JP2011197670A - Color filter composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a new color filter composition improved in heat resistance, light resistance and contrast.SOLUTION: The color filter composition contains a phthalocyanine derivative and a yellow dye, wherein the phthalocyanine derivative is expressed by formula (1). In formula (1), M represents a nonmetal, metal, metal oxide or metal halide; and Zto Zeach independently represent formulae (2) to (5). In formulae (2) to (5), p represents an integer of 0 to 4; q represents an integer of 0 to 3; r represents an integer of 0 to 2; s represents an integer of 0 to 6; and Rto Reach independently represent, for example, an alkyl group having 1 to 8 carbon atoms which may be substituted with a nitro group, amino group, hydroxyl group or halogen atom.

Description

  The present invention relates to a color filter composition containing a phthalocyanine derivative and a yellow dye.

  Color filters used in liquid crystal displays, imaging devices, etc. are generally formed by forming red, green, and blue primary color pixels and a black matrix that is a light shielding layer provided between these pixels on a transparent substrate such as glass. It is manufactured. For these pixels and black matrix, a photosensitive coloring composition is applied onto a substrate, heated and dried (prebaked) to form a coating film, and the coating film is exposed to ultraviolet rays, exposed to light, further developed and unexposed. The portion is formed by removing the portion by alkali washing, further post-curing (post-baking), and removing the unexposed portion by washing with alkali.

  Currently, liquid crystal display devices using the color filters are being developed for desktop monitor applications in addition to conventional notebook PC applications. In addition, a large-sized LCD TV that has further improved the color reproducibility of desktop monitors has been developed recently, and a pigment dispersion using a specific pigment as a colorant is used to display vivid colors such as printed matter. Thus, a combination for improving the color reproducibility of the color filter has been proposed (for example, Patent Document 1).

  However, the color filter based on the pigment dispersion method has a problem of causing a decrease in contrast due to disturbance of polarization of light caused by scattering of light by the pigment surface, and the problem becomes particularly noticeable as the liquid crystal screen becomes larger. Yes. In the pigment dispersion method, attempts have been made to improve the contrast by suppressing light scattering by further miniaturizing the pigment to be used. However, the pigment dispersion method has reached its limit. In recent years, the use of a solid-state image sensor has been demanded to further increase the definition of the color filter, and the pigment dispersion method is not suitable for applications requiring a fine pattern such as a solid-state image sensor.

  On the other hand, it is known that a yellow dye is used for the green part of the color filter, and it is also known to use a phthalocyanine dye and an azo dye in combination in order to realize such a green color. In some cases, the problem is low contrast, heat resistance and light resistance are insufficient, and further improvements are desired. Further, conventional phthalocyanine dyes have a problem of low contrast even when used alone, and there are cases where heat resistance and light resistance are low, and improvement thereof is desired.

JP 2004-176000 A

  Accordingly, an object of the present invention is to provide a color filter composition containing a novel phthalocyanine derivative and a yellow dye, which have improved heat resistance, light resistance and contrast.

  As a result of intensive studies to solve the above problems, the present inventors have found that a color filter composition containing a phthalocyanine derivative having a specific structure and a yellow dye has heat resistance, light resistance and contrast. The inventors have found that the present invention has been improved and have completed the present invention.

That is, the object is a color filter composition comprising a phthalocyanine derivative and a yellow pigment,
The phthalocyanine derivative has 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 a halogen atom:
It is achieved by a color filter composition represented by

  ADVANTAGE OF THE INVENTION According to this invention, the color filter composition containing the novel phthalocyanine derivative with improved heat resistance, light resistance, and contrast and a yellowish pigment | dye can be provided.

The present invention is a color filter composition comprising a phthalocyanine derivative and a yellow pigment,
The phthalocyanine derivative has 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 a halogen atom:
It is a color filter composition shown by these.

  In this application, a color filter composition containing a phthalocyanine derivative and a yellow dye is provided, but it is characteristic whether it is a phthalocyanine derivative alone or a yellow dye alone. In particular, the phthalocyanine derivative alone is characteristic. Therefore, in this application, it must be considered that the invention of a single phthalocyanine derivative and the invention of a yellow pigment simple substance are also provided.

  First, the phthalocyanine derivative alone will be described.

  The phthalocyanine derivative of the present invention has 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 a halogen atom.

  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) 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 (n) is not particularly limited, and can be appropriately selected depending on desired effects (gram absorption coefficient, solvent solubility, heat resistance, light absorption at 710 nm, 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 1-5, and preferably 1 to 3, more preferably 1 or 2 The number is particularly preferably one. 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.

  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):

XH-Ar (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”.

  Subsequently, the yellow dye of the present invention will be described. As the yellow dye, an azo yellow dye is preferable. At this time, the number of azo groups (—N═N—) is not particularly limited, but is preferably 1 to 4, more preferably 1 to 3, further preferably 1 to 2, and the structure of a yellow dye. It is preferably present in. The yellow pigment may be in the form of a salt.

  Although there is no restriction | limiting in particular also in the specific example of this salt, A sulfonate, carboxylate, etc. are mentioned. The cations forming these salts are not particularly limited, but considering solubility in solvents, alkali metal salts such as lithium salts, sodium salts and potassium salts; ammonium salts; and ethanolamine salts and alkylamine salts. Organic amine salts and the like are preferred. In particular, alkylamine salts are particularly preferred from the viewpoints of solvent solubility and solubility in resins. Moreover, there is no restriction | limiting in particular also in carbon number of the alkyl in this case, Preferably it is 1-24, More preferably, it is 2-20. In addition, the alkyl may be linear or branched. Preferably, it is linear from the viewpoint of solvent solubility. Such alkyl groups include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, tert-butyl, pentyl, isopentyl, trioctyl, tributyl, tert- Pentyl group, neopentyl group, hexyl group, isohexyl group, heptyl group, octyl group, nonyl group, decyl group, undecyl group, dodecyl group, 2-ethylhexyl group, tridecyl group, tetradecyl group, pentadecyl group, hexadecyl group, heptadecyl group, Examples thereof include linear, branched or cyclic alkyl groups such as octadecyl group, nonadecyl group, eicosyl group, heneicosyl group, docosyl group and the like. In particular, a trioctyl group and a tributyl group are preferable. Therefore, trioctylamine salt, tributylamine salt and the like are preferable.

  In addition, when the yellow pigment is an azo dye or a salt thereof represented by the following formula (A) or (I), the viewpoint that the rise of the spectrum near 450 to 500 nm is sharp and the purity of the color as yellow is high. Is preferable.

In the above formula,
Q is a substituted or unsubstituted alkyl group having 1 to 5 carbon atoms, a substituted or unsubstituted alkoxy group having 1 to 5 carbon atoms, a halogen atom, a nitro group, a sulfo group, a sulfamoyl group, an N-substituted sulfamoyl group, an alkoxy group. An aryl group having at least one group selected from the group consisting of a carbonyl group and an N-substituted carbamoyl group, or a substituted or unsubstituted heteroaryl group,
D ¹ is a hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 12 carbon atoms, a substituted or unsubstituted aralkyl group having 7 to 20 carbon atoms, — (R ₅ O) _r R ₆ , —COR ₇ , or A substituted or unsubstituted aryl group having 6 to 20 carbon atoms, wherein R ₅ is an alkylene group having 1 to 3 carbon atoms, and R ₆ is a hydrogen atom or an alkyl group having 1 to 8 carbon atoms. , R is an integer of 0-4, R ₇ is a substituted or unsubstituted alkyl group of 1-8,
D ² is a substituted or unsubstituted alkyl group having 1 to 5 carbon atoms, a substituted or unsubstituted amino group,
D ³ is a hydrogen atom, a -CN or -CONH _2,
D ⁴ and D ⁵ are each independently a substituted or unsubstituted amino group.

  First, formula (A):

An azo dye or a salt thereof represented by

  Q is a substituted or unsubstituted alkyl group having 1 to 5 carbon atoms, a substituted or unsubstituted alkoxy group having 1 to 5 carbon atoms, a halogen atom, a nitro group, a sulfo group, a sulfamoyl group, an N-substituted sulfamoyl group, an alkoxy group. An aryl group having at least one group selected from the group consisting of a carbonyl group and an N-substituted carbamoyl group (hereinafter also referred to as “one group”), or a substituted or unsubstituted heteroaryl group . Of the “one group”, preferably, it has at least one sulfo group from the viewpoint of high solubility in a resist adjusting solution, and from the viewpoint of high heat resistance, a halogen atom. It is also preferable to have. From the viewpoints of heat resistance and solubility, it is also preferred that an N-substituted sulfamoyl group is present. Or it is also preferable to have an N-substituted carbamoyl group from the viewpoint of heat resistance and solubility.

In the present specification, an aryl group is a residue obtained by removing one hydrogen atom from an aromatic hydrocarbon ring, and includes a phenyl group (—C ₆ H ₅ ) and the like. In the present specification, the aryl group is a concept including a condensed polycyclic aromatic hydrocarbon group. Moreover, the aromatic hydrocarbon may be couple | bonded with the other connector. Thus, specifically, phenyl, biphenyl, terphenyl, naphthyl, anthracyl, tetracenyl, pentacenyl, perylenyl, and the like are included. Among them, a phenyl group, a naphthyl group and the like are preferable. Moreover, heteroaryl means what contains the nitrogen atom, the oxygen atom, and the sulfur atom in the ring of aromatic hydrocarbon. Examples thereof include pyridine, pyrazine, pyrimidine, pyridazine, pyrazole, benzopyrazine, triazabenzene, benzothiazole and the like. Further, “having one kind of group” means that at least one hydrogen atom of the aryl group is substituted with such “one kind of group”. At this time, there are no particular restrictions on the position to be replaced and the number to be replaced. If the aryl group is a phenyl group, an integer of 1 to 2 is preferred. In addition, as long as there is one position, the position may be 2nd, 3rd or 4th, and 4th is preferable from the viewpoint of high heat resistance. Any combination may be used as long as it is two, but the third, fourth, second, fourth, second and fifth positions are preferred, and the third and fourth positions are particularly preferred from the viewpoint of high heat resistance. Although the number of substituents of the naphthyl group is not particularly limited, an integer of 1 to 2 is preferable. In addition, as long as there is one position, any of positions 2 to 8 may be used. Any combination of two may be used.

  Examples of the alkyl group having 1 to 5 carbon atoms include methyl group, ethyl group, n-propyl group, iso-propyl group, n-butyl group, iso-butyl group, sec-butyl group, t-butyl group, and n-pentyl. Group and the like. Examples of the substituent of the substituted or unsubstituted alkyl group having 1 to 5 carbon atoms include a substituted or unsubstituted alkyl group having 1 to 5 carbon atoms and a substituted or unsubstituted alkoxy group having 1 to 5 carbon atoms. Can be mentioned. This example is the same as that described later, and specifically includes a methoxy group and the like.

  Examples of the substituted or unsubstituted alkoxy group having 1 to 5 carbon atoms include methoxy group, ethoxy group, n-propoxy group, iso-propoxy group, n-butoxy group, iso-butoxy group, sec-butoxy group, t-butoxy group. Group, n-pentoxy group, pentoxy group and the like.

  Moreover, as a halogen atom, a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom are mentioned. Among these, a fluorine atom, a chlorine atom, and a bromine atom are preferable.

The nitro group is a group represented by —NO ₂ .

The sulfo group is a group represented by —SO ₃ H. Here, the sulfo group may be in the form of a salt, and examples of the salt include alkali metal salts such as sodium salt and potassium salt.

The sulfamoyl group is a group represented by —SO ₂ NH ₂ .

Further, N- substituted sulfamoyl _group, -SO 2 _{N (R 8)} a group represented by the ₂ groups. At this time, the case where R ₈ is a hydrogen atom at the same time is excluded. Here, each R ₈ is independently a hydrogen atom, — (R ₅ O) _r R ₆ , an alkyl group having 1 to 12 carbon atoms (the hydrogen atom of the alkyl group is an alkoxy group, a hydroxy group, a dimethylamino group). The methylene group contained in the alkyl group having 1 to 12 carbon atoms may be —O-substituted), an aryl group having 6 to 20 carbon atoms, or 7 to 20 carbon atoms. Are preferably an aralkyl group or an acyl group having 2 to 10 carbon atoms.

In the description of “— (R ₅ O) _r R ₆ ”, the above is similarly valid. In this case, R ₈ is independently preferably a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, or — (R ₅ O) _r R ₆ . Preferred combinations of R ₈ is a hydrogen atom, a combination of an alkyl group having 1 to 12 carbon atoms _{;-( R 5 O) r R 6} , - ( is a combination of _{R 5 O)} r R _6. In this case, R ₅ is preferably an ethylene group or a propylene group, r is preferably 1 or 2, and R ₆ is preferably a methyl group, an ethyl group or a propyl group.

The alkyl group having 1 to 12 carbon atoms of R ₈ may be linear, branched or cyclic. More preferably, it is a C1-C10 alkyl group.

The alkyl group of R ₈ is, for example, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert-butyl group, methylbutyl group, 1,1,3, 3-tetramethylbutyl group, methylhexyl group (1-methylhexyl group, 1,5-dimethylhexyl group etc.), ethylhexyl group (2-ethylhexyl group etc.), cyclopentyl group, cyclohexyl group, methylcyclohexyl group (2-methyl) Cyclohexyl group, etc.), heptyl group, octyl group, nonyl group, decanyl group, dodecanyl group and the like. Examples of the substituted alkyl group having 1 to 12 carbon atoms include a methoxyethyl group, a 2-methoxy-1-methyl group, an ethylalkoxypropyl group (such as 3- (2-ethylhexyloxy) propyl group), and a tetrahydrofuranylalkyl group (2 -Tetrahydrofuranylmethyl group etc.), glycidyl group, hydroxypropyl group (2-hydroxypropyl group, 3-hydroxypropyl group etc.), etc. can be illustrated.

The aryl group of R ₈ may be unsubstituted or substituted with an alkyl group, a hydroxyl group, a sulfo group (including an alkali metal salt form such as a sodium salt), and the like.
The aryl group preferably has 6 to 20 carbon atoms, more preferably 6 to 10 carbon atoms.
Specific examples include a substituted or unsubstituted phenyl group such as a phenyl group, a hydroxyphenyl group (such as 4-hydroxyphenyl group), and a trifluoromethylphenyl group (such as 4-trifluoromethylphenyl group).

The alkyl of the aralkyl group represented by R ₈ may be linear, branched or cyclic. The carbon number of the aralkyl group is preferably 7-20, more preferably 7-10. Examples of the aralkyl include phenylalkyl groups such as a benzyl group, a phenylpropyl group (such as 1-methyl-3-phenylpropyl group), and a phenylbutyl group (such as 3-amino-1-phenylbutyl group).

The acyl group of R ₈ may be unsubstituted, or an aliphatic hydrocarbon group, an alkoxyl group, or the like may be substituted. The acyl group preferably has 2 to 10 carbon atoms, more preferably 6 to 10 carbon atoms. Examples of the acyl group include an acetyl group, a benzoyl group, and a methoxybenzoyl group (such as a p-methoxybenzoyl group).

R ₈ is, for example, each independently a hydrogen atom, — (R ₅ O) _r R ₆ (wherein R ₅ is preferably an ethylene group or a propylene group, and r is 1 or 2). R ₆ is preferably a methyl group, an ethyl group or a propyl group), a methylbutyl group (such as 1,1,3,3-tetramethylbutyl group), a methylhexyl group (1,5 -Dimethylhexyl group, etc.), ethylhexyl group (2-ethylhexyl group, etc.), methylcyclohexyl group (2-methylcyclohexyl group, etc.), phenylpropyl group (1-methyl-3-phenylpropyl group, etc.), phenyl Branched carbon such as butyl group (such as 3-amino-1-phenylbutyl group) and alkoxypropyl group (such as 3- (2-ethylhexyloxy) propyl group) It is preferably an alkyl group, or an aralkyl group having.

Alkoxycarbonyl group, a group represented by _{-COOR 10.} R ₁₀ is preferably a substituted or unsubstituted alkyl group having 1 to 8 carbon atoms. In this case, the substituent is preferably an alkoxy group having 1 to 8 carbon atoms, and specific examples thereof are as described above. Those are equally valid, for example, a methoxyethyl group is preferred. R ₁₀ may be represented by — (R ₅ O) _r R ₆ , and the above description is equally applicable to these descriptions. In this case, R ₅ is preferably a methylene group or an ethylene group, r is preferably 1 or 2, and R ₆ is preferably a methyl group, an ethyl group or a propyl group. When this alkoxycarbonyl group is introduced into an aryl group, two or more may be introduced from the viewpoint that the brightness is improved when combined with a green pigment by shortening the wavelength, and the solubility in the adjustment liquid is also improved. preferable.

The N-substituted carbamoyl group is a group represented by CON (R ₉ ) ₂ . Here, R ₉ is the same as R ₈ . At this time, from the viewpoints of heat resistance and solubility in the adjustment liquid, preferably, each is an optionally substituted alkyl group having 1 to 12 carbon atoms, more preferably an alkyl group having 1 to 10 carbon atoms. It is.

  As described above, the substituted or unsubstituted heteroaryl group means that the heteroaryl contains a nitrogen atom, an oxygen atom, or a sulfur atom in the ring of the aromatic hydrocarbon. Examples thereof include pyridine, pyridine, pyrazine, pyrimidine, pyridazine, pyrazole, benzopyrazine, triazabenzene, benzothiazole and the like. Examples of the substituent include a cyano group, a sulfamoyl group, an N-substituted sulfamoyl group, a substituted alkyl group having 1 to 12 carbon atoms, and a hydroxyl group. These descriptions are equally valid for what has been described above.

D ¹ is a hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 12 carbon atoms, a substituted or unsubstituted aralkyl group having 7 to 20 carbon atoms, — (R ₅ O) _r R ₆ , —COR ₇ , or A substituted or unsubstituted aryl group having 6 to 20 carbon atoms, wherein R ₅ is an alkylene group having 1 to 3 carbon atoms, and R ₆ is a hydrogen atom or an alkyl group having 1 to 8 carbon atoms. , R is an integer of 0 to 4, and R ₇ is a substituted or unsubstituted alkyl group of 1 to 8.

  The substituted or unsubstituted alkyl group having 1 to 12 carbon atoms may be linear, branched or cyclic. As carbon number of an alkyl group, it is 1-12, Preferably it is 1-11. Examples of the alkyl group having 1 to 12 carbon atoms include methyl group, ethyl group, propyl group, ison-propyl group, n-butyl group, isobutyl group, sec-butyl group, tert-butyl group, pentyl group, isopentyl group, A trioctyl group, tributyl group, tert-pentyl group, neopentyl group, hexyl group, isohexyl group, heptyl group, octyl group, nonyl group, decyl group, undecyl group, dodecyl group and the like are preferable. Of these, an ethyl group, an n-propyl group, and an n-butyl group are preferable.

  Moreover, there is no restriction | limiting in particular as a substituent. For example, an alkyl group having 1 to 8 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, a hydroxyl group, and a sulfo group are preferable. Examples of the alkyl group having 1 to 8 carbon atoms include methyl group, ethyl group, n-propyl group, iso-propyl group, n-butyl group, iso-butyl group, sec-butyl group, t-butyl group, n -Pentyl group, n-hexyl group, cyclohexyl group, n-heptyl group, n-octyl group and the like can be mentioned. Examples of the alkoxy group having 1 to 8 carbon atoms include methoxy group, ethoxy group, n-propoxy group, iso-propoxy group, n-butoxy group, iso-butoxy group, sec-butoxy group, t-butoxy group and n-pentoxy group. Group, pentoxy group, n-hexoxy group, cyclohexoxy group, n-pentoxy group, n-octoxy group and the like.

  Accordingly, examples of the substituted or unsubstituted alkyl group having 1 to 12 carbon atoms include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group, and a tert-butyl group. Group, methylbutyl group (such as 1,1,3,3-tetramethylbutyl group), methylhexyl group (such as 1-methylhexyl group and 1,5-dimethylhexyl group), ethylhexyl group (such as 2-ethylhexyl group), It may be substituted with a methylpentyl group, a cyclopentyl group, a cyclohexyl group, a methylcyclohexyl group (such as a 2-methylcyclohexyl group), or a cyclohexylalkyl group. Examples of the alkyl group include an alkoxypropyl group (such as 3- (2-ethylhexyloxy) propyl group), ethylthioethyl group, methylpropyl group, 2-sulfoethyl group, ethylmethyl group, cyclohexyl group, iso-propoxypropyl, butylpentyl. Group, tetrahydrofuranylalkyl group (such as 2-tetrahydrofuranylmethyl group), glycidyl group, hydroxyethyl group, hydroxypropyl group (such as 2-hydroxypropyl group, 3-hydroxypropyl group) and the like.

  Further, the substituted or unsubstituted aralkyl group having 7 to 20 carbon atoms may be linear, branched or cyclic. The aralkyl group has 7 to 20 carbon atoms, preferably 7 to 10 carbon atoms. Examples of the aralkyl include phenylalkyl groups such as a benzyl group, a phenylpropyl group (such as 1-methyl-3-phenylpropyl group), and a phenylbutyl group (such as 3-amino-1-phenylbutyl group).

_Further, - in _{(R 5 O) r R 6} , examples of _{R 5,} an alkylene group having 1 to 3 carbon atoms, _{R 6} is a hydrogen atom or an alkyl group having 1 to 8 carbon atoms. Examples of the alkylene group having 1 to 3 carbon atoms include a methylene group, an ethylene group, an n-propylene group, and an iso-propylene group. Preferably, they are an ethylene group and a propylene group. Examples of the alkyl group having 1 to 8 carbon atoms include methyl group, ethyl group, n-propyl group, iso-propyl group, n-butyl group, iso-butyl group, sec-butyl group, t-butyl group, n -Pentyl group, n-hexyl group, cyclohexyl group, n-heptyl group, n-octyl group and the like can be mentioned. Moreover, r is an integer of 0-4, Preferably it is an integer of 1-3. R ₆ is a hydrogen atom or an alkyl group having 1 to 8 carbon atoms. Examples of the alkyl group having 1 to 8 carbon atoms include methyl group, ethyl group, n-propyl group, iso-propyl group, n-butyl group, iso-butyl group, sec-butyl group, t-butyl group, and n-pentyl. Group, cyclopentyl group, n-hexyl group, cyclohexyl group, n-heptyl group, n-octyl group and the like. Of these, a hydrogen atom and a methyl group are preferred from the viewpoint of high solvent solubility. R is an integer of 0 to 4, preferably 1 to 3, and more preferably 1 to 2.

In -COR _{7, R 7} is a substituted or unsubstituted 1-8 alkyl group, a methyl group, an ethyl group, n- propyl group, iso- propyl, n- butyl, iso- butyl group, sec -Butyl group, t-butyl group, n-pentyl group, n-hexyl group, cyclohexyl group, n-heptyl group, n-octyl group and the like can be mentioned, and a methyl group is preferable. In addition, there is no restriction | limiting in particular as a substituent as a substituent. For example, an alkyl group having 1 to 8 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, and the like are preferable, and specific examples thereof are also appropriate as described above, and specifically, a methoxy group and the like are preferable.

  Examples of the substituted or unsubstituted aryl group having 6 to 20 carbon atoms include phenyl group, hydroxyphenyl group (such as 4-hydroxyphenyl group), trifluoromethylphenyl group (such as 4-trifluoromethylphenyl group), and the like. .

Of D ¹ , a methyl group, an ethyl group, a propyl group, an n-butyl group, and the like are particularly preferable.

D ² is a substituted or unsubstituted alkyl group having 1 to 5 carbon atoms, a substituted or unsubstituted amino group.

  Examples of the alkyl group having 1 to 5 carbon atoms include methyl group, ethyl group, n-propyl group, iso-propyl group, n-butyl group, iso-butyl group, sec-butyl group, t-butyl group, and n-pentyl. Group and the like. Of these, a methyl group, an ethyl group, and the like are preferable. In particular, a methyl group is preferable from the viewpoint of high color density as yellowish pigment. Moreover, as a substituent in this case, a C1-C5 alkyl group, a C1-C5 alkoxy group, etc. are mentioned.

The unsubstituted amino group of the substituted or unsubstituted amino group is represented by —NH ₂ . The substituted amino group is represented by —N (R ₁₁ ) ₂ . Examples of R ₁₁ are each independently a substituted or unsubstituted alkyl group having 1 to 5 carbon atoms, and the explanation given above is similarly valid, and for example, a methoxymethyl group is preferred.

D ³ is a hydrogen atom, —CN or —CONH ₂ . Among these, -CN is preferable from the viewpoint of high solvent solubility.

  Subsequently, the formula (I):

An azo dye or a salt thereof represented by

As for Q, the contents described above are similarly valid. D ² is a substituted or unsubstituted alkyl group having 1 to 5 carbon atoms, a substituted or unsubstituted amino group.

D ⁴ and D ⁵ are each independently a substituted or unsubstituted amino group. Specifically, D ⁴ and D ⁵ are preferably those listed in the table shown below.

  In addition, each of the azo dyes (a) or salts thereof and the azo dyes (a) or salts thereof may be bonded to each other at any position to form a dimer.

Among the above, preferred specific yellow dyes of the present invention are listed below.
Needless to say, the present invention is not limited to these.

  Further, the yellow pigment that can be used in the present invention is not limited to the above, for example,

It may be.

  Among the above, the dye 46 and the dye 47 are particularly preferable from the viewpoint of high heat resistance. The dye 46 is preferably a trioctylamine salt from the viewpoint of high solvent solubility, and the dye 47 is trioctylamine salt or tributylamine salt from the viewpoint of high solvent solubility. Preferably there is. The dye 62 is also preferable from the viewpoint of high heat resistance. The dye 63 and the dye 64 are also preferable from the viewpoint of high solubility in a solvent. The dye 65 is also preferable from the viewpoint of high heat resistance. The dye 66 is also preferable from the viewpoint of high solubility in the adjustment liquid.

  The yellow colorant of the present invention can be produced by using a diazonium salt coupling method, as is well known in the dye field. Moreover, you may prepare by purchasing a commercial item.

The diazonium salt can be obtained, for example, by diazotizing the amine containing Q (that is, “Q-NH ₂ ”) with nitrous acid, nitrite or nitrite.

The anion of the diazonium salt may be inorganic or organic, for example, fluoride ion, chloride ion, bromide ion, iodide ion, perchlorate ion, hypochlorite ion, CH ₃ —COO ⁻ , Ph -COO- ^{and the} like.

  Therefore, the yellow dye of the present invention comprises such a diazonium salt and the following (A ') or (I'):

It can manufacture by making the at least 1 compound shown by react. Here, D ^{1 to} D ⁵ are the same as those described in (a) to (b).
The reaction conditions in this case can be set by referring to or appropriately combining known knowledge.

  The color filter composition of the present invention contains the phthalocyanine compound described above and a yellow dye.

  In the color filter composition of the present invention, the blending amount of the phthalocyanine compound of the present invention and the yellow dye is not particularly limited, but when the phthalocyanine compound of the present invention is 100 parts by mass, the yellow dye is preferable. Is 0 to 300 parts by mass, more preferably 10 to 100 parts by mass, and still more preferably 15 to 80 parts by mass.

  The above yellow azo dyes may be used alone with phthalocyanine dyes, or a mixture of two or three kinds may be used. When two to three kinds of dyes are used, the solubility of each dye is improved, and as a result, the color purity as a color filter may be improved or the luminance may be improved.

  In the case of using a mixture, there is no problem even if a yellow dye having a structure other than the azo dye as shown below is mixed and used.

  Moreover, it is preferable that the color filter composition of this invention contains a dispersing agent further as needed. There is no limitation in particular as a dispersing agent used for this invention. Representative examples of such dispersants include, for example, polyurethanes, polyacrylates and the like in organic solvent systems, unsaturated polyamides, polycarboxylic acid (partial) amine salts, polycarboxylic acid ammonium salts, polycarboxylic acid alkylamine salts, Polysiloxanes, long-chain polyaminoamide phosphates, hydroxyl group-containing polycarboxylic acid esters, their modified products, amides formed by the reaction of poly (lower alkylene imines) and polyesters having free carboxylic acid groups and their salts Such as water-soluble resin such as (meth) acrylic acid-styrene copolymer, (meth) acrylic acid- (meth) acrylic acid ester copolymer, styrene-maleic acid copolymer, polyvinyl alcohol, polyvinylpyrrolidone, etc. Water-soluble polymer compounds; sodium lauryl sulfate, poly Xylethylene alkyl ether sulfate, sodium dodecylbenzene sulfonate, alkali salt of styrene-acrylic acid copolymer, sodium stearate, sodium alkyl naphthalene sulfonate, sodium alkyl diphenyl ether disulfonate, lauryl sulfate monoethanolamine, lauryl sulfate triethanol Anionic surfactants such as amines, ammonium lauryl sulfate, monoethanolamine stearate, sodium stearate, sodium lauryl sulfate, monoethanolamine of styrene-acrylic acid copolymer, polyoxyethylene alkyl ether phosphate ester; polyoxyethylene Lauryl ether, polyoxyethylene nonylphenyl ether, polyoxyethylene alkyl ether phosphate ester, polio Nonionic surfactants such as siethylene sorbitan monostearate and polyethylene glycol monolaurate; alkylbetaines such as alkyldimethylaminoacetic acid betaine, and amphoteric surfactants such as alkylimidazoline, which may be used alone or in combination of two or more Can be mixed and used.

Among these, a phosphoric acid dispersant or a dispersant having an amine structure is excellent in dispersibility and is preferably used. Examples of the phosphoric acid-based dispersant or the dispersant having an amine structure include, for example, Solsperse series manufactured by Avicia, Disperbyk series manufactured by BYK Chemie, Efka series manufactured by Efka, and the like. The acid value is preferably 20 to 170 mg KOH, more preferably 100 to 150 mg / KOH, or the amine value is 1 to 100 mg KOH / g, more preferably 30 to 90 mg KOH / g.
The amount of the dispersant is usually 3 to 80 parts by mass, preferably 5 to 40 parts by mass with respect to 100 parts by mass of the yellow pigment of the present invention.

  If necessary, a compound such as a known dispersion aid may be added. These compounds are compounds that mediate between the pigment and the dispersant, and are considered to have a function of improving dispersion stability by being electrically and chemically adsorbed to the pigment surface and the dispersant.

  Examples of such a dispersion aid include anionic activators such as polycarboxylic acid type polymer activators and polysulfonic acid type polymer activators, and nonionic activators such as polyoxyethylene and polyoxylene brolock polymers. Among them, preferred are anthraquinone, phthalocyanine, metal phthalocyanine, quinacridone, azo chelate, azo, isoindolinone, pyranthrone, indanthrone, anthrapyrimidine, dibromoanthanthrone, flavanthrone. A pigment derivative having a base such as a base, perylene, perinone, quinophthalone, thioindigo, dioxazine, etc., and having introduced a substituent such as a hydroxyl group, a carboxyl group, a sulfonic acid group, a carbonamide group, or a sulfonamide group. Can be mentioned. Of these, phthalocyanine-based and metal phthalocyanine sulfonamide compounds are particularly effective.

  As explained in the Background section, color filters used in liquid crystal displays and imaging devices are generally made of a transparent substrate such as glass, red, green, and blue primary color pixels, and a light-shielding layer provided between these pixels. It is manufactured by forming a black matrix.

  Since the present invention is characterized in that it contains a phthalocyanine compound and a yellow dye, a method for producing a color filter can be applied by appropriately referring to known knowledge or combining them. For example, the method disclosed in Japanese Patent Laid-Open No. 10-160921 is preferable for producing the color filter of the present invention, but it is not limited thereto.

First, a black matrix is formed on a glass substrate.
Next, a photosensitive resin composition containing the phthalocyanine compound of the present invention and a yellow dye is applied on a glass substrate by spin coating or the like and dried. Next, after that, exposure is performed through a photomask as necessary. Thereafter, alkali development is performed as necessary to obtain a colored pattern (colored layer). Thereafter, if necessary, a transparent overcoat layer (protective film) is formed to protect the colored layer and flatten the surface. Furthermore, a transparent conductive film is formed as needed. Thus, it can be set as a color filter.

  Hereinafter, the method for producing the color filter of the present invention will be described more specifically.

  First, a color filter composition is prepared. The color filter composition of the present invention includes the phthalocyanine compound of the present invention and a yellow dye, but preferably further includes a solvent, a photosensitive resin composition, a dispersant, and the like.

Examples of the solvent that can be used in the present invention include toluene, xylene, benzene, ethylbenzene, tetralin, styrene, cyclohexane, dichloromethane, chloroform, ethyl chloride, 1,1,1-trichloroethane, 1-chlorobutane, cyclohexyl chloride, and trans. -Dichloroethylene, cyclohexanol, methyl cellosolve, n-propanol, n-butanol, 2-ethylbutanol, n-heptanol, 2-ethylhexanol, butoxyethanol, diacetone alcohol, benzaldehyde, γ-butyrolactone, acetone, methyl ethyl ketone, dibutyl ketone , Methyl-i-butyl ketone, methyl-i-amyl ketone, cyclohexane, acetophenone, methylal, furan, β-β-dichloroe Ether, dioxane, tetrahydrofuran, ethyl acetate, n-butyl acetate, amyl acetate, n-butyl acetate, cyclohexylamine, ethanolamine, dimethylformamide, acetonitrile, nitromethane, nitroethane, 2-nitropropane, nitrobenzene, dimethylsulfoxide, diethylene glycol dimethyl ether , Diethylene glycol monomethyl ether, propylene glycol monomethyl ether acetate (PGMEA), ethylene glycol monomethyl ether acetate, cyclohexanone, N-methylpyrrolidone and the like.
Among them, diethylene glycol dimethyl ether, propylene glycol monomethyl ether acetate, cyclohexanone, and the like are preferable from the viewpoint of boiling point and viscosity.

  The phthalocyanine compound is preferably 2 to 20% by mass, more preferably 8 to 12% by mass, and the yellow pigment is preferably 0.1 to 20% by mass, more preferably 1 to 10% by mass with respect to the solvent. It is.

Next, the photosensitive resin composition that can be used in the present invention undergoes a chemical reaction by the action of light, resulting in a change in solubility or affinity for the solvent or a change from liquid to solid. For example, an acrylic resin liquid is used as a binder resin (base polymer), and a photosensitive monomer (photopolymerizable monomer) composed of various acrylic acid esters or methacrylic acid esters and a photopolymerization initiator are added thereto. A photopolymerization type photosensitive resin composition or a photodimerization type photosensitive resin composition using an acrylic resin liquid to be photodimerized can be mentioned, among which a photopolymerization type photosensitive resin composition is preferable.
The term “acrylic resin liquid” as used herein means a solution obtained by dissolving an acrylic resin in a solvent to be used so as to have an appropriate viscosity, and includes a solvent-free liquid acrylic resin liquid. That is, in the composition of the present invention, a solvent is not necessarily required, and even if it is a solventless composition, the photosensitive resin composition is in a liquid state and can uniformly dissolve the above-described dye, In addition, a solvent may not be used as long as the color filter composition can have an appropriate viscosity. In this case, a usable dye can be selected by measuring the solubility of the dye in advance using toluene or toluene and diethylene glycol dimethyl ether.

The acrylic resin preferably has a number average molecular weight in the range of 30,000 to 200,000, and preferably in the range of 40,000 to 100,000.
That is, if the pigment used in the conventional pigment dispersion method is dispersed in an acrylic resin having a large number average molecular weight and a large viscosity, various problems occur. However, as described above in the present invention. Since a soluble pigment is used, it can be dissolved in a resin having a high viscosity. In addition, the acrylic resin is highly soluble in the resin of the dye and can contain the dye at a high concentration as compared with other resins such as polyimide, and as a result, forms a colored layer with high transparency and a clear color. And has a better effect on the control of light resistance and absorption wavelength of the colored layer.

  As said acrylic resin, 10 mass% or more among the monomer and oligomer which comprise it is 1 or more types chosen from acrylic acid, methacrylic acid, acrylic ester, and methacrylic ester, Acrylic acid or methacrylic acid is used. Preferably 1-50 mass%, More preferably, it is 5-35 mass%, Preferably it contains 10-90 mass parts of acrylic acid ester or methacrylic acid, More preferably, it contains 30-80 mass%.

  As monomers and oligomers constituting the acrylic resin, acrylic acid, methacrylic acid, methyl acrylate, methyl methacrylate, propyl acrylate, propyl methacrylate, butyl acrylate, butyl methacrylate, 2-ethylhexyl acrylate, 2-ethylhexyl methacrylate, octyl acrylate, octyl Methacrylate, benzyl acrylate, benzyl methacrylate, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl acrylate, 2-hydroxypropyl methacrylate, acrylamide, methacrylamide, N-hydroxymethylacrylamide, acrylonitrile, styrene, vinyl acetate, Maleic acid, fumaric acid, polyethylene glycol Examples include acrylate, trimethylolpropane triacrylate, trimethylolpropane trimethacrylate, pentaerythritol triacrylate, dipentaerythritol hexaacrylate, dipentaerythritol hexaacrylate caprolactone adduct hexaacrylate, melamine acrylate, epoxy acrylate prepolymer, acrylic As the resin, (meth) acrylic acid, hydroxyalkyl (meth) acrylate, acrylic resin obtained by polymerizing various alkyl (meth) acrylates, (meth) acrylic acid, hydroxyalkyl (meth) acrylate, various alkyl (meth) Acrylic resin obtained by polymerizing acrylate, benzyl (meth) acrylate, styrene, (meth) acrylic acid, various alkyls ( Data) acrylic resin obtained by polymerizing the acrylate.

  In addition, examples of the photosensitive monomer that can be a component of the photosensitive resin coloring composition of the present invention include monomers constituting the acrylic resin, and preferably trimethylolpropane trimethacrylate, dipentaerythritol hexaacrylate, penta Examples include polyfunctional (meth) acrylates such as erythritol triacrylate and pentaerythritol tetraacrylate.

  Moreover, 40-90 mass parts is preferable with respect to 100 mass parts of said acrylic resins, and, as for the usage-amount of a photosensitive monomer, 60-70 mass parts is more preferable.

Examples of the photopolymerization initiator that can be a composition component of the photopolymerizable photosensitive resin composition include, for example, benzoin alkyl ether compounds, acetophenone compounds, benzophenone compounds, phenyl ketone compounds, thioxanthone compounds, triazine compounds, Examples include imidazole compounds and anthraquinone compounds.
More specifically, 4-phenoxydichloroacetophenone, 4-t-butyl-dichloroacetophenone, diethoxyacetophenone, 1- (4-isopropylphenyl) -2-hydroxy-2-methylpropan-1-one, 1-hydroxy Acetophenone compounds such as cyclohexyl phenyl ketone, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butan-1-one, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzyldimethyl ketal, etc. Benzoin alkyl ether compounds, benzophenone, benzoylbenzoic acid, methyl benzoylbenzoate, 4-phenylbenzophenone, hydroxybenzophenone, acrylated benzophenone, 4-benzoyl- Benzophenone compounds such as' -methyldiphenyl sulfide, thioxanthone compounds such as thioxanthone, 2-chlorothioxanthone, 2-methylthioxanthone, isopropylthioxanthone 2,4-diisopropylthioxanthone, 2,4,6- Trichloro-s-triazine, 2-phenyl-4,6-bis (trichloromethyl) -s-triazine, 2- (p-methoxyphenyl) -4,6-bis (trichloromethyl) -s-triazine, 2- ( p-tolyl) -4,6-bis (trichloromethyl) -s-triazine, 2-pienyl-4,6-bis (trichloromethyl) -s-triazine, 2,4-bis (trichloromethyl) -6-styryl -S-triazine, 2- (naphth-1-yl) -4,6-bis (trichloromethyl)- -Triazine, 2- (4-methoxy-naphth-1-yl) -4,6-bis (trichloromethyl) -s-triazine, 2,4-trichloromethyl- (piperonyl) -6-triazine, 2,4- Triazine compounds such as trichloromethyl (4'-methoxystyryl) -6-triazine, 2- (2,3-dichlorophenyl) -4,5-diphenylimidazole dimer, 2- (2,3-dichlorophenyl) -4 , 5-bis (3-methoxyphenyl) -imidazole dimer, 2- (2,3-dichlorophenyl) -4,5-bis (4-methoxyphenyl) -imidazole dimer, 2- (2,3- Dichlorophenyl) -4,5-bis (4-chlorophenyl) -imidazole dimer, 2- (2,3-dichlorophenyl) -4,5-di (2-furyl) -imida Zole, imidazole compounds such as 2,2′-bis (2-chlorophenyl) -4,5,4 ′, 5′-tetraphenyl-1,2′-biimidazole, Irgacure 369, Irgacure 907 (both are Ciba Geigyca And acetophenone compounds such as trade names).

  The addition amount of the photopolymerization initiator is not particularly limited, but for acetophenone compounds (Irgacure 369, etc.), a photosensitive monomer (photopolymerizable monomer; for example, dipentaerythritol hexaacrylate, etc.) is 100. When it is set as a mass part, it is desirable to add in the ratio of preferably 1-30 mass parts, more preferably 5-15 mass parts.

  In addition, arbitrary components, such as a thermal polymerization inhibitor, can be added to the composition of this invention as needed.

The thermal polymerization inhibitor is added for the purpose of improving storage stability. For example, hydroquinone, p-methoxyphenol, di-t-butyl-p-cresol, pyrogallol, t-butylcatechol, benzoquinone, 4 , 4'-thiobis (3-methyl-6-t-butylphenol), 2,2'-methylene (4-methyl-6-t-butylphenol), 2- (mercaptobenzimidazole), and the like.
Moreover, you may add a photodegradation prevention agent as needed.

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).

<Reference 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.

<Reference 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 the reference 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 maximum absorption wavelength, gram extinction coefficient, and heat resistance of the phthalocyanine derivative thus obtained were measured in exactly the same manner as in Reference Example 1, and the results are summarized in Table 4.

<Reference 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 the reference example 1 was performed, and about 10.95g (The yield of 96.9 mol% with respect to the intermediate body 1 and 4-nitrophthalonitrile) was obtained.

  The maximum absorption wavelength, gram extinction coefficient, and heat resistance of the phthalocyanine derivative thus obtained were measured in exactly the same manner as in Reference Example 1, and the results are summarized in Table 4.

<Reference 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 the reference example 1 was performed, and about 11.2 g (yield 99.6 mol% with respect to the intermediate body 1 and a pyridine-2,3- dicarbonitrile) was obtained.

  The maximum absorption wavelength, gram extinction coefficient, and heat resistance of the phthalocyanine derivative thus obtained were measured in exactly the same manner as in Reference Example 1, and the results are summarized in Table 4.

<Reference 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 the reference example 1 was performed, and about 11.0g (The yield of 97.3 mol% with respect to the intermediate body 1 and 2, 3- dicyano naphthalene) was obtained.

  The maximum absorption wavelength, gram extinction coefficient, and heat resistance of the phthalocyanine derivative thus obtained were measured in exactly the same manner as in Reference Example 1, and the results are summarized in Table 4.

<Reference 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 the reference example 1 was performed, and about 10.95g (The yield with respect to the intermediate body 1 and 2,3-dibromo-6,7-dicyanonaphthalene was 95.1 mol%) was obtained.

  The maximum absorption wavelength, gram extinction coefficient, and heat resistance of the phthalocyanine derivative thus obtained were measured in exactly the same manner as in Reference Example 1, and the results are summarized in Table 4.

<Reference 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 the reference example 1 was performed, and about 11.3 g (yield 100.4 mol% with respect to the intermediate body 1 and 4-aminophthalonitrile) was obtained.

  The maximum absorption wavelength, gram extinction coefficient, and heat resistance of the phthalocyanine derivative thus obtained were measured in exactly the same manner as in Reference Example 1, and the results are summarized in Table 4.

<Reference 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 the reference example 1 was performed, and about 11.3 g (yield 100.4 mol% with respect to the intermediate body 1 and 4-hydroxyphthalonitrile) was obtained.

  The maximum absorption wavelength, gram extinction coefficient, and heat resistance of the phthalocyanine derivative thus obtained were measured in exactly the same manner as in Reference Example 1, and the results are summarized in Table 4.

<Reference 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 the reference 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 maximum absorption wavelength, gram extinction coefficient, and heat resistance of the phthalocyanine derivative thus obtained were measured in exactly the same manner as in Reference Example 1, and the results are summarized in Table 4.

<Reference 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 Reference Example 1 was performed, and about 11.2 g (yield 98.9 mol% with respect to the intermediate body 1 and 4, 5- dichlorophthalonitrile) was obtained.

  The maximum absorption wavelength, gram extinction coefficient, and heat resistance of the phthalocyanine derivative thus obtained were measured in exactly the same manner as in Reference Example 1, and the results are summarized in Table 4.

<Reference 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 the reference example 1 was performed, and about 10.45g (The yield with respect to the intermediate body 1 and 2, 3- dicyano pyrazine was 94.3 mol%) was obtained.

  The maximum absorption wavelength, gram extinction coefficient, and heat resistance of the phthalocyanine derivative thus obtained were measured in exactly the same manner as in Reference Example 1, and the results are summarized in Table 4.

<Reference 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 the reference 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.

<Reference 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 the reference example 1 was performed, and about 10.0 g (yield 90.7 mol% with respect to the intermediate body 1 and the intermediate body 4) was obtained.

  The maximum absorption wavelength, gram extinction coefficient, and heat resistance of the phthalocyanine derivative thus obtained were measured in exactly the same manner as in Reference Example 1, and the results are summarized in Table 4.

<Reference 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 the reference example 1 was performed, and about 10.55g (The yield of 90.5 mol% with respect to the intermediate body 5 and a phthalonitrile) was obtained.

  The maximum absorption wavelength, gram extinction coefficient, and heat resistance of the phthalocyanine derivative thus obtained were measured in exactly the same manner as in Reference Example 1, and the results are summarized in Table 4.

  The structures of Reference 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 reference 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 Reference 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.

<Reference Example 15>
The maximum absorption wavelength, gram extinction coefficient, and heat resistance of the phthalocyanine derivative obtained in Reference Example 2 were exactly the same as in Reference Example 1, except that the heat resistance was evaluated by the following 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. Table 3 shows the relationship between the thickness of the film and the corresponding reference example.

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

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

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

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

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

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

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

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

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

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

<Reference Example 26>
In Reference Example 15, the same procedure as in Reference Example 15 was followed except that the phthalocyanine derivative obtained in Reference Example 2 was replaced with the phthalocyanine derivative obtained in Reference Example 13, and the maximum absorption wavelength, gram extinction coefficient and heat resistance were The results are summarized in Table 1.

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

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

<Reference 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 Reference Example 1 was performed, and about 5.7 g (yield 82.0 mol% with respect to the intermediate body 6 and phthalonitrile) was obtained.

  The maximum absorption wavelength, gram extinction coefficient, and heat resistance of the phthalocyanine derivative thus obtained were measured in exactly the same manner as in Reference Example 1, and the results are summarized in Table 4.

<Reference 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 the reference 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 maximum absorption wavelength, gram extinction coefficient, and heat resistance of the phthalocyanine derivative thus obtained were measured in exactly the same manner as in Reference Example 1, and the results are summarized in Table 4.

<Reference 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 the reference example 1 was performed, and about 3.9g (The yield with respect to the intermediate body 8 and a phthalonitrile 77.0 mol%) was obtained.

  The maximum absorption wavelength, gram extinction coefficient, and heat resistance of the phthalocyanine derivative thus obtained were measured in exactly the same manner as in Reference Example 1, and the results are summarized in Table 4.

<Reference 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 the reference example 1 was performed, and about 12.25 g (yield 99.5 mol% with respect to the intermediate body 9 and a phthalonitrile) was obtained.

  The maximum absorption wavelength, gram extinction coefficient, and heat resistance of the phthalocyanine derivative thus obtained were measured in exactly the same manner as in Reference Example 1, and the results are summarized in Table 4.

<Reference 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 the reference example 1 was performed, and about 4.5g (The intermediate body 10 and the yield of 78.3 mol% with respect to a phthalonitrile) was obtained.

  The maximum absorption wavelength, gram extinction coefficient, and heat resistance of the phthalocyanine derivative thus obtained were measured in exactly the same manner as in Reference Example 1, and the results are summarized in Table 4.

<Reference 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 Reference Example 1 was performed, and about 7.85 g (yield 99.8 mol% with respect to the intermediate body 1 and the intermediate body 11) was obtained.

  The maximum absorption wavelength, gram extinction coefficient, and heat resistance of the phthalocyanine derivative thus obtained were measured in exactly the same manner as in Reference Example 1, and the results are summarized in Table 4.

<Reference 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 the reference 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 maximum absorption wavelength, gram extinction coefficient, and heat resistance of the phthalocyanine derivative thus obtained were measured in exactly the same manner as in Reference Example 1, and the results are summarized in Table 4.

<Reference 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 the reference 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 maximum absorption wavelength, gram extinction coefficient, and heat resistance of the phthalocyanine derivative thus obtained were measured in exactly the same manner as in Reference Example 1, and the results are summarized in Table 4.

<Reference 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 the reference 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 maximum absorption wavelength, gram extinction coefficient, and heat resistance of the phthalocyanine derivative thus obtained were measured in exactly the same manner as in Reference Example 1, and the results are summarized in Table 4.

<Reference 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 same operation as in Reference Example 1 was performed to obtain about 6.1 g (yield: 91.9 mol% based on intermediate 15 and phthalonitrile).

  The maximum absorption wavelength, gram extinction coefficient, and heat resistance of the phthalocyanine derivative thus obtained were measured in exactly the same manner as in Reference Example 1, and the results are summarized in Table 4.

<Reference 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 the reference 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 maximum absorption wavelength, gram extinction coefficient, and heat resistance of the phthalocyanine derivative thus obtained were measured in exactly the same manner as in Reference Example 1, and the results are summarized in Table 4.

<Reference 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 the reference 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 maximum absorption wavelength, gram extinction coefficient, and heat resistance of the phthalocyanine derivative thus obtained were measured in exactly the same manner as in Reference Example 1, and the results are summarized in Table 4.

<Reference 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 the reference 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 maximum absorption wavelength, gram extinction coefficient, and heat resistance of the phthalocyanine derivative thus obtained were measured in exactly the same manner as in Reference Example 1, and the results are summarized in Table 4.

<Reference 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 Reference 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 maximum absorption wavelength, gram extinction coefficient, and heat resistance of the phthalocyanine derivative thus obtained were measured in exactly the same manner as in Reference Example 1, and the results are summarized in Table 4.

<Reference 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 the reference 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 maximum absorption wavelength, gram extinction coefficient, and heat resistance of the phthalocyanine derivative thus obtained were measured in exactly the same manner as in Reference Example 1, and the results are summarized in Table 4.

<Reference 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 the reference example 1 was performed, and about 5.52g (The yield of 97.2 mol% with respect to the intermediate body 21 and a phthalonitrile) was obtained.

  The maximum absorption wavelength, gram extinction coefficient, and heat resistance of the phthalocyanine derivative thus obtained were measured in exactly the same manner as in Reference Example 1, and the results are summarized in Table 4.

<Reference Example 44>
In Reference Example 15, the same procedure as in Reference Example 15 was followed except that the phthalocyanine derivative obtained in Reference Example 2 was replaced with the phthalocyanine derivative obtained in Reference Example 28, and the maximum absorption wavelength, gram extinction coefficient and heat resistance were The results are summarized in Table 4.

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

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

<Reference Example 47>
In Reference Example 15, the same procedure as in Reference Example 15 was followed, except that the phthalocyanine derivative obtained in Reference Example 2 was replaced with the phthalocyanine derivative obtained in Reference Example 32, and the maximum absorption wavelength, gram extinction coefficient, and heat resistance. The results are summarized in Table 4.

<Reference Example 48>
In Reference Example 15, the same procedure as in Reference Example 15 was followed except that the phthalocyanine derivative obtained in Reference Example 2 was replaced with the phthalocyanine derivative obtained in Reference Example 33, and the maximum absorption wavelength, gram extinction coefficient and heat resistance were The results are summarized in Table 4.

<Reference Example 49>
In Reference Example 15, the same procedure as in Reference Example 15 was followed, except that the phthalocyanine derivative obtained in Reference Example 2 was replaced with the phthalocyanine derivative obtained in Reference Example 35, and the maximum absorption wavelength, gram extinction coefficient, and heat resistance. The results are summarized in Table 4.

<Reference Example 50>
In Reference Example 15, the same procedure as in Reference Example 15 was followed, except that the phthalocyanine derivative obtained in Reference Example 2 was replaced with the phthalocyanine derivative obtained in Reference Example 36, and the maximum absorption wavelength, gram extinction coefficient, and heat resistance. The results are summarized in Table 4.

<Reference Example 51>
In Reference Example 15, the same procedure as in Reference Example 15 was followed except that the phthalocyanine derivative obtained in Reference Example 2 was replaced with the phthalocyanine derivative obtained in Reference Example 38, and the maximum absorption wavelength, gram extinction coefficient and heat resistance were The results are summarized in Table 4.

<Reference Example 52>
In Reference Example 15, the same procedure as in Reference Example 15 was followed except that the phthalocyanine derivative obtained in Reference Example 2 was replaced with the phthalocyanine derivative obtained in Reference Example 41, and the maximum absorption wavelength, gram extinction coefficient and heat resistance were The results are summarized in Table 4.

<Reference Example 53>
In Reference Example 15, the same procedure as in Reference Example 15 was followed except that the phthalocyanine derivative obtained in Reference Example 2 was replaced with the phthalocyanine derivative obtained in Reference Example 42, and the maximum absorption wavelength, gram extinction coefficient and heat resistance were 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 the reference example 1 was performed, and about 3.8 g (yield of 84.9 mol% with respect to the intermediate body 6) was obtained.

  The maximum absorption wavelength, gram extinction coefficient, and heat resistance of the phthalocyanine derivative thus obtained were measured in exactly the same manner as in Reference 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 Reference 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 Reference Examples 1-14 and 28-43 have a gram extinction coefficient (compared to the β-position 4-substituted phthalocyanine derivative synthesized in Comparative Reference Example 1 and the β-position 8-substituted phthalocyanine derivