen halide (for example, hydrogen chloride or hydrogen fluoride) generated during the reaction. Specific examples of the trapping agent when using the trapping agent include potassium carbonate, sodium carbonate, potassium hydroxide, sodium hydroxide, calcium carbonate, calcium hydroxide, magnesium hydroxide, magnesium chloride and magnesium carbonate. Of these, potassium carbonate, calcium carbonate and calcium hydroxide are preferred. Further, the amount of the trapping agent used when the trapping agent is used is not particularly limited as long as it is an amount capable of efficiently removing hydrogen halide and the like generated during the reaction. It is 0-4.0 mol, Preferably it is 1.0-2 mol.

  The reaction conditions for the phthalonitrile derivative and the precursor are not particularly limited as long as the reaction of both proceeds to obtain the desired phthalonitrile derivative. Specifically, the reaction temperature is usually 20 to 150 ° C, preferably 40 to 120 ° C. Moreover, reaction time is 0.5 to 60 hours normally, Preferably it is 1 to 50 hours.

  By the above reaction, the phthalonitrile derivative (1) of the formula (2 ′) into which the substituent (a) and / or the substituent (b) is introduced is obtained. After the reaction, crystallization, filtration, washing and drying may be performed according to a conventionally known method. By such an operation, the phthalonitrile derivative can be obtained efficiently and with high purity.

  The cyclization reaction includes at least one selected from the group consisting of phthalonitrile derivatives (1) to (4) of formulas (2 ′) to (5 ′), a metal, a metal oxide, a metal carbonyl, and a metal halide. And one selected from the group consisting of organic acid metals is preferably reacted in a molten state or in an organic solvent.

  The metal, metal oxide, metal carbonyl, metal halide, and organic acid metal that can be used at this time are not particularly limited as long as those corresponding to M of the phthalocyanine derivative of the formula (1) obtained after the reaction can be obtained. For example, metals such as iron, copper, zinc, vanadium, titanium, indium and tin listed in the item M in the above formula (1), chlorides, bromides, iodides, etc. of the metals Metal oxides such as vanadium oxide, titanyl oxide and copper oxide, organic acid metals such as acetate, complex compounds such as acetylacetonate, and metal carbonyls such as carbonyl iron. Specifically, metals such as iron, copper, zinc, vanadium, titanium, indium, magnesium, and tin; metal halides such as chloride, bromide, and iodide of the metal, such as vanadium chloride, titanium chloride, and chloride Copper, zinc chloride, cobalt chloride, nickel chloride, iron chloride, indium chloride, aluminum chloride, tin chloride, gallium chloride, germanium chloride, magnesium chloride, copper iodide, zinc iodide, cobalt iodide, indium iodide, iodide Aluminum, gallium iodide, copper bromide, zinc bromide, cobalt bromide, aluminum bromide, gallium bromide; vanadium monoxide, vanadium trioxide, vanadium tetroxide, vanadium pentoxide, titanium dioxide, iron monoxide, three Iron dioxide, iron trioxide, manganese oxide, nickel monoxide, cobalt monoxide, cobalt dioxide , Cobalt dioxide, cuprous oxide, cupric oxide, copper trioxide, barium oxide, zinc oxide, germanium monoxide, germanium dioxide and other metal oxides; copper acetate, zinc acetate, cobalt acetate, copper benzoate, And organic acid metals such as zinc benzoate; and complex compounds such as acetylacetonate; and metal carbonyls such as cobalt carbonyl, iron carbonyl and nickel carbonyl. Of these, metals, metal oxides and metal halides are preferable, metal halides are more preferable, vanadium iodide, copper iodide and zinc iodide are more preferable, and iodine is more preferable. Copper iodide and zinc iodide, particularly preferably zinc iodide. When zinc iodide is used, the central metal is zinc. Among metal halides, it is preferable to use iodide because it has excellent solubility in solvents and resins, and the spectrum of the obtained phthalocyanine derivative is sharp and easily fits in a desired wavelength. The detailed mechanism of sharpening the spectrum when using iodide during the cyclization reaction is unknown, but when iodide is used, the iodine remaining in the phthalocyanine derivative after the reaction is not compatible with the phthalocyanine derivative. It is presumed that iodine is present between the layers of the phthalocyanine derivative due to the action. However, the mechanism is not limited to the above mechanism. In order to obtain the same effect as when metal iodide is used in the cyclization reaction, the obtained phthalocyanine derivative may be treated with iodine.

  In the above embodiment, the cyclization reaction can be carried out in the absence of a solvent, but it is preferably carried out using an organic solvent. The organic solvent may be any inert solvent that has low reactivity with the phthalonitrile derivative as a starting material, and preferably does not exhibit reactivity. For example, benzene, toluene, xylene, nitrobenzene, monochlorobenzene, o -Inert solvents such as chlorotoluene, dichlorobenzene, trichlorobenzene, 1-chloronaphthalene, 1-methylnaphthalene, ethylene glycol, and benzonitrile; methanol, ethanol, 1-propanol, 2-propanol, 1- Alcohols such as butanol, 1-hexanol, 1-pentanol, 1-octanol; and pyridine, N, N-dimethylformamide, N, N-dimethylacetamide, N-methyl-2-pyrrolidinone, N, N-dimethylacetophenone, Triethylamine, tri n- butylamine, dimethyl sulfoxide, aprotic polar solvents such as sulfolane. Of these, 1-chloronaphthalene, 1-methylnaphthalene, 1-octanol, dichlorobenzene and benzonitrile are preferably used, and more preferably 1-octanol, dichlorobenzene and benzonitrile are used. These solvents may be used alone or in combination of two or more.

  The reaction conditions between the metal compound and at least one selected from the group consisting of the phthalonitrile derivatives (1) to (4) of formulas (2 ′) to (5 ′) in the above embodiment are the conditions under which the reaction proceeds. There is no particular limitation as long as it is present. For example, at least one selected from the group consisting of the phthalonitrile derivatives (1) to (4) is preferably 1 to 500 parts by mass, more preferably 10 to 350 parts by mass with respect to 100 parts by mass of the organic solvent. It is.

  Further, the metal compound is preferably charged in a range of 0.8 to 2.0 mol, more preferably 0.8 to 1.5 mol, with respect to 4 mol of the phthalonitrile derivative.

  The cyclization conditions are not particularly limited, but the reaction is preferably performed at a reaction temperature of 30 to 250 ° C, more preferably 80 to 200 ° C. Although reaction time is not specifically limited, Preferably it is 3 to 24 hours.

  Moreover, although the said reaction may be performed in air | atmosphere atmosphere, it is preferable to carry out in inert gas atmosphere (For example, under distribution | circulation of nitrogen gas, helium gas, argon gas, etc.).

  After the cyclization reaction, crystallization, filtration, washing and drying may be performed according to a conventionally known method. By such an operation, the phthalocyanine derivative can be obtained efficiently and with high purity.

As described above, in the present invention, “at this time, among all the groups introduced as R ^{1 to} R ⁴ , 0.05 or more and less than 3 are hydrogen atoms, and 1 to 6 are One of the characteristics is that it came up with the technical idea that it is a substituent (a) and the balance is a halogen atom. Therefore, once it is determined, the desired phthalocyanine derivative can be produced by appropriately referring to or combining conventionally known knowledge.

  Thus, for example, the following formula:

  In the most recent formula, a is preferably 0.25 or more and less than 4, and “4-a” is preferably 2 or more, a phthalonitrile derivative represented by the following formula:

  In the most recent formula, a is preferably 0.25 or more and less than 4, and “4-a” is preferably 2 or more, a phthalonitrile derivative represented by the following formula:

  In the most recent formula, a is preferably 0.25 or more and less than 4, and “4-a” is preferably 2 or more, a phthalonitrile derivative represented by the following formula:

  In the most recent formula, a is preferably 0.25 or more and less than 4, and “4-a” is preferably 2 or more, a phthalonitrile derivative represented by the following formula:

  In the most recent formula, a is preferably 0.25 or more and less than 4, and b is preferably 0.2 or more and less than 4, provided that “4-ab” is more than 0, preferably 2 or more. A phthalonitrile derivative represented by the following formula:

  In the most recent formula, a is preferably 0.25 or more and less than 4, and b is preferably 0 or more and less than 3.75, provided that “4-ab” is more than 0, preferably 2 or more. "C / (c + d)" and "d / (c + d)" are for indicating an arbitrary ratio of chlorine atom and bromine atom, c is preferably 0 to 3.9, and d is Preferably it is 0-4, the phthalonitrile derivative represented by the following formula:

  In the most recent formula, a is preferably 0.25 or more and less than 4, and b is preferably 0 or more and less than 3.75, and when b is a group containing an ester group, b is 0.2 or more and less than 4 Preferably, wherein “4-a-b” and “4-a” are each greater than 0, more preferably 2 or more, and a phthalonitrile derivative represented by:

Where p can be an integer from 0 to 3 (ie, at least one “hydrogen atom” is introduced) and s can be an integer from 0 to 5 (ie, at least one “hydrogen atom”). And one or more phthalonitrile derivatives represented by:
A metal compound;
Of all groups introduced as R ^{1 to} R ⁴ , 0.05 to less than 3 are hydrogen atoms, 1 to 6 are substituents (a), and the rest The phthalocyanine derivative of the present invention can be produced by cyclization reaction so that “is a halogen atom”.

  According to the present invention, a phthalocyanine derivative having high solubility in an ether solvent and improved heat resistance can be provided. The phthalocyanine derivative of the present invention can be dissolved in an ether solvent. Therefore, even a resin that is relatively selectively dissolved in an ether solvent can be used. It can also be used for applications in which a phthalocyanine dye is applied to a plastic that may be dissolved when a solvent other than an ether solvent is used. In addition, the phthalocyanine derivative of the present invention has improved heat resistance. Therefore, adaptability to the external environment is significantly high, and it can be used for various purposes. Moreover, the phthalocyanine derivative of the present invention retains high visible light transmittance, high near-infrared cut efficiency, and near-infrared selective absorption, in addition to excellent compatibility with resins, heat resistance, light resistance, and weather resistance.

<Second of the present invention>
2nd of this invention is a filter for flat panel displays containing the phthalocyanine derivative of this invention.

  The phthalocyanine derivative of the present invention has a translucent or transparent and heat ray shielding material for the purpose of shielding heat rays, a heat ray absorbing laminated glass for automobiles, a heat ray shielding film or a heat ray shielding resin glass, a high visible light transmittance and Filters for plasma display with high near-infrared light cutting efficiency, near-infrared absorbers for non-contact fixing toners such as flash fixing, near-infrared absorbers for thermal insulation fibers, camouflage performance against infrared reconnaissance (camouflage) Performance) infrared absorbent for fiber, optical recording medium using semiconductor laser, liquid crystal display filter with xenon lamp as backlight, near-infrared absorbing dye for writing or reading in optical character reader, Infrared photosensitizer, photothermal exchange agent such as thermal transfer and thermal stencil, laser beam Tumor treatment that absorbs light in the long-wavelength region with good tissue permeability, such as laser heat-fusing photo-heat exchanger, near-infrared absorption filter, anti-eyestrain or photoconductive material Photosensitive dye, color cathode ray tube selective absorption filter, color toner, inkjet ink, anti-counterfeiting ink, anti-counterfeiting bar code ink, near-infrared absorbing ink, marking agent for photographic and film positioning, and goggles It exhibits excellent effects when used in lenses, shielding plates, dyeing agents for sorting when plastics are recycled, and preheating aids when molding PET bottles. In particular, considering the above-described characteristics, the phthalocyanine derivative of the present invention can be suitably used for a heat ray shielding material, a flat display filter, and a near infrared absorbing material.

  Since the phthalocyanine derivative having a specific structure as described above exhibits a maximum absorption wavelength in a specific wavelength region of 640 to 750 nm, light in these regions can be selectively cut. For this reason, when the phthalocyanine derivative of the present invention is used in a flat panel display, for example, light in an unnecessary near infrared region (700 to 750 nm) emitted by a PDP or LCD or an impure red wavelength (so-called crimson) 640-700 nm) is cut off, for example, the malfunction of the optical communication system is prevented from being induced, and at the same time, the effect of reproducing a clear red color is expected. In particular, since PDP shows extra large light emission in the vicinity of 710 nm, the phthalocyanine derivative of the present invention which absorbs light at 710 nm and has high visible light transmittance such as 520 nm is useful.

  Therefore, this invention relates also to the filter for flat panel displays containing the phthalocyanine derivative of this invention. The flat panel display filter is preferably used for a plasma display or a liquid crystal display, and particularly preferably used for a plasma display.

  The filter of the present invention is essential to contain the phthalocyanine derivative of the present invention, but may further contain a dye having another maximum absorption wavelength.

Other dyes that can be used in such a case are appropriately selected according to the maximum absorption wavelength desired depending on the application. For example, a near-infrared absorbing dye of 800 to 1000 nm or an orange neon light of 570 to 600 nm is used. Examples include absorbing dyes. Among these, examples of the near infrared absorbing dye having a wavelength of 800 to 1000 nm include cyanine dyes, phthalocyanine dyes, nickel complex dyes, and diimonium dyes. Among these, phthalocyanine dyes include phthalocyanine dyes described in JP-A No. 2001-106869, particularly phthalocyanine [CuPc (2,5-Cl ₂₎ produced in Example 8 of JP-A No. 2001-106869. PhO) ₈ {2,6- (CH ₃ ) ₂ PhO} ₄ (PhCH ₂ NH) ₄ ] (λmax: 807 nm), phthalocyanine [VOPc (2,5-Cl ₂ PhO) produced in Example 7 of the publication ) ₈ {2,6- (CH ₃ ) ₂ PhO} ₄ (PhCH ₂ NH) ₄ ] (λmax: 870 nm), phthalocyanine [VOPc (PhS) ₈ {2,6- (CH ₃ ) ₂ PhO} ₄ (PhCH ₂ NH) ₄ ] (λmax: 912 nm); a film described in JP-A No. 2004-18561 Talocyanine dyes, especially phthalocyanine [VOPc (PhS) ₈ {2,6- (CH ₃ ) ₂ PhO} ₄ {CH ₃ CH ₂ O (CH ₂ ), produced in Example 8 of JP-A-2004-18561 ₃ NH} ₄ ] (λmax: 928 nm), phthalocyanine [VOPc (4- (CH ₃ O) PhS) ₈ {2,6- (CH ₃ ) ₂ PhO} ₄ {CH produced in Example 17 of the publication ₃ (CH ₂ ) ₃ CH (C ₂ H ₅ ) CH ₂ NH} ₄ ] (λmax: 962 nm);

A phthalocyanine compound [hereinafter also referred to as {CuPc (3-methoxycarbonylphenoxy) ₈ (2-chlorobenzylamino) ₇ F}] (λmax: 916 nm), represented by the following formula:

A phthalocyanine compound [hereinafter also referred to as {CuPc (3-methoxycarbonylphenoxy) ₈ (2-ethylhexylamino) ₈ }] (λmax: 963 nm) or the like is preferably used. In this case, in consideration of durability and weather resistance, it is particularly preferable that the central metal of the phthalocyanine skeleton of the phthalocyanine dye having a wavelength of 800 to 1000 nm is copper. Moreover, the phthalocyanine compound described in the Example of Unexamined-Japanese-Patent No. 10-78509 can also be used. Examples of the diimonium dye include (N, N, N ′, N′-tetrakis (p-diethylaminophenyl) -p-benzoquinone-bis (imonium) hexafluoroantimonate, N, N, N ′, N′— Tetrakis (p-dibutylaminophenyl) -p-phenylenediamine-bis (bis (trifluoromethanesulfonyl) imidic acid) imonium salt (trade name: CIR-1085, manufactured by Nippon Carlit Co., Ltd.), N, N, N ′, N '-Tetrakis (p-dibutylaminophenyl) -p-phenylenediamine-bis (hexafluoroantimonic acid) imonium salt (trade name: CIR-1081, manufactured by Nippon Carlit Co., Ltd.), diimonium cation and bis (trifluoromethanesulfone) Diimonium dye composed of imide anion (manufactured by Nippon Carlit Co., Ltd., trademark: CIR- L) and the like are preferably used, and as the nickel complex dye, Bis (1,2-diphenylene-1,2-dithiol) nickel is preferably used, and as the cyanine dye, a stabilized cyanine dye is used. Here, the stabilized cyanine dye is a salt compound composed of a cyanine cation and a quencher anion, and examples of the cyanine cation include cation No. 1 and No. 1 shown below. In addition, as the quencher anion, for example, the following compounds of anions No. 11 and No. 22 can be preferably used, and a salt compound appropriately combined with these is preferably used as a stabilized cyanine dye. Is done.

  Examples of dyes that absorb orange neon light of 570 to 600 nm include tetraazaporphyrin dyes, cyanine dyes, squarylium dyes, anthraquinone dyes, subphthalocyanine dyes, phthalocyanine dyes, polymethyl dyes, polyazo dyes. System dyes and the like. Among these, tetra-t-butyl-tetraazaporphyrin / copper complex, tetra-t-butyl-tetraazaporphyrin / vanadium complex and the like are preferably used as the tetraazaporphyrin-based dye. Further, as the cyanine dye and squarylium dye, cyanine dyes and squarylium dyes described in JP-A No. 2002-189422 are preferably used. As the subphthalocyanine dye, a subphthalocyanine dye described in JP-A No. 2006-124593 is preferably used. In view of durability and weather resistance, it is particularly preferable that the central metal of the phthalocyanine skeleton of the 570-600 nm phthalocyanine dye is copper.

  In addition to the phthalocyanine compound, a dye having a maximum absorption wavelength at 600 to 750 nm may be included. As such a dye, specifically, 1-ethyl-2- [3-chloro-5- (1-ethyl-2 (1H) -quinolinylidene) -1,3-pentadienyl represented by the following formula: ] Quinolium bromide (106 times; λmax: 694.4 nm), 1,3,3-trimethyl-2- [5- (1,3,3-trimethyl-2 (1H) -benz [e] indolinylidene) -1,3-pentadienyl] -3H-benz [e] indolinium perchlorate (119 times; λmax: 675.6 nm), 3-ethyl-2- [5- (3-ethyl-2-benzothiazolinylidene) ) -1,3-pentadienyl] benzothiazolium iodide (475 times; λmax: 651.6 nm) and the like. In the above, the magnification in parentheses is the magnification of absorbance at the maximum absorption wavelength with respect to the absorbance at 460 nm, and the maximum absorption wavelength (λmax) is shown in parentheses. In addition, the said other pigment | dye may be used independently or may be used with the form of 2 or more types of mixtures.

  The flat panel display filter of the present invention contains a dye / phthalocyanine dye (hereinafter, also simply referred to as “dye / phthalocyanine dye”) that can be used in a flat panel display filter. The term “containing in the base material” as used in the invention means not only that it is contained inside the base material, but also a state where it is applied to the surface of the base material, a state where it is sandwiched between the base material and the like. Examples of the substrate include a transparent resin plate, a transparent film, and transparent glass. A method for producing the flat panel display filter of the present invention using the phthalocyanine derivative is not particularly limited, and for example, the following three methods can be used.

  That is, (1) A method of kneading a dye / phthalocyanine dye in a resin and thermoforming it to produce a resin plate or film; (6) A paint (liquid or paste-like material) containing the dye / phthalocyanine dye; (4) A method of coating a transparent resin plate, a transparent film or a transparent glass plate; (3) A method of producing a laminated resin plate, a laminated resin film, a laminated glass or the like by containing a dye / phthalocyanine dye in an adhesive; and (4 ) Dye / phthalocyanine dye is contained in an adhesive, and this is applied to a film subjected to an antireflection treatment and attached to a PDP panel or PDP front filter glass.

  In the present invention, since it is installed in front of the display in order to cut near-infrared light emitted from the display, if the visible light transmittance is low, the sharpness of the image is reduced, so the visible light transmittance of the filter is high. It needs to be at least 40%, preferably 60% or more. The near infrared light cut region is 750 to 1100 nm, preferably 800 to 1000 nm, and the average light transmittance in the region is designed to be 20% or less, preferably 15% or less. Therefore, if necessary, two or more dyes / phthalocyanine dyes 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. It is also possible to produce a filter containing only the color tone dye and to bond it later. In particular, when an electromagnetic wave cut layer such as sputtering is provided, the color tone is important because the hue may be greatly different from the original filter color.

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 that block electromagnetic waves emitted from the flat panel display can be provided. Their manufacturing method is not particularly limited. For example, for the electromagnetic wave cut layer, a sputtering method such as a metal oxide can be used. Usually, In ₂ O ₃ (ITO) to which Sn is added is generally used, but the dielectric layer and the metal layer are formed on the substrate. By alternately laminating by sputtering or the like, it is possible to cut light of 1100 nm or more from near infrared rays, far infrared rays to electromagnetic waves. The dielectric layer is a transparent metal oxide such as indium oxide or zinc oxide, and the metal layer is generally silver or a silver-palladium alloy, and usually three layers and five layers starting from the dielectric layer. 7 or 11 layers are laminated. In this case, the heat generated from the display can be cut at the same time, but since the dye / phthalocyanine dye has an excellent heat ray shielding effect, the heat resistance effect can be further improved. As the substrate, a filter containing a dye / phthalocyanine dye may be used as it is, or may be bonded to a filter containing the dye / phthalocyanine dye after sputtering on a resin film or glass. Moreover, when actually performing electromagnetic wave cutting, it is necessary to install an electrode for grounding. In order to suppress the reflection of the surface and improve the transmittance of the filter, the antireflection layer is made of an inorganic substance such as a metal oxide, fluoride, boride, carbide, nitride, sulfide, vacuum deposition method, sputtering method, There are a method of laminating a single layer or a multilayer by an ion plating method, an ion beam assist method, or the like, a method of laminating a resin having a different refractive index, such as an acrylic resin or a fluororesin, in a single layer or a multilayer. Moreover, the film which gave the antireflection process can also be affixed on this filter. Further, if necessary, a non-glare (AG) layer can be provided. The non-glare (AG) layer can be formed by coating fine particles of silica, melamine, acrylic, etc. with ink in order to scatter transmitted light for the purpose of widening the viewing angle of the filter. The ink can be cured by thermal curing or photocuring. Further, a non-glare-treated film can be pasted on the filter. Further, if necessary, a hard coat layer can be provided.

  The configuration of the filter for the flat panel 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. In addition, when combining an electromagnetic wave cut layer, a filter containing a near infrared ray absorbing compound is used as a base material, and an electromagnetic wave cut layer is provided thereon, or a filter containing a near infrared ray absorbing compound and a filter having an electromagnetic wave cutting ability are provided. Can be made by pasting together. In that case, an antireflection layer can be further produced on both sides, or if necessary, an antireflection layer can be produced on one side and a non-glare layer can be produced on the opposite side. In addition, when adding a dye having absorption in the visible region for color correction, the method is not limited.

Hereinafter, examples and comparative examples will be described. However, the technical scope of the present invention is not limited only to the following examples. In the names of the following compounds, Pc represents a phthalocyanine nucleus, and PN represents phthalonitrile. In the names of the following compounds, “α- (substituent A) _a , β- (substituent A) _x-a PN (0 <a <x)” or “α- (substituent A) _a , β- (Substituent A) _x-a Pc (0 <a <x) ”means that the obtained phthalonitrile compound or phthalocyanine derivative has an average of a at the α-position and an average of x-a at the β-position. Means that a total of x substituents A have been introduced at the α-position and the β-position.

<Synthesis Example 1>
Phthalonitrile compound [α-{(4-COOC ₂ H ₄ OCH ₃ ) C ₆ H ₄ O} _a , β-{(4-COOC ₂ H ₄ OCH ₃ ) C ₆ H ₄ O} _1-a Cl ₃ PN ] (0 ≦ a <1) (Intermediate 1) In a 150 ml flask, 7.98 g (0.030 mol) of tetrachlorophthalonitrile (hereinafter abbreviated as TCPN) and methyl cellosolve p-hydroxybenzoate5. 95 g (0.030 mol) and 31.91 g of acetonitrile were added and stirred for about 30 minutes using a magnetic stirrer until the internal temperature was stabilized at 40 ° C., and then 4.56 g (0.033 mol) of potassium carbonate. Was allowed to react for about 3 hours. After cooling, the solvent was distilled off from the solution obtained by suction filtration by evaporation under conditions of about 110 ° C. × 1 hour. Furthermore, it vacuum-dried at about 110 degreeC overnight, and about 13.1g (yield of 102.4 mol% with respect to TCPN) was obtained.

<Synthesis Example 2>
Phthalonitrile compound [α-{(4-COOC ₂ H ₄ OCH ₃ ) C ₆ H ₄ O} _a , α-{(2,6-Cl ₂ ) C ₆ H ₃ S} _b, β-{(4- COOC ₂ H ₄ OCH ₃ ) C ₆ H ₄ O} _0.8-a , β-{(2,6-Cl ₂ ) C ₆ H ₃ S} _0.2-b Cl ₃ PN] (0 ≦ a < 0.8,0 ≦ b <0.2) (Intermediate 2) Synthesis In a 150 ml flask, 5.32 g (0.020 mol) TCPN and 3.14 g (0.016 mol) methyl cellosolve p-hydroxybenzoate. Then, 21.27 g of acetonitrile was added and stirred for about 30 minutes using a magnetic stirrer until the internal temperature was stabilized at 40 ° C., and then 3.04 g (0.022 mol) of potassium carbonate was added and the reaction was continued for about 2 hours. I let you. After the reaction, 0.72 g (0.004 mol) of 2,6-dichlorothiophenol was added to the flask, and the reaction was further continued for about 4 hours. After cooling, the same process as in Synthesis Example 1 was performed to obtain about 8.3 g (yield 98.8 mol% based on TCPN).

<Synthesis Example 3>
Phthalonitrile compounds [α-{(4-COOC ₂ H ₄ OCH ₃ ) C ₆ H ₄ O} _a , β-{(4-COOC ₂ H ₄ OCH ₃ ) C ₆ H ₄ O} _1-a F ₃ PN ] (0 ≦ a <1) (Intermediate 3) Synthesis of 8.00 g (0.040 mol) of tetrafluorophthalonitrile (hereinafter abbreviated as TFPN) and methyl cellosolve p-hydroxybenzoate in a 150 ml flask. 93 g (0.040 mol) and 32.01 g of acetonitrile were added, and after stirring for about 30 minutes using a magnetic stirrer until the internal temperature was stabilized at 40 ° C., 6.08 g (0.044 mol) of potassium carbonate Was allowed to react for about 4 hours. After cooling, the solvent was distilled off from the solution obtained by suction filtration by evaporation under conditions of about 110 ° C. × 1 hour. Furthermore, it vacuum-dried at about 110 degreeC overnight, and about 15.4g (The yield of 107.3 mol% with respect to TFPN) was obtained.

<Synthesis Example 4>
Synthesis of Phthalonitrile Compound [α-{(CH ₃ CH (OCH ₃ ) C ₂ H ₄ OOC) C ₂ H ₄ S} H ₃ PN] (Intermediate 4) In a 150 ml flask, 10 g of 3-nitrophthalonitrile (0 .0578 mol), 11.11 g (0.0578 mol) of 3-methoxybutyl 3-mercaptopropionate, and 40 g of acetonitrile, and stirred for about 30 minutes using a magnetic stirrer until the internal temperature was stabilized at 60 ° C. Thereafter, 8.79 g (0.0636 mol) of potassium carbonate was added and allowed to react for about 6 hours. After cooling, the same process as in Synthesis Example 1 was performed to obtain about 18.3 g (yield: 99.4 mol% based on 3-nitrophthalonitrile).

<Synthesis Example 5>
Phthalonitrile compound [α-{(4-SO ₃ C ₂ H ₄ OCH ₃ ) C ₆ H ₄ O} _a , β-{(4-SO ₃ C ₂ H ₄ OCH ₃ ) C ₆ H ₄ O} _{1- a Cl 3 PN] (0 ≦} a <1) synthesis 150ml flask (intermediate 5), TCPN13.30g (0.050 mol) and p- phenolsulfonic acid methyl cellosolve 12.10 g (0.050 mol) Then, 53.18 g of acetonitrile was added and stirred for about 30 minutes using a magnetic stirrer until the internal temperature was stabilized at 75 ° C., and then 7.60 g (0.055 mol) of potassium carbonate was added for about 8 hours. Reacted. After cooling, the solvent was distilled off from the solution obtained by suction filtration by evaporation under conditions of about 110 ° C. × 1 hour. Furthermore, it vacuum-dried at about 110 degreeC overnight, and about 23.0g (yield 99.6 mol% with respect to TCPN) was obtained.

<Synthesis Example 6>
Phthalonitrile compound [α-{(4-COOCH ₃ ) C ₆ H ₄ O} _a , β-{(4-COOCH ₃ ) C ₆ H ₄ O} _1.5-a Cl _2.5 PN] (0 ≦ a <1.5) Synthesis of (Intermediate 6) In a 150 ml flask, 4.25 g (0.016 mol) of TCPN, 3.65 g (0.024 mol) of methyl p-hydroxybenzoate, benzonitrile (hereinafter referred to as BN) 13.19 g was charged and stirred for about 30 minutes using a magnetic stirrer until the internal temperature was stabilized at 80 ° C. Then, 3.65 g (0.026 mol) of potassium carbonate was charged for about 4 hours. Reacted. After cooling, the solvent was distilled off from the solution obtained by suction filtration by evaporation under conditions of about 110 ° C. × 1 hour. Furthermore, it vacuum-dried at about 110 degreeC overnight, and about 6.5 g (yield 98.6 mol% with respect to TCPN) was obtained.

<Synthesis Example 7>
Phthalonitrile compound [α-{(4-COOC ₂ H ₄ OCH ₃ ) C ₆ H ₄ O} _a , β-{(4-COOC ₂ H ₄ OCH ₃ ) C ₆ H ₄ O} _0.6-a Cl _3.4 Synthesis of PN] (0 ≦ a <0.6) (Intermediate 7) In a 150 ml flask, 4.25 g (0.016 mol) of TCPN and 1.88 g of methyl cellosolve p-hydroxybenzoate (0.010 Mol) and 13.19 g of BN were added and stirred for about 30 minutes using a magnetic stirrer until the internal temperature was stabilized at 80 ° C., and then 1.46 g (0.011 mol) of potassium carbonate was added. Reacted for hours. After cooling, the solvent was distilled off from the solution obtained by suction filtration by evaporation under conditions of about 110 ° C. × 1 hour. Furthermore, it vacuum-dried at about 110 degreeC overnight, and about 5.7g (yield of 98.3 mol% with respect to TCPN) was obtained.

<Synthesis Example 8>
Phthalonitrile compound [α-{(4-COOC ₂ H ₄ OCH ₃ ) C ₆ H ₄ O} _a , β-{(4-COOC ₂ H ₄ OCH ₃ ) C ₆ H ₄ O} _0.3-a Cl _3.7 Synthesis of PN] (0 ≦ a <0.3) (Intermediate 8) In a 150 ml flask, 4.25 g (0.016 mol) of TCPN and 0.94 g of methyl cellosolve p-hydroxybenzoate (0.005 Mol) and 13.19 g of BN were added and stirred for about 30 minutes using a magnetic stirrer until the internal temperature was stabilized at 80 ° C., and then 0.73 g (0.005 mol) of potassium carbonate was added and about 4 Reacted for hours. After cooling, the solvent was distilled off from the solution obtained by suction filtration by evaporation under conditions of about 110 ° C. × 1 hour. Furthermore, it vacuum-dried at about 110 degreeC overnight, and about 4.9g (yield of 98.0 mol% with respect to TCPN) was obtained.

<Synthesis Example 9>
Phthalonitrile compound [α-{(4-COOC ₂ H ₄ OCH ₃ ) C ₆ H ₄ O} _a , α-{(2-OCH ₃ -4-COOC ₂ H ₄ OCH ₃ ) C ₆ H ₃ O} _b , Β-{(4-COOC ₂ H ₄ OCH ₃ ) C ₆ H ₄ O} _0.8-a , β-{(2-OCH ₃ -4-COOC ₂ H ₄ OCH ₃ ) C ₆ H ₃ O} Synthesis of _0.2-b Cl ₃ PN] (0 ≦ a <0.8, 0 ≦ b <0.2) (Intermediate 9) In a 150 ml flask, 6.65 g (0.025 mol) of TCPN and p-hydroxy 3.92 g (0.020 mol) of methyl cellosolve benzoate, 1.13 g (0.005 mol) of methyl cellosolve vanillate and 26.59 g of acetonitrile were added, and the internal temperature was 40 ° C. using a magnetic stirrer. After stirring for about 30 minutes until stable Was charged potassium carbonate 3.80 g (0.028 mol) was allowed to react for about 4 hours. After cooling, the solvent was distilled off from the solution obtained by suction filtration by evaporation under conditions of about 110 ° C. × 1 hour. Furthermore, it vacuum-dried at about 110 degreeC overnight, and about 10.7g (yield 99.5 mol% with respect to TCPN) was obtained.

<Synthesis Example 10>
Phthalonitrile compound _{[α - {(2-COOC} 2 H 4 OCH 3) C 10 H 8 -6-O} a, β - {(2-COOC 2 H 4 OCH 3) C 10 H 8 -6-O} Synthesis of _1-a Cl ₃ PN] (0 ≦ a <1) (Intermediate 10) In a 150 ml flask, 3.46 g (0.013 mol) of TCPN and 3.20 g of 6-hydroxy-2-naphthoic acid methyl cellosolve ( 0.013 mol) and 10.72 g of BN were added, and after stirring for about 30 minutes until the internal temperature was stabilized at 80 ° C. using a magnetic stirrer, 1.98 g (0.014 mol) of potassium carbonate was added. For about 4 hours. After cooling, the solvent was distilled off from the solution obtained by suction filtration by evaporation under conditions of about 110 ° C. × 1 hour. Furthermore, it vacuum-dried at about 110 degreeC overnight, and about 6.1g (yield of 98.4 mol% with respect to TCPN) was obtained.

<Synthesis Example 11>
Synthesis of phthalonitrile compound [α-{(4-CN) C ₆ H ₄ O} H ₃ PN] (intermediate 11) In a 150 ml flask, 25.10 g (0.145 mol) of 3-nitrophthalonitrile and 4-cyano 17.79 g (0.149 mol) of phenol and 100.42 g of acetonitrile were added, and the mixture was stirred for about 30 minutes using a magnetic stirrer until the internal temperature was stabilized at 85 ° C. Then, 22.04 g (0. 160 mol) was added and allowed to react for about 4 hours. After cooling, 100.42 g of distilled water was added dropwise to the solution obtained by suction filtration to precipitate crystals. After suction filtration, the taken-out crystals were vacuum-dried at about 60 ° C. overnight to obtain about 34.05 g (yield of 95.8 mol% based on 3 nitrophthalonitrile).

<Synthesis Example 12>
Synthesis of phthalonitrile compound [α-{(2-NO ₂ ) C ₆ H ₄ O} H ₃ PN] (intermediate 12) In a 150 ml flask, 25.10 g (0.145 mol) of 3 nitrophthalonitrile and 2- 24.21 g (0.174 mol) of nitrophenol and 100.42 g of acetonitrile were added, and the mixture was stirred for about 30 minutes using a magnetic stirrer until the internal temperature was stabilized at 85 ° C. Then, 24.05 g (0 .174 mol) was added and allowed to react for about 24 hours. After cooling, 200 g of distilled water was added dropwise to the solution obtained by suction filtration to precipitate crystals. After suction filtration, the taken out crystals were vacuum-dried at about 60 ° C. overnight to obtain about 36.1 g (yield 93.9 mol% based on 3 nitrophthalonitrile).

<Synthesis Example 13>
Phthalonitrile compounds [α-{(4-COOC ₂ H ₄ OCH ₃ ) C ₆ H ₄ O} _a , α-{(2-C ₆ H ₅ ) C ₆ H ₄ O} _b , β-{(4- COOC ₂ H ₄ OCH ₃ ) C ₆ H ₄ O} _0.9-a , β-{(2-C ₆ H ₅ ) C ₆ H ₄ O} _0.1-b Cl ₃ PN] (0 ≦ a < 0.9, 0 ≦ b <0.1) (Intermediate 13) Synthesis In a 150 ml flask, 4.25 g (0.016 mol) TCPN and 2.83 g (0.014 mol) methyl cellosolve p-hydroxybenzoate. Then, 0.27 g (0.002 mol) of o-phenylphenol and 13.19 g of BN were added and stirred for about 30 minutes using a magnetic stirrer until the internal temperature was stabilized at 80 ° C., and then 2.43 g of potassium carbonate. (0.018 mol) was added and allowed to react for about 4 hours. After cooling, the solvent was distilled off from the solution obtained by suction filtration by evaporation under conditions of about 110 ° C. × 1 hour. Furthermore, it vacuum-dried at about 110 degreeC overnight, and about 6.7g (yield of 98.5 mol% with respect to TCPN) was obtained.

<Synthesis Example 14>
Phthalonitrile compound [α-{(4-COOC ₂ H ₄ OCH ₃ ) C ₆ H ₄ O} _a , α-{(2-COOCH ₃ ) C ₆ H ₄ S} _b , β-{(4-COOC _{2 H 4 OCH 3) C 6 H} 4 O} 0.8-a, β - {(2-COOCH 3) C 6 H 4 S} 0.2-b Cl 3 PN] (0 ≦ a <0.8, Synthesis of 0 ≦ b <0.2 (intermediate 14) In a 150 ml flask, 4.25 g (0.016 mol) of TCPN, 2.51 g (0.013 mol) of methyl cellosolve p-hydroxybenzoate, methyl thiosalicylate 0.54 g (0.003 mol) and 13.19 g of BN were added and stirred for about 30 minutes using a magnetic stirrer until the internal temperature was stabilized at 80 ° C., and then 2.43 g (0.018 mol) of potassium carbonate. ) And allowed to react for about 4 hours After cooling, the solvent was distilled off from the solution obtained by suction filtration by evaporation under conditions of about 110 ° C. × 1 hour. Furthermore, it vacuum-dried at about 110 degreeC overnight, and about 6.6g (yield 98.5 mol% with respect to TCPN) was obtained.

<Synthesis Example 15>
Phthalonitrile compounds [α-{(4-COOC ₂ H ₄ OCH ₃ ) C ₆ H ₄ O} _a , α-{(4-OCH ₃ ) C ₆ H ₄ O} _b , β-{(4-COOC _{2 H 4 OCH 3) C 6 H} 4 O} 0.9-a, β - {(4-OCH 3) C 6 H 4 O} 0.1-b Cl 3 PN] (0 ≦ a <0.9, Synthesis of 0 ≦ b <0.1 (intermediate 15) In a 150 ml flask, 4.25 g (0.016 mol) of TCPN, 2.83 g (0.014 mol) of methyl cellosolve p-hydroxybenzoate, 4-methoxy 0.20 g (0.002 mol) of phenol and 13.19 g of BN were added and stirred for about 30 minutes using a magnetic stirrer until the internal temperature was stabilized at 80 ° C. Then, 2.43 g (0.018) of potassium carbonate was added. Mol) was added and allowed to react for about 4 hours. After cooling, the solvent was distilled off from the solution obtained by suction filtration by evaporation under conditions of about 110 ° C. × 1 hour. Furthermore, it vacuum-dried at about 110 degreeC overnight, and about 6.6g (yield 98.5 mol% with respect to TCPN) was obtained.

<Synthesis Example 16>
Phthalonitrile compound [α-{(4-COOC ₂ H ₄ OCH ₃ ) C ₆ H ₄ O} _a , α-{(2-C (CH ₃ ) ₃ ) C ₆ H ₄ O} _b , β-{( _{4-COOC 2 H 4 OCH 3} ) C 6 H 4 O} 0.9-a, β - {(2-C (CH 3) 3) C 6 H 4 O} 0.1-b Cl 3 PN] ( Synthesis of 0 ≦ a <0.9, 0 ≦ b <0.1) (Intermediate 16) In a 150 ml flask, 4.25 g (0.016 mol) of TCPN and 2.83 g of methyl cellosolve p-hydroxybenzoate (0 .014 mol), 0.24 g (0.002 mol) of 2-tert-butylphenol, and 13.19 g of BN were added, and the mixture was stirred for about 30 minutes using a magnetic stirrer until the internal temperature was stabilized at 80 ° C. About 2.43 g (0.018 mol) of potassium carbonate was added. The reaction was performed for 4 hours. After cooling, the solvent was distilled off from the solution obtained by suction filtration by evaporation under conditions of about 110 ° C. × 1 hour. Furthermore, it vacuum-dried at about 110 degreeC overnight, and about 6.6g (yield 98.5 mol% with respect to TCPN) was obtained.

<Synthesis Example 17>
Phthalonitrile compounds [α-{(4-COOC ₂ H ₄ OCH ₃ ) C ₆ H ₄ O} _a , α-{(3-COOC ₂ H ₅ ) C ₆ H ₄ O} _b , β-{(4- COOC ₂ H ₄ OCH ₃ ) C ₆ H ₄ O} _0.7-a , β-{(3-COOC ₂ H ₅ ) C ₆ H ₄ O} _0.3-b Cl ₃ PN] (0 ≦ a < 0.7, 0 ≦ b <0.3) Synthesis of Intermediate 17) In a 150 ml flask, 4.25 g (0.016 mol) of TCPN and 2.20 g (0.011 mol) of methyl cellosolve p-hydroxybenzoate. Then, 0.8 g (0.005 mol) of ethyl 3-hydroxybenzoate and 13.19 g of BN were added and stirred for about 30 minutes using a magnetic stirrer until the internal temperature was stabilized at 80 ° C., and then potassium carbonate 2 .43 g (0.018 mol) was charged and about 4 o'clock It was made to react between. After cooling, the solvent was distilled off from the solution obtained by suction filtration by evaporation under conditions of about 110 ° C. × 1 hour. Furthermore, it vacuum-dried at about 110 degreeC overnight, and about 6.5 g (yield 97.0 mol% with respect to TCPN) was obtained.

<Synthesis Example 18>
Phthalonitrile compound [α-{(4-COOC ₂ H ₄ OCH ₃ ) C ₆ H ₄ O} _a , α- {C ₆ F ₅ O} _b , β-{(4-COOC ₂ H ₄ OCH ₃ ) C ₆ H ₄ O} _0.8-a , β- {C ₆ F ₅ O} _0.2-b Cl ₃ PN] (0 ≦ a <0.8, 0 ≦ b <0.2) (Intermediate 18 In a 150 ml flask, 13.30 g (0.050 mol) of TCPN, 7.85 g (0.040 mol) of methyl cellosolve p-hydroxybenzoate, 1.84 g (0.010 mol) of pentafluorophenol, acetonitrile 53 .18 g was added and stirred for about 30 minutes using a magnetic stirrer until the internal temperature was stabilized at 40 ° C., then 7.60 g (0.055 mol) of potassium carbonate was added and allowed to react for about 5 hours. . After cooling, the solvent was distilled off from the solution obtained by suction filtration by evaporation under conditions of about 110 ° C. × 1 hour. Furthermore, it vacuum-dried at about 110 degreeC overnight, and about 21.3g (yield 100.4 mol% with respect to TCPN) was obtained.

<Synthesis Example 19>
Phthalonitrile compound [α-{(4-COOC ₂ H ₄ OCH ₃ ) C ₆ H ₄ O} _a , α-{(3,5-Br ₂ -4-COOC ₂ H ₄ OCH ₃ ) C ₆ H ₂ O } _B , β-{(4-COOC ₂ H ₄ OCH ₃ ) C ₆ H ₄ O} _0.8-a , β-{(3,5-Br ₂ -4-COOC ₂ H ₄ OCH ₃ ) C ₆ H ₂ O} _0.2-b Cl ₃ PN] (0 ≦ a <0.8, 0 ≦ b <0.2) (Intermediate 19) In a 150 ml flask, 13.30 g (0.050 mol) of TCPN was added. And 7.85 g (0.040 mol) of p-hydroxybenzoic acid methyl cellosolve, 3.54 g (0.010 mol) of 3,5-dibromo-4-hydroxybenzoic acid methyl cellosolve, and 53.18 g of acetonitrile. Using a magnetic stirrer, the internal temperature is 0 After stirring for about 30 minutes to stabilize the ° C., was about 3 hours by introducing potassium carbonate 7.60 g (0.055 mol). After cooling, the solvent was distilled off from the solution obtained by suction filtration by evaporation under conditions of about 110 ° C. × 1 hour. Furthermore, it vacuum-dried at about 110 degreeC overnight, and about 23.0g (yield 100.6 mol% with respect to TCPN) was obtained.

<Synthesis Example 20>
Phthalonitrile compound [α-{(4-COOC ₂ H ₄ OCH ₃ ) C ₆ H ₄ O} _a , α-{(4-CF ₃ ) C ₆ H ₄ O} _b , β-{(4-COOC _{2 H 4 OCH 3) C 6 H} 4 O} 0.9-a, β - {(4-CF 3) C 6 H 4 O} 0.1-b Cl 3 PN] (0 ≦ a <0.9, Synthesis of 0 ≦ b <0.1 (intermediate 20) In a 150 ml flask, 4.25 g (0.016 mol) of TCPN, 2.83 g (0.014 mol) of methyl cellosolve p-hydroxybenzoate, 4-hydroxy After adding 0.26 g (0.002 mol) of benzotrifluoride and 13.19 g of BN and stirring with a magnetic stirrer for about 30 minutes until the internal temperature is stabilized at 80 ° C., 2.43 g (0 .018 mole) and let it react for about 4 hours . After cooling, the solvent was distilled off from the solution obtained by suction filtration by evaporation under conditions of about 110 ° C. × 1 hour. Furthermore, it vacuum-dried at about 110 degreeC overnight, and about 6.7g (yield of 98.5 mol% with respect to TCPN) was obtained.

<Synthesis Example 21>
(Precursor synthesis example 1)
Synthesis of phthalonitrile precursor [Br _0.33 Cl _3.67 PN] (Precursor 1)
Into a 150 ml flask, 16.15 g (0.060 mol) of TCPN and 64.46 g of N-methylpyrrolidone were added and stirred for about 30 minutes using a magnetic stirrer until the internal temperature was stabilized at 80 ° C., followed by bromination. Potassium 7.22g (0.060mol) was added and reacted for about 72 hours. After cooling, the filtrate obtained by removing inorganic salts by suction filtration was evaporated to obtain a brown solid. 30 g of methanol and 50 g of water were added to the solid, and the mixture was stirred and washed for 1 hour, followed by filtration to obtain 15.11 g of a white solid (yield based on TCPN: 89.8 mol%). Moreover, the obtained white solid was a mixture of TCPN (70 mol%), bromotrichlorophthalonitrile (27 mol%), and dibromodichlorophthalonitrile (3 mol%) by composition analysis by gas chromatography.

Phthalonitrile compound [α-{(4-COOC ₂ H ₄ OCH ₃ ) C ₆ H ₄ O} _a , α- {C ₆ H ₅ O} _b , β-{(4-COOC ₂ H ₄ OCH ₃ ) C ₆ H ₄ O} _0.5-a , β- {C ₆ H ₅ O} _0.2-b Cl ₃ PN] (0 ≦ a < _0.5 , 0 ≦ b <0.2) (Intermediate 21 In a 150 ml flask, 4.21 g (0.015 mol) of the precursor 1 obtained in Precursor Synthesis Example 1, 1.49 g (0.008 mol) of methyl cellosolve p-hydroxybenzoate, phenol 0 .30 g (0.003 mol) and 17.33 g of BN were added and stirred for about 30 minutes using a magnetic stirrer until the internal temperature was stabilized at 80 ° C., and then 1.85 g (0.14 mol) of potassium carbonate. Was allowed to react for about 12 hours. After cooling, the solvent was distilled off from the solution obtained by suction filtration by evaporation under conditions of about 110 ° C. × 1 hour. Furthermore, it vacuum-dried at about 110 degreeC overnight, and about 5.6 g (yield 100.3 mol% with respect to the precursor 1) was obtained.

<Synthesis Example 22>
Synthesis of phthalonitrile compound [β-{(2-COOCH ₃ ) C ₆ H ₄ O} PN] (intermediate 22) In a 150 ml flask, 25.10 g (0.145 mol) of 4-nitrophthalonitrile and methyl salicylate 30 .89 g (0.203 mol), potassium carbonate 22.04 g (0.16 mol), n-tetrabutylammonium bromide 0.93 g (0.003 mol), and acetonitrile 100.42 g were added, and the internal temperature was 80 ° C. It was made to react for about 40 hours, stirring using a magnetic stirrer. After cooling, a mixed solution of 50 g of methanol and 150 g of water was added dropwise to the solution obtained by suction filtration to precipitate crystals. After the obtained crystals were suction filtered, washing and purification were performed by adding a mixed solution of 200 g of methanol and 200 g of water and stirring and washing again. After suction filtration, the extracted crystal was vacuum-dried at about 60 ° C. overnight to obtain about 34.8 g (yield: 86.3 mol% based on 4-nitrophthalonitrile).

<Example 1>
Phthalocyanine derivatives [ZnPc- {α- (4-COOC ₂ H ₄ OCH ₃ ) C ₆ H ₄ O} _x , {β- (4-COOC ₂ H ₄ OCH ₃ ) C ₆ H ₄ O} _3.8-x Synthesis of H _0.8 Cl _11.4 ] (0 ≦ x <3.8) In a 150 ml flask, 10.1 g (0.024 mol) of Intermediate 1 obtained in Synthesis Example 1 and 0.16 g of phthalonitrile. (0.001 mol), 3.46 g of BN were added, stirred for about 1 hour using a magnetic stirrer under nitrogen flow (10 ml / min) until the internal temperature was stabilized at 160 ° C., and then 2.22 g of zinc iodide. (0.007 mol) was added and allowed to react for about 12 hours. After cooling, the reaction solution was evaporated under conditions of 140 ° C. × 1 hr and the solvent was distilled off. Then, the resulting solid was added to the sum of the weight of intermediate 1 and phthalonitrile used in the phthalocyanination reaction (10 Methyl Cellosolve (6.9 g) corresponding to the weight obtained by subtracting the weight of BN (3.46 g) from .37 g) was added, and the mixture was stirred and dissolved to prepare a crystallization solution. Next, the prepared crystallization solution was dropped into methanol (103.8 g) corresponding to 10 times the sum of the weight of intermediate 1 and phthalonitrile used in the phthalocyanination reaction, and stirred for 30 minutes. Thereafter, distilled water (72.6 g) corresponding to 7 times the sum of the weight of the intermediate was added dropwise over 30 minutes. After completion of the addition, the mixture was further stirred for 30 minutes to precipitate crystals. The obtained crystals were suction filtered, and then 1/2 times the amount of methanol (51.9 g) at the time of crystallization was added again and stirred for 30 minutes, and then 1/2 times the amount of distilled water at the time of crystallization (36 .3 g) was added dropwise over 30 minutes, and after completion of the addition, the mixture was further stirred for 30 minutes for washing and purification. After suction filtration, the taken-out crystal was vacuum-dried at about 60 ° C. overnight to obtain about 10.7 g (yield of 99.2 mol% based on intermediate 1 and phthalonitrile).

(Measurement of maximum absorption wavelength and Gram extinction coefficient)
The maximum absorption wavelength (λmax) and Gram extinction coefficient of the obtained phthalocyanine derivative were measured in a methanol solution containing 0.8 wt% of methyl cellosolve using a spectrophotometer (manufactured by Hitachi, Ltd .: U-2910). . The measurement method was as follows.

0.04 g of the phthalocyanine derivative obtained in a 50 ml volumetric flask was dissolved in 20 g of methyl cellosolve, and methanol was added so that the meniscus of the solution coincided with the marked line of the 50 ml volumetric flask. Next, 1 ml of the prepared solution is taken using a pipette, and all of the taken solution is put into a 50 ml volumetric flask and diluted with methanol, so that the meniscus of the solution matches the marked line of the 50 ml volumetric flask. did. The solution thus prepared was placed in a 1 cm square Pyrex cell, and the transmission spectrum was measured using a spectrophotometer. Further, when the measured absorbance is A, the gram extinction coefficient was calculated by the following formula.
Gram extinction coefficient = (A × 5000) / (0.08 × 1000) Table 4 summarizes the results thus measured.

(Evaluation of heat resistance)
To 0.125 g of the obtained phthalocyanine derivative, 0.42 g of a maleimide binder polymer 38.7 wt% propylene glycol monomethyl ether acetate (hereinafter abbreviated as PGMEA) manufactured by Nippon Shokubai Co., Ltd. and 1.22 g of PGMEA, dipentaerythritol hexaacrylate 0.112 g and 0.01 g (IRGACURE 369) manufactured by Ciba Specialty Chemicals Co., Ltd. were added, dissolved and mixed to prepare a resin coating solution. The obtained resin coating liquid was applied to a glass plate using a bar coater so that the dye concentration in the dry film was 30 wt% and the dry film thickness was 2 μm, and dried at 80 ° C. for 30 minutes. The absorption spectrum of the coating glass plate thus obtained was measured with a spectrophotometer (manufactured by Hitachi, Ltd .: U-2910), and this was used as the spectrum before heating. Next, the coated glass plate whose spectrum before heating was measured was heat-treated at 220 ° C. for 20 minutes. The absorption spectrum of the heat-treated coated glass plate was measured with a spectrophotometer, and this was used as the spectrum after heating. The absorbance from 380 nm to 900 nm in each spectrum before and after heating measured in this way was integrated, and the difference between the absorbance before and after heating was measured. Further, ΔE was calculated by the following equation, where E _{1 was} the spectrum before heating, E _{2 was} the spectrum after heating, and ΔE was the difference in measured absorbance.

  The results thus measured are summarized in Table 4 below.

(Evaluation of solubility)
To 0.1 g of the obtained phthalocyanine derivative, 0.9 g of PGMEA was added to prepare a preparation solution containing 10 wt% of the dye. The prepared solution was stirred with a magnetic stirrer for 1 hour, and then the entire amount was collected with a syringe and filtered using a membrane filter (φ = 0.45 μm). When the prepared solution can pass through the membrane filter without clogging, conduct a filtration test to determine that the dye is dissolved in the prepared solution. The solubility was evaluated by Δ when the case was observed and × when the filter was clogged.

<Example 2>
[ZnPc- {α- (4-COOC ₂ H ₄ OCH ₃ ) C ₆ H ₄ O} _x , {α- (2,6-Cl ₂ ) C ₆ H ₃ S} _y , {β- (4-COOC _{2 H 4 OCH 3) C 6} H 4 O} 2.88-x {β- (2,6-Cl 2) C 6 H 3 S} 0.72-y, H 1.6 Cl 10.8] ( Synthesis of 0 ≦ x <2.88, 0 ≦ y <0.72) In a 150 ml flask, 12.67 g (0.030 mol) of intermediate 2 obtained in Synthesis Example 2 and 0.43 g of phthalonitrile (0 0.003 mol) and 4.36 g of BN were added and stirred for about 1 hour using a magnetic stirrer until the internal temperature was stabilized at 160 ° C. under a nitrogen flow (10 ml / min), and then 2.93 g (0 .009 mol) was added and allowed to react for about 10 hours. After cooling, the completely same operation as Example 1 was performed, and about 13.2g (The intermediate body 2 and the yield of 96.8 mol% with respect to a phthalonitrile) was obtained.

  The phthalocyanine derivative thus obtained was measured for the maximum absorption wavelength, gram extinction coefficient, and heat resistance by exactly the same operation as in Example 1, and the results are summarized in Table 4.

<Example 3>
Phthalocyanine derivatives [ZnPc- {α- (4-COOC ₂ H ₄ OCH ₃ ) C ₆ H ₄ O} _x , {β- (4-COOC ₂ H ₄ OCH ₃ ) C ₆ H ₄ O} _3.8-x , (Β-NO ₂ ) _0.2 H _0.6 Cl _11.4 ] (0 ≦ x <3.8) In a 150 ml flask, intermediate 1, 10.64 g (0 0.025 mol), 0.23 g (0.001 mol) of 4-nitrophthalonitrile, and 3.62 g of BN, and under nitrogen flow (10 ml / min) until the internal temperature is stabilized at 160 ° C. using a magnetic stirrer. After stirring for about 1 hour, 2.31 g (0.007 mol) of zinc iodide was added and allowed to react for about 9 hours. After cooling, the completely same operation as Example 1 was performed, and about 10.95g (The yield of 96.9 mol% with respect to the intermediate body 1 and 4-nitro phthalonitrile) was obtained.

  The phthalocyanine derivative thus obtained was measured for the maximum absorption wavelength, gram extinction coefficient, and heat resistance by exactly the same operation as in Example 1, and the results are summarized in Table 4.

<Example 4>
Zinc phthalocyanine derivatives _{[Zn (C 32 N 8.2)} - {α- (4-COOC 2 H 4 OCH 3) C 6 H 4 O} x, {β- (4-COOC 2 H 4 OCH 3) C 6 Synthesis of H ₄ O} _3.8-x H _0.6 Cl _11.4 ] (0 ≦ x <3.8) Into a 150 ml flask, Intermediate 1, 10.64 g (0. 025 mol), 0.17 g (0.001 mol) of pyridine-2,3-dicarbonitrile, and 3.60 g of BN were added, and the internal temperature was changed to 160 ° C. using a magnetic stirrer under nitrogen flow (10 ml / min). After stirring for about 1 hour until stabilized, 2.31 g (0.007 mol) of zinc iodide was added and allowed to react for about 9 hours. After cooling, the completely same operation as Example 1 was performed, and about 11.2 g (yield 99.6 mol% with respect to the intermediate body 1 and pyridine-2,3-dicarbonitrile) was obtained.

  The phthalocyanine derivative thus obtained was measured for the maximum absorption wavelength, gram extinction coefficient, and heat resistance by exactly the same operation as in Example 1, and the results are summarized in Table 4.

<Example 5>
Zinc phthalocyanine derivative [Zn (C _32.8 N ₈ )-{α- (4-COOC ₂ H ₄ OCH ₃ ) C ₆ H ₄ O} _x , {β- (4-COOC ₂ H ₄ OCH ₃ ) C ₆ Synthesis of H ₄ O} _3.8-x H _1.2 Cl _11.4 ] (0 ≦ x <3.8) Intermediate 1, 10.64 g (0. 025 mol), 0.23 g (0.001 mol) of 2,3-dicyanonaphthalene, and 3.62 g of BN, and under nitrogen flow (10 ml / min) until the internal temperature is stabilized at 160 ° C. using a magnetic stirrer. After stirring for about 1 hour, 2.31 g (0.003 mol) of zinc iodide was added and allowed to react for about 9 hours. After cooling, the completely same operation as Example 1 was performed, and about 11.0g (The yield with respect to the intermediate body 1 and 2, 3- dicyano naphthalene was 97.3 mol%) was obtained.

  The phthalocyanine derivative thus obtained was measured for the maximum absorption wavelength, gram extinction coefficient, and heat resistance by exactly the same operation as in Example 1, and the results are summarized in Table 4.

<Example 6>
Zinc phthalocyanine derivative [Zn (C _32.8 N ₈ )-{α- (4-COOC ₂ H ₄ OCH ₃ ) C ₆ H ₄ O} _x , {β- (4-COOC ₂ H ₄ OCH ₃ ) C ₆ Synthesis of H ₄ O} _3.8-x H _0.8 Cl _11.4 Br _0.4 ] (0 ≦ x <3.8) Intermediates 1 and 10 obtained in Synthesis Example 1 were added to a 150 ml flask. 64 g (0.025 mol), 2,3-dibromo-6,7-dicyanonaphthalene 0.44 g (0.001 mol) and BN 3.69 g were added, and under a nitrogen flow (10 ml / min), a magnetic stirrer was added. After stirring for about 1 hour until the internal temperature was stabilized at 160 ° C., 2.31 g (0.007 mol) of zinc iodide was added and allowed to react for about 12 hours. After cooling, the completely same operation as Example 1 was performed, and about 10.95g (The yield of 95.1 mol% with respect to the intermediate body 1 and 2, 3- dibromo-6,7- dicyano naphthalene) was obtained.

  The phthalocyanine derivative thus obtained was measured for the maximum absorption wavelength, gram extinction coefficient, and heat resistance by exactly the same operation as in Example 1, and the results are summarized in Table 4.

<Example 7>
Phthalocyanine derivatives [ZnPc- {α- (4-COOC ₂ H ₄ OCH ₃ ) C ₆ H ₄ O} _x , {β- (4-COOC ₂ H ₄ OCH ₃ ) C ₆ H ₄ O} _3.8-x , (Β-NH ₂ ) _0.2 H _0.6 Cl _11.4 ] (0 ≦ x <3.8) In a 150 ml flask, intermediate 1, 10.64 g (0 0.025 mol), 0.19 g (0.001 mol) of 4-aminophthalonitrile, and 3.61 g of BN were added, until the internal temperature was stabilized at 160 ° C. using a magnetic stirrer under nitrogen flow (10 ml / min). After stirring for about 1 hour, 2.31 g (0.007 mol) of zinc iodide was added and allowed to react for about 12 hours. After cooling, the completely same operation as Example 1 was performed, and about 11.3g (The yield with respect to the intermediate body 1 and 4-aminophthalonitrile was 100.4 mol%) was obtained.

  The phthalocyanine derivative thus obtained was measured for the maximum absorption wavelength, gram extinction coefficient, and heat resistance by exactly the same operation as in Example 1, and the results are summarized in Table 4.

<Example 8>
Phthalocyanine derivatives [ZnPc- {α- (4-COOC ₂ H ₄ OCH ₃ ) C ₆ H ₄ O} _x , {β- (4-COOC ₂ H ₄ OCH ₃ ) C ₆ H ₄ O} _3.8-x , (Β-OH) _0.2 H _0.6 Cl _11.4 ] (0 ≦ x <3.8) In a 150 ml flask, Intermediate 1, 10.64 g (0. 025 mol), 0.19 g (0.001 mol) of 4-hydroxyphthalonitrile, and 3.61 g of BN were added, and under a nitrogen flow (10 ml / min), a magnetic stirrer was used to stabilize the internal temperature at 160 ° C. After stirring for 1 hour, 2.31 g (0.007 mol) of zinc iodide was added and allowed to react for about 12 hours. After cooling, the completely same operation as Example 1 was performed, and about 11.3g (The yield of 100.4 mol% with respect to the intermediate body 1 and 4-hydroxyphthalonitrile) was obtained.

  The phthalocyanine derivative thus obtained was measured for the maximum absorption wavelength, gram extinction coefficient, and heat resistance by exactly the same operation as in Example 1, and the results are summarized in Table 4.

<Example 9>
Phthalocyanine derivatives [ZnPc- {α- (4-COOC ₂ H ₄ OCH ₃ ) C ₆ H ₄ O} _x , {β- (4-COOC ₂ H ₄ OCH ₃ ) C ₆ H ₄ O} _3.8-x , (Β-C (CH ₃ ) ₃ ) _0.2 H _0.6 Cl _11.4 ] (0 ≦ x <3.8) Intermediates 1 and 10 obtained in Synthesis Example 1 were placed in a 150 ml flask. .64 g (0.025 mol), 4-tert-butylphthalonitrile 0.24 g (0.001 mol), and BN 3.63 g were added, and the internal temperature was measured using a magnetic stirrer under nitrogen flow (10 ml / min). After stirring for about 1 hour until stabilized at 160 ° C., 2.31 g (0.007 mol) of zinc iodide was added and allowed to react for about 12 hours. After cooling, the completely same operation as Example 1 was performed, and about 11.0g (The yield of 97.2 mol% with respect to the intermediate body 1 and 4-tert- butyl phthalonitrile) was obtained.

  The phthalocyanine derivative thus obtained was measured for the maximum absorption wavelength, gram extinction coefficient, and heat resistance by exactly the same operation as in Example 1, and the results are summarized in Table 4.

<Example 10>
Phthalocyanine derivatives [ZnPc- {α- (4-COOC ₂ H ₄ OCH ₃ ) C ₆ H ₄ O} _x , {β- (4-COOC ₂ H ₄ OCH ₃ ) C ₆ H ₄ O} _3.8-x Synthesis of H _0.4 Cl _11.8 ] (0 ≦ x <3.8) In a 150 ml flask, Intermediate 1, 10.64 g (0.025 mol) obtained in Synthesis Example 1, 4,5-dichloro After adding 0.26 g (0.001 mol) of phthalonitrile and 3.63 g of BN, the mixture was stirred for about 1 hour using a magnetic stirrer under a nitrogen flow (10 ml / min) until the internal temperature was stabilized at 160 ° C. Zinc halide (2.31 g, 0.007 mol) was added and allowed to react for about 12 hours. After cooling, the completely same operation as Example 1 was performed, and about 11.2 g (yield 98.9 mol% with respect to the intermediate body 1 and 4, 5- dichloro phthalonitrile) was obtained.

  The phthalocyanine derivative thus obtained was measured for the maximum absorption wavelength, gram extinction coefficient, and heat resistance by exactly the same operation as in Example 1, and the results are summarized in Table 4.

<Example 11>
Zinc phthalocyanine derivatives _{[Zn (C 32 N 8.08)} - {α- (4-COOC 2 H 4 OCH 3) C 6 H 4 O} x, {β- (4-COOC 2 H 4 OCH 3) C 6 Synthesis of H ₄ O} _3.96-x H _0.08 Cl _11.88 ] (0 ≦ x <3.96) In a 150 ml flask, Intermediate 1, 10.64 g (0. 025 mol), 0.03 g (0.0003 mol) of 2,3-dicyanopyrazine, and 3.56 g of BN, and under nitrogen flow (10 ml / min) until the internal temperature is stabilized at 160 ° C. using a magnetic stirrer. After stirring for about 1 hour, 2.22 g (0.007 mol) of zinc iodide was added and allowed to react for about 12 hours. After cooling, the completely same operation as Example 1 was performed, and about 10.45g (The yield of 94.3 mol% with respect to the intermediate body 1 and 2, 3- dicyano pyrazine) was obtained.

  The phthalocyanine derivative thus obtained was measured for the maximum absorption wavelength, gram extinction coefficient, and heat resistance by exactly the same operation as in Example 1, and the results are summarized in Table 4.

<Example 12>
Phthalocyanine derivatives [ZnPc- {α- (4-COOC ₂ H ₄ OCH ₃ ) C ₆ H ₄ O} _x , {β- (4-COOC ₂ H ₄ OCH ₃ ) C ₆ H ₄ O} _3.8-x Synthesis of H _0.8 F _11.4 ] (0 ≦ x <3.8) In a 150 ml flask, the intermediate 3 obtained in Synthesis Example 3, 8.99 g (0.025 mol), 0.17 g of phthalonitrile. (0.001 mol), 3.05 g of BN were added, stirred for about 1 hour using a magnetic stirrer under nitrogen flow (10 ml / min) until the internal temperature was stabilized at 160 ° C., and then 2.31 g of zinc iodide. (0.007 mol) was added and allowed to react for about 12 hours. After cooling, the completely same operation as Example 1 was performed, and about 8.95g (The intermediate body 3 and the yield of 93.3 mol% with respect to a phthalonitrile) was obtained.

<Example 13>
Phthalocyanine derivatives _{[ZnPc-α - {(CH} 3 CH (OCH 3) C 2 H 4 OOC) C 2 H 4 S} 0.2, {α- (4-COOC 2 H 4 OCH 3) C 6 H 4 O }, _X , {β- (4-COOC ₂ H ₄ OCH ₃ ) C ₆ H ₄ O} _3.8-x H _0.6 Cl _11.4 ] (0 ≦ x <3.8) in a 150 ml flask The intermediate 1, 10.21 g (0.024 mol) obtained in Synthesis Example 1, the intermediate 4 obtained in Synthesis Example 4, 0.40 g (0.001 mol), and 3.54 g of BN were added, After stirring for about 1 hour under a nitrogen flow (10 ml / min) using a magnetic stirrer until the internal temperature is stabilized at 160 ° C., 2.22 g (0.007 mol) of zinc iodide is added and the reaction is continued for about 12 hours. I let you. After cooling, the completely same operation as Example 1 was performed, and about 10.0g (The yield of 90.7 mol% with respect to the intermediate body 1 and the intermediate body 4) was obtained.

  The phthalocyanine derivative thus obtained was measured for the maximum absorption wavelength, gram extinction coefficient, and heat resistance by exactly the same operation as in Example 1, and the results are summarized in Table 4.

<Example 14>
Phthalocyanine derivatives [ZnPc- {α- (4-SO ₃ C ₂ H ₄ OCH ₃ ) C ₆ H ₄ O} _x , {β- (4-SO ₃ C ₂ H ₄ OCH ₃ ) C ₆ H ₄ O} _{3 .8-x} H _0.8 Cl _11.4 ] (0 ≦ x <3.8) In a 150 ml flask, 11.05 g (0.024 mol) of intermediate 5 obtained in Synthesis Example 5 was added to phthalo 0.16 g (0.001 mol) of nitrile and 3.75 g of BN were added, stirred for about 1 hour using a magnetic stirrer under nitrogen flow (10 ml / min) until the internal temperature was stabilized at 160 ° C., and then iodinated. Zinc 2.22 g (0.007 mol) was added and allowed to react for about 12 hours. After cooling, the completely same operation as Example 1 was performed, and about 10.55 g (yield 90.5 mol% with respect to the intermediate body 5 and a phthalonitrile) was obtained.

  The phthalocyanine derivative thus obtained was measured for the maximum absorption wavelength, gram extinction coefficient, and heat resistance by exactly the same operation as in Example 1, and the results are summarized in Table 4.

  The structures of Examples 1 to 14 are summarized in Table 1. Table 2 shows the relationship between the intermediates prepared in each synthesis example and the phthalonitrile derivatives mixed in each example.

In the present invention, among all the groups introduced as R ^{1 to} R ⁴ , 0.05 or more and less than 3 are hydrogen atoms, 1 to 6 are substituents (a), and The remainder is a halogen atom.

  Here, a method of counting the number of hydrogen atoms, substituents (a), and halogen atoms is shown below.

  For example, taking Example 1 as an example, (i) Intermediate 1 and (ii) phthalonitrile are mixed.

  (I) Intermediate 1 is prepared by including mixing tetrachlorophthalonitrile (TCPN) and methyl cellosolve p-hydroxybenzoate. Tetrachlorophthalonitrile (TCPN) has four chlorine atoms, one of which is derived from methyl cellosolve p-hydroxybenzoate as can be seen from the “number of substituents” item in Table 2. Substituent (a) is substituted. The remaining three remain chlorine atoms. Thus, as a result, 1 unit of intermediate 1 has 3.0 chlorine atoms, 1.0 substituent (a) derived from methyl cellosolve of p-hydroxybenzoate, 2 This is a form in which 0 cyano groups are introduced.

  (Ii) Phthalonitrile is a form in which 4.0 hydrogen atoms and 2.0 cyano groups are introduced into the benzene ring.

  In order to produce a phthalocyanine derivative, both (i) intermediate 1 and (ii) phthalonitrile each require four units, and are further mixed at a blend ratio shown in Table 2, resulting in a substituent group. The number of (a) is calculated by 1.0 (number of substituents) × 4 (units) × 0.95 (blend ratio) and is 3.8. The number of hydrogen atoms is calculated by 4.0 × 4 (unit) × 0.05 (blend ratio), and becomes 0.8. The number of halogen atoms is calculated by 3.0 (number of substituents) × 4 (units) × 0.95 (blend ratio), and becomes 11.4.

<Example 15>
The maximum absorption wavelength, gram extinction coefficient and heat resistance of the phthalocyanine derivative obtained in Example 2 were exactly the same as in Example 1 except that the heat resistance was evaluated by the following method of heat resistance evaluation method (2). The results were measured and the results are summarized in Table 4.

<Heat resistance evaluation method (2)>
To 0.125 g of the obtained phthalocyanine derivative, 0.42 g of a maleimide-based binder polymer 38.7 wt% propylene glycol monomethyl ether acetate (hereinafter abbreviated as PGMEA) manufactured by Nippon Shokubai Co., Ltd. and 20.0 g of PGMEA, dipentaerythritol hexaacrylate 0.112 g and 0.01 g (IRGACURE 369) manufactured by Ciba Specialty Chemicals Co., Ltd. were added, dissolved and mixed to prepare a resin coating solution. The obtained resin coating liquid was applied to a glass plate using a bar coater so that the dye concentration in the dry film was 30 wt% and the dry film thickness was 0.1 μm, and dried at 80 ° C. for 30 minutes. The absorption spectrum of the coating glass plate thus obtained was measured with a spectrophotometer (manufactured by Hitachi, Ltd .: U-2910), and this was used as the spectrum before heating. Next, the coated glass plate whose spectrum before heating was measured was heat-treated at 220 ° C. for 20 minutes. The absorption spectrum of the heat-treated coated glass plate was measured with a spectrophotometer, and this was used as the spectrum after heating. The absorbance from 380 nm to 900 nm in each spectrum before and after heating measured in this way was integrated, and the difference between the absorbance before and after heating was measured. Further, ΔE was calculated by the following equation, where E _{1 was} the spectrum before heating, E _{2 was} the spectrum after heating, and ΔE was the difference in measured absorbance.

  The results thus measured are summarized in Table 4 below. A table showing the relationship between the thickness of the film and the corresponding examples is summarized in Table 3.

<Example 16>
In Example 15, the same procedure as in Example 15 was followed, except that the phthalocyanine derivative obtained in Example 2 was replaced with the phthalocyanine derivative obtained in Example 3, and the maximum absorption wavelength, gram extinction coefficient and heat resistance were The results are summarized in Table 4.

<Example 17>
In Example 15, the same procedure as in Example 15 was followed, except that the phthalocyanine derivative obtained in Example 2 was replaced with the phthalocyanine derivative obtained in Example 4, and the maximum absorption wavelength, gram extinction coefficient and heat resistance were The results are summarized in Table 4.

<Example 18>
In Example 15, the same procedure as in Example 15 was followed, except that the phthalocyanine derivative obtained in Example 2 was replaced with the phthalocyanine derivative obtained in Example 5, and the maximum absorption wavelength, gram extinction coefficient and heat resistance were The results are summarized in Table 4.

<Example 19>
In Example 15, the same procedure as in Example 15 was followed, except that the phthalocyanine derivative obtained in Example 2 was replaced with the phthalocyanine derivative obtained in Example 6, and the maximum absorption wavelength, gram extinction coefficient and heat resistance were The results are summarized in Table 4.

<Example 20>
In Example 15, the same procedure as in Example 15 was followed except that the phthalocyanine derivative obtained in Example 2 was replaced with the phthalocyanine derivative obtained in Example 7, and the maximum absorption wavelength, gram extinction coefficient and heat resistance were The results are summarized in Table 4.

<Example 21>
In Example 15, the same procedure as in Example 15 was followed, except that the phthalocyanine derivative obtained in Example 2 was replaced with the phthalocyanine derivative obtained in Example 8, and the maximum absorption wavelength, gram extinction coefficient and heat resistance were The results are summarized in Table 4.

<Example 22>
In Example 15, the same procedure as in Example 15 was followed, except that the phthalocyanine compound obtained in Example 2 was replaced with the phthalocyanine compound obtained in Example 9, and the maximum absorption wavelength, gram extinction coefficient and heat resistance were The results are summarized in Table 4.

<Example 23>
In Example 15, the same procedure as in Example 15 was followed except that the phthalocyanine derivative obtained in Example 2 was replaced with the phthalocyanine derivative obtained in Example 10, and the maximum absorption wavelength, gram extinction coefficient and heat resistance were The results are summarized in Table 4.

<Example 24>
In Example 15, the same procedure as in Example 15 was followed, except that the phthalocyanine derivative obtained in Example 2 was replaced with the phthalocyanine derivative obtained in Example 11, and the maximum absorption wavelength, gram extinction coefficient and heat resistance were The results are summarized in Table 4.

<Example 25>
In Example 15, the same procedure as in Example 15 was followed, except that the phthalocyanine derivative obtained in Example 2 was replaced with the phthalocyanine derivative obtained in Example 12, and the maximum absorption wavelength, gram extinction coefficient and heat resistance were The results are summarized in Table 4.

<Example 26>
In Example 15, the same procedure as in Example 15 was followed, except that the phthalocyanine derivative obtained in Example 2 was replaced with the phthalocyanine derivative obtained in Example 13, and the maximum absorption wavelength, gram extinction coefficient and heat resistance were The results are summarized in Table 4.

<Example 27>
In Example 15, the same procedure as in Example 15 was followed except that the phthalocyanine derivative obtained in Example 2 was replaced with the phthalocyanine derivative obtained in Example 14, and the maximum absorption wavelength, gram extinction coefficient and heat resistance were The results are summarized in Table 4.

  The correspondence between Examples 15 to 27 and Examples 2 to 14 is summarized below.

<Example 28>
Phthalocyanine derivatives [ZnPc- {α- (4-COOCH ₃ ) C ₆ H ₄ O} _x , {β- (4-COOCH ₃ ) C ₆ H ₄ O} _5.7-x H _0.8 Cl _9.5 ] (0 ≦ x <5.7) In a 150 ml flask, Intermediate 6, obtained in Synthesis Example 6, 6.59 g (0.015 mol), phthalonitrile 0.10 g (0.001 mol), BN6 .69 g was added and stirred for about 1 hour using a magnetic stirrer until the internal temperature was stabilized at 160 ° C. under nitrogen flow (10 ml / min), and then 1.39 g (0.004 mol) of zinc iodide was added. And reacted for about 12 hours. After cooling, the completely same operation as Example 1 was performed, and about 5.7g (The intermediate body 6 and the yield of 82.0 mol% with respect to a phthalonitrile) was obtained.

  The phthalocyanine derivative thus obtained was measured for the maximum absorption wavelength, gram extinction coefficient, and heat resistance by exactly the same operation as in Example 1, and the results are summarized in Table 4.

<Example 29>
Phthalocyanine derivatives [ZnPc- {α- (4-COOC ₂ H ₄ OCH ₃ ) C ₆ H ₄ O} _x , {β- (4-COOC ₂ H ₄ OCH ₃ ) C ₆ H ₄ O} _2.28-x Synthesis of H _0.8 Cl _12.92 ] (0 ≦ x <2.28) In a 150 ml flask, intermediate 7,5.43 g (0.015 mol) obtained in Synthesis Example 7 and 0.10 g of phthalonitrile were prepared. (0.001 mol), 5.53 g of BN were added, stirred for about 1 hour under a nitrogen flow (10 ml / min) using a magnetic stirrer until the internal temperature was stabilized at 160 ° C., and then 1.39 g of zinc iodide. (0.004 mol) was added and allowed to react for about 12 hours. After cooling, the completely same operation as Example 1 was performed, and about 5.3g (The yield of 91.6 mol% with respect to the intermediate body 7 and a phthalonitrile) was obtained.

  The phthalocyanine derivative thus obtained was measured for the maximum absorption wavelength, gram extinction coefficient, and heat resistance by exactly the same operation as in Example 1, and the results are summarized in Table 4.

<Example 30>
Phthalocyanine derivatives [ZnPc- {α- (4-COOC ₂ H ₄ OCH ₃ ) C ₆ H ₄ O} _x , {β- (4-COOC ₂ H ₄ OCH ₃ ) C ₆ H ₄ O} _1.14-x Synthesis of H _0.8 Cl _14.06 ] (0 ≦ x <1.14) In a 150 ml flask, 4.78 g (0.015 mol) of intermediate 8 obtained in Synthesis Example 8 and 0.10 g of phthalonitrile. (0.001 mol), 4.81 g of BN were added, stirred for about 1 hour using a magnetic stirrer under nitrogen flow (10 ml / min) until the internal temperature was stabilized at 160 ° C., and then 1.39 g of zinc iodide. (0.004 mol) was added and allowed to react for about 12 hours. After cooling, the completely same operation as Example 1 was performed, and about 3.9 g (yield 77.0 mol% with respect to the intermediate body 8 and a phthalonitrile) was obtained.

  The phthalocyanine derivative thus obtained was measured for the maximum absorption wavelength, gram extinction coefficient, and heat resistance by exactly the same operation as in Example 1, and the results are summarized in Table 4.

<Example 31>
Phthalocyanine derivative [ZnPc- {α- (4-COOC ₂ H ₄ OCH ₃ ) C ₆ H ₄ O} _x , {α- (2-OCH ₃ -4-COOC ₂ H ₄ OCH ₃ ) C ₆ H ₃ O} _{y, {β- (4-COOC} 2 H 4 OCH 3) C 6 H 4 O} 2.72-x, {β- (2-OCH 3 -4-COOC 2 H 4 OCH 3) C 6 H 3 O } _0.68-y H _2.4 Cl _10.2 ] (0 ≦ x <2.72, 0 ≦ y <0.68) Intermediates 9 and 11 obtained in Synthesis Example 9 were added to a 150 ml flask. .22 g (0.026 mol), phthalonitrile 0.59 g (0.005 mol), and BN 3.94 g are added, and the internal temperature is stabilized at 160 ° C. using a magnetic stirrer under nitrogen flow (10 ml / min). After stirring for about 1 hour, 2.69 g of zinc iodide 0.008 mol) was about 12 hours and was charged. After cooling, the completely same operation as Example 1 was performed, and about 12.25g (The intermediate body 9 and the yield of 99.5 mol% with respect to a phthalonitrile) was obtained.

  The phthalocyanine derivative thus obtained was measured for the maximum absorption wavelength, gram extinction coefficient, and heat resistance by exactly the same operation as in Example 1, and the results are summarized in Table 4.

<Example 32>
Phthalocyanine derivatives _{[ZnPc- {α- (2-COOC} 2 H 4 OCH 3) C 10 H 8 -6-O} x, {β- (2-COOC 2 H 4 OCH 3) C 10 H 8 -6-O } Synthesis of _3.8-x H _0.8 Cl _11.4 ] (0 ≦ x <3.8) In a 150 ml flask, Intermediate 10, 5.47 g (0.012 mol) obtained in Synthesis Example 10 was added. , 0.08 g (0.001 mol) of phthalonitrile, and 5.55 g of BN were added, and the mixture was stirred for about 1 hour using a magnetic stirrer under nitrogen flow (10 ml / min) until the internal temperature was stabilized at 160 ° C. Zinc iodide (1.06 g, 0.003 mol) was added and allowed to react for about 12 hours. After cooling, the completely same operation as Example 1 was performed, and about 4.5g (The yield of 78.3 mol% with respect to the intermediate body 10 and a phthalonitrile) was obtained.

  The phthalocyanine derivative thus obtained was measured for the maximum absorption wavelength, gram extinction coefficient, and heat resistance by exactly the same operation as in Example 1, and the results are summarized in Table 4.

<Example 33>
Phthalocyanine derivatives [ZnPc- {α- (4-COOC ₂ H ₄ OCH ₃ ) C ₆ H ₄ O} _x , {α- (4-CN) C ₆ H ₄ O} _0.96 , {β- (4- Synthesis of COOC ₂ H ₄ OCH ₃ ) C ₆ H ₄ O} _3.04-x H _2.88 Cl _9.12 ] (0 ≦ x <3.04) In a 150 ml flask, the intermediate obtained in Synthesis Example 1 Body 1, 6.38 g (0.015 mol), intermediate 11 obtained in Synthesis Example 11, 1.16 g (0.005 mol), and BN 7.55 g were charged under nitrogen flow (10 ml / min). After stirring for about 1 hour using a magnetic stirrer until the internal temperature was stabilized at 160 ° C., 1.73 g (0.005 mol) of zinc iodide was added and allowed to react for about 12 hours. After cooling, the completely same operation as Example 1 was performed, and about 7.85g (The yield of 99.8 mol% with respect to the intermediate body 1 and the intermediate body 11) was obtained.

  The phthalocyanine derivative thus obtained was measured for the maximum absorption wavelength, gram extinction coefficient, and heat resistance by exactly the same operation as in Example 1, and the results are summarized in Table 4.

<Example 34>
Phthalocyanine derivatives [ZnPc- {α- (4-COOC ₂ H ₄ OCH ₃ ) C ₆ H ₄ O} _x , {α- (4-NO ₂ ) C ₆ H ₄ O} _0.68 , {β- (4 Synthesis of —COOC ₂ H ₄ OCH ₃ ) C ₆ H ₄ O} _{3.32- xH 2.04} Cl _9.96 ] (0 ≦ x <3.32) Obtained in Synthesis Example 1 in a 150 ml flask. Intermediate 1, 6.38 g (0.015 mol), Intermediate 12 obtained in Synthesis Example 12, 0.81 g (0.003 mol), and BN 7.20 g were added, and under nitrogen flow (10 ml / min) After stirring for about 1 hour using a magnetic stirrer until the internal temperature was stabilized at 160 ° C., 1.59 g (0.005 mol) of zinc iodide was added and allowed to react for about 12 hours. After cooling, the completely same operation as Example 1 was performed, and about 7.45g (The yield of 99.4 mol% with respect to the intermediate body 1 and the intermediate body 12) was obtained.

  The phthalocyanine derivative thus obtained was measured for the maximum absorption wavelength, gram extinction coefficient, and heat resistance by exactly the same operation as in Example 1, and the results are summarized in Table 4.

<Example 35>
Phthalocyanine derivatives [ZnPc- {α- (4-COOC ₂ H ₄ OCH ₃ ) C ₆ H ₄ O} _x , {α- (2-C ₆ H ₅ ) C ₆ H ₄ O} _y , {β- (4 _{-COOC 2 H 4 OCH 3) C} 6 H 4 O} 3.42-x, {β- (2-C 6 H 5) C 6 H 4 O} 0.38-y H 0.8 Cl 11.4 ] (0 ≦ x <3.42, 0 ≦ y <0.38) In a 150 ml flask, the intermediate 13 obtained in Synthesis Example 13, 6.35 g (0.015 mol), phthalonitrile 0.10 g (0.001 mol), 6.45 g of BN were added, stirred for about 1 hour with a magnetic stirrer until the internal temperature was stabilized at 160 ° C. under nitrogen flow (10 ml / min), and then 1.39 g of zinc iodide. (0.004 mol) was added and allowed to react for about 12 hours. After cooling, the completely same operation as Example 1 was performed, and about 6.45g (The intermediate body 13 and the yield of 96.2 mol% with respect to a phthalonitrile) was obtained.

  The phthalocyanine derivative thus obtained was measured for the maximum absorption wavelength, gram extinction coefficient, and heat resistance by exactly the same operation as in Example 1, and the results are summarized in Table 4.

<Example 36>
Phthalocyanine derivatives [ZnPc- {α- (4-COOC ₂ H ₄ OCH ₃ ) C ₆ H ₄ O} _x , {α- (2-COOCH ₃ ) C ₆ H ₄ S} _y , {β- (4-COOC _{2 H 4 OCH 3) C 6} H 4 O} 3.04-x, {β- (2-COOCH 3) C 6 H 4 S} 0.76-y H 0.8 Cl 11.4] (0 ≦ Synthesis of x <3.04, 0 ≦ y <0.76) In a 150 ml flask, Intermediate 14, obtained in Synthesis Example 14, 6.30 g (0.015 mol), phthalonitrile 0.10 g (0.001) Mol), 6.40 g of BN were added, stirred under a nitrogen flow (10 ml / min) for about 1 hour using a magnetic stirrer until the internal temperature was stabilized at 160 ° C., and then 1.39 g of zinc iodide (0.004 Mol) was added and allowed to react for about 12 hours. After cooling, the completely same operation as Example 1 was performed, and about 6.35g (The intermediate body 14 and the yield of 95.4 mol% with respect to a phthalonitrile) was obtained.

  The phthalocyanine derivative thus obtained was measured for the maximum absorption wavelength, gram extinction coefficient, and heat resistance by exactly the same operation as in Example 1, and the results are summarized in Table 4.

<Example 37>
Phthalocyanine derivatives [ZnPc- {α- (4-COOC ₂ H ₄ OCH ₃ ) C ₆ H ₄ O} _x , {α- (4-OCH ₃ ) C ₆ H ₄ O} _y , {β- (4-COOC _{2 H 4 OCH 3) C 6} H 4 O} 3.42-x, {β- (4-OCH 3) C 6 H 4 O} 0.38-y H 0.8 Cl 11.4] (0 ≦ Synthesis of x <3.42, 0 ≦ y <0.38) In a 150 ml flask, Intermediate 15, obtained in Synthesis Example 15, 6.28 g (0.015 mol), phthalonitrile 0.10 g (0.001) Mol) and 6.38 g of BN were added, stirred under a nitrogen flow (10 ml / min) for about 1 hour using a magnetic stirrer until the internal temperature was stabilized at 160 ° C., and then 1.39 g of zinc iodide (0.004 Mol) was added and allowed to react for about 12 hours. After cooling, the completely same operation as Example 1 was performed, and about 6.1g (The yield of 91.9 mol% with respect to the intermediate body 15 and a phthalonitrile) was obtained.

  The phthalocyanine derivative thus obtained was measured for the maximum absorption wavelength, gram extinction coefficient, and heat resistance by exactly the same operation as in Example 1, and the results are summarized in Table 4.

<Example 38>
Phthalocyanine derivatives [ZnPc- {α- (4-COOC ₂ H ₄ OCH ₃ ) C ₆ H ₄ O} _x , {α- (2-C (CH ₃ ) ₃ ) C ₆ H ₄ O} _y , {β- (4-COOC ₂ H ₄ OCH ₃ ) C ₆ H ₄ O} _3.42-x , {β- (2-C (CH ₃ ) ₃ ) C ₆ H ₄ O} _0.38-y H _0.8 Synthesis of Cl _11.4 ] (0 ≦ x <3.42, 0 ≦ y <0.38) In a 150 ml flask, the intermediate 16 obtained in Synthesis Example 16, 6.32 g (0.015 mol), phthalo Nitrile (0.10 g) (0.001 mol) and BN (6.42 g) were added, stirred for about 1 hour using a magnetic stirrer under nitrogen flow (10 ml / min) until the internal temperature was stabilized at 160 ° C., and then iodinated. 1.39 g (0.004 mol) of zinc was added and allowed to react for about 12 hours. After cooling, the completely same operation as Example 1 was performed, and about 6.65g (The intermediate body 16 and the yield of 99.6 mol% with respect to a phthalonitrile) was obtained.

  The phthalocyanine derivative thus obtained was measured for the maximum absorption wavelength, gram extinction coefficient, and heat resistance by exactly the same operation as in Example 1, and the results are summarized in Table 4.

<Example 39>
Phthalocyanine derivatives [ZnPc- {α- (4-COOC ₂ H ₄ OCH ₃ ) C ₆ H ₄ O} _x , {α- (3-COOC ₂ H ₅ ) C ₆ H ₄ O} _y , {β- (4 _{-COOC 2 H 4 OCH 3) C} 6 H 4 O} 2.66-x, {β- (3-COOC 2 H 5) C 6 H 4 O} 1.14-y H 0.8 Cl 11.4 ] (0 ≦ x <2.66, 0 ≦ y <1.14) In a 150 ml flask, Intermediate 17, 6.25 g (0.015 mol) obtained in Synthesis Example 17 and 0.10 g of phthalonitrile were prepared. (0.001 mol), 6.35 g of BN were added, stirred for about 1 hour using a magnetic stirrer until the internal temperature was stabilized at 160 ° C. under nitrogen flow (10 ml / min), and then 1.39 g of zinc iodide. (0.004 mol) was added and allowed to react for about 12 hours. After cooling, the completely same operation as Example 1 was performed, and about 6.56g (The intermediate body 17 and the yield of 99.3 mol% with respect to a phthalonitrile) was obtained.

  The phthalocyanine derivative thus obtained was measured for the maximum absorption wavelength, gram extinction coefficient, and heat resistance by exactly the same operation as in Example 1, and the results are summarized in Table 4.

<Example 40>
Phthalocyanine derivatives [ZnPc- {α- (4-COOC ₂ H ₄ OCH ₃ ) C ₆ H ₄ O} _x , {α-C ₆ F ₅ O} _y , {β- (4-COOC ₂ H ₄ OCH ₃ ) C ₆ H ₄ O} _2.72-x , {β-C ₆ F ₅ O} _0.68-y H _2.4 Cl _10.2 ] (0 ≦ x <2.72, 0 ≦ y <0. 68) Synthesis: Intermediate 18, 11.00 g (0.026 mol), phthalonitrile 0.59 g (0.005 mol), and BN 3.86 g obtained in Synthesis Example 18 were introduced into a 150 ml flask, and nitrogen flow was performed. Under stirring (10 ml / min), the mixture was stirred for about 1 hour using a magnetic stirrer until the internal temperature was stabilized at 160 ° C., and then 2.69 g (0.008 mol) of zinc iodide was added and allowed to react for about 12 hours. . After cooling, the completely same operation as Example 1 was performed, and about 12.05g (The intermediate body 18 and the yield of 99.7 mol% with respect to a phthalonitrile) was obtained.

  The phthalocyanine derivative thus obtained was measured for the maximum absorption wavelength, gram extinction coefficient, and heat resistance by exactly the same operation as in Example 1, and the results are summarized in Table 4.

<Example 41>
Phthalocyanine derivative [ZnPc- {α- (4-COOC ₂ H ₄ OCH ₃ ) C ₆ H ₄ O} _x , {α- (3,5-Br ₂ -4-COOC ₂ H ₄ OCH ₃ ) C ₆ H _{2 O} y, {β- (4} -COOC 2 H 4 OCH 3) C 6 H 4 O} 2.72-x, {β- (3,5-Br 2 -4-COOC 2 H 4 OCH 3) C Synthesis of ₆ H ₂ O} _0.68-y H _2.4 Cl _10.2 ] (0 ≦ x <2.72, 0 ≦ y <0.68) In a 150 ml flask, the intermediate obtained in Synthesis Example 19 No. 19, 10.97 g (0.024 mol), phthalonitrile 0.54 g (0.004 mol), and BN 3.84 g were added, and the internal temperature was 160 using a magnetic stirrer under nitrogen flow (10 ml / min). After stirring for about 1 hour until stabilized at ℃, zinc iodide 2 48g were (0.008 mol) was about 12 hours and was charged. After cooling, the completely same operation as Example 1 was performed, and about 11.5g (The intermediate body 19 and the yield of 96.0 mol% with respect to a phthalonitrile) was obtained.

  The phthalocyanine derivative thus obtained was measured for the maximum absorption wavelength, gram extinction coefficient, and heat resistance by exactly the same operation as in Example 1, and the results are summarized in Table 4.

<Example 42>
Phthalocyanine derivatives [ZnPc- {α- (4-COOC ₂ H ₄ OCH ₃ ) C ₆ H ₄ O} _x , {α- (4-CF ₃ ) C ₆ H ₄ O} _y , {β- (4-COOC _{2 H 4 OCH 3) C 6} H 4 O} 3.42-x, {β- (4-CF 3) C 6 H 4 O} 0.38-y H 0.8 Cl 11.4] (0 ≦ Synthesis of x <3.42, 0 ≦ y <0.38) In a 150 ml flask, Intermediate 20, obtained in Synthesis Example 20, 6.33 g (0.015 mol), phthalonitrile 0.10 g (0.001) Mol) and 6.43 g of BN were added and stirred for about 1 hour using a magnetic stirrer until the internal temperature was stabilized at 160 ° C. under a nitrogen flow (10 ml / min), and then 1.39 g of zinc iodide (0.004 Mol) was added and allowed to react for about 12 hours. After cooling, the completely same operation as Example 1 was performed, and about 6.57g (The intermediate body 20 and the yield of 98.2 mol% with respect to a phthalonitrile) was obtained.

  The phthalocyanine derivative thus obtained was measured for the maximum absorption wavelength, gram extinction coefficient, and heat resistance by exactly the same operation as in Example 1, and the results are summarized in Table 4.

<Example 43>
Phthalocyanine derivatives [ZnPc- {α- (4-COOC ₂ H ₄ OCH ₃ ) C ₆ H ₄ O} _x , {α-C ₆ H ₅ O} _y , {β- (4-COOC ₂ H ₄ OCH ₃ ) _{C 6 H 4 O} 1.9-} x {β-C 6 H 5 O} 0.76-y H 0.8 Br 1.22 Cl 11.32] (0 ≦ x <1.9,0 ≦ y <0.76) Synthesis Into a 150 ml flask was charged Intermediate 21, 5.58 g (0.015 mol) obtained in Synthesis Example 21, 0.10 g (0.001 mol) phthalonitrile, and 5.68 g BN. The mixture was stirred for about 1 hour under a nitrogen flow (10 ml / min) using a magnetic stirrer until the internal temperature was stabilized at 160 ° C. Then, 1.32 g (0.004 mol) of zinc iodide was added for about 12 hours. Reacted. After cooling, the completely same operation as Example 1 was performed, and about 5.52g (The intermediate body 21 and the yield of 97.2 mol% with respect to a phthalonitrile) was obtained.

  The phthalocyanine derivative thus obtained was measured for the maximum absorption wavelength, gram extinction coefficient, and heat resistance by exactly the same operation as in Example 1, and the results are summarized in Table 4.

<Example 44>
In Example 15, the same procedure as in Example 15 was followed, except that the phthalocyanine derivative obtained in Example 2 was replaced with the phthalocyanine derivative obtained in Example 28. The results are summarized in Table 4.

<Example 45>
In Example 15, the same procedure as in Example 15 was followed except that the phthalocyanine derivative obtained in Example 2 was replaced with the phthalocyanine derivative obtained in Example 30, and the maximum absorption wavelength, gram extinction coefficient and heat resistance were The results are summarized in Table 4.

<Example 46>
In Example 15, the same procedure as in Example 15 was followed, except that the phthalocyanine derivative obtained in Example 2 was replaced with the phthalocyanine derivative obtained in Example 31, and the maximum absorption wavelength, gram extinction coefficient and heat resistance were The results are summarized in Table 4.

<Example 47>
In Example 15, the same procedure as in Example 15 was followed, except that the phthalocyanine derivative obtained in Example 2 was replaced with the phthalocyanine derivative obtained in Example 32. The results are summarized in Table 4.

<Example 48>
In Example 15, the same procedure as in Example 15 was followed except that the phthalocyanine derivative obtained in Example 2 was replaced with the phthalocyanine derivative obtained in Example 33. The results are summarized in Table 4.

<Example 49>
In Example 15, the same procedure as in Example 15 was followed except that the phthalocyanine derivative obtained in Example 2 was replaced with the phthalocyanine derivative obtained in Example 35. The results are summarized in Table 4.

<Example 50>
In Example 15, the same procedure as in Example 15 was followed except that the phthalocyanine derivative obtained in Example 2 was replaced with the phthalocyanine derivative obtained in Example 36. The results are summarized in Table 4.

<Example 51>
In Example 15, the same procedure as in Example 15 was followed, except that the phthalocyanine derivative obtained in Example 2 was replaced with the phthalocyanine derivative obtained in Example 38. The results are summarized in Table 4.

<Example 52>
In Example 15, the same procedure as in Example 15 was followed, except that the phthalocyanine derivative obtained in Example 2 was replaced with the phthalocyanine derivative obtained in Example 41. The results are summarized in Table 4.

<Example 53>
In Example 15, the same procedure as in Example 15 was followed except that the phthalocyanine derivative obtained in Example 2 was replaced with the phthalocyanine derivative obtained in Example 42. The results are summarized in Table 4.

<Comparative Example 1>
Synthesis of phthalocyanine compound [ZnPc- {β- (2-COOCH ₃ ) C ₆ H ₄ O} ₄ H ₁₂ ] In a 150 ml flask, Intermediate 22, 4.17 g (0.015 mol) obtained in Synthesis Example 22 was added. , 1.32 g (0.004 mol) of zinc iodide and 30.94 g of benzonitrile were added, and the reaction was carried out for about 5 hours while stirring with a magnetic stirrer under an internal temperature of 185 ° C. under nitrogen flow (10 ml / min). I let you. After cooling, the completely same operation as Example 1 was performed, and about 3.8 g (yield of 84.9 mol% with respect to the intermediate body 6) was obtained.

  The phthalocyanine derivative thus obtained was measured for the maximum absorption wavelength, gram extinction coefficient, and heat resistance by exactly the same operation as in Example 1, and the results are summarized in Table 4.

<Comparative example 2>
The phthalocyanine compound {ZnPc (3-COOCH ₃ PhO) ₆ (3-COOHPhO) ₂ F ₈ } described in Example 18 of JP-A-2008-50599 is treated in exactly the same manner as in Example 1, The gram extinction coefficient, absorbance ratio and heat resistance were measured and the results are summarized in Table 4.

  The phthalocyanine derivatives synthesized in Examples 1 to 14 and 28 to 43 have a gram extinction coefficient (εg) as compared with the β-position 4-substituted phthalocyanine derivative synthesized in Comparative Example 1 and the β-position 8-substituted phthalocyanine derivative synthesized in Comparative Example 2. Although no superiority was observed, the heat resistance was improved more than twice as compared with the β-substituted 4-substituted phthalocyanine derivative having high heat resistance synthesized in Comparative Example 1. Moreover, compared with the comparative examples 1 and 2, the phthalocyanine derivatives of Examples 1 to 14 and 28 to 43 showed remarkably superior solvent solubility.

  In addition, in the ratio of absorbance at 710 nm where extra light emission of PDP is observed and 520 nm, which is a typical visible light wavelength, when the phthalocyanine derivative of the present application is used, the absorbance ratio is 2 compared to Comparative Examples 1 and 2. The effect of being able to efficiently cut light of 710 nm was more than twice as large.

  Furthermore, the heat resistance in Examples 15 to 27 and 44 to 53 is improved by 2 times or more compared to Comparative Example 1, and the ratio of absorbance at 710 nm and 520 nm is improved by 2 times or more compared to Comparative Examples 1 and 2. did. For this reason, even in the case of a thin film having a dry film thickness of 0.1 μm, it has been shown that the phthalocyanine derivative of the present application exhibits excellent heat resistance and can efficiently cut light of 710 nm.

  In addition, this application is based on the Japan patent application 2010-043405 for which it applied on February 26, 2010, The content of an indication is referred as a whole by reference.

Claims (3)

Following formula (1):

In the above formula (1),
M represents zinc or copper ;
Z ^{1 to} Z ⁴ are each independently the following formulas (2) to (5):

And
In the above formulas (2) to (5),
p is an integer of 0 to 4,
q is an integer of 0 to 3,
r is an integer from 0 to 2,
s is an integer from 0 to 6,
R ¹ to R ⁴ are each independently, a nitro group, an amino group, a hydroxyl group, an alkyl group having a carbon number of 1-8, an alkyl group substituted by a halogen atom having 1 to 8 carbon atoms, substituent (a), substituents (b) and -S-L-a or a substituent selected from Ranaru group (a) or a halogen atom,
L is an alkylene group of carbon number 1 to 3, A is a C OO J, this time, J is an alkyl group having 1 to 8 carbon atoms which have a alkoxy group having 1 to 8 carbon atoms ,
The substituent (a) is represented by the following formula (6), (6 ′) or (6 ″):

In the above formulas (6), (6 ′) and (6 ″), R ⁵ is an alkoxy group having 1 to 8 carbon atoms or a halogen atom, and R ⁶ is an alkylene group having 1 to 3 carbon atoms. , R ⁷ is an alkyl group having 1 to 8 carbon atoms, t is an integer of 0 to 4, u is an integer of 0 to 4, and t ′ is an integer of 0 to 6. And
The substituent (b) is represented by the following formula (7):

In the above formula (7), X is an oxygen atom or a sulfur atom, Ar is a phenyl group or a naphthyl group substituted with R ^8, this time, R ⁸ are each independently a hydrogen atom, a cyano group, a nitro group, COOY, OY, a halogen atom, an aryl group, an alkyl group or an alkyl group having 1 to 8 carbon atoms having 1 to 8 carbon atoms substituted with a halogen atom, this time, Y is C 1 -C 8 alkyl group, in represented,
At this time, among all the groups introduced as R ^{1 to} R ⁴ , 0.05 or more and less than 3 are hydrogen atoms, 1 to 6 are substituents (a), and the balance Is a halogen atom, and 1 to 6 of the substituents (a) are the substituents (a).
A phthalocyanine derivative represented by: Wherein the substituents (A), is 1-4, wherein a substituent (a), a phthalocyanine derivative of claim 1. A flat panel display filter comprising the phthalocyanine derivative according to claim 1 .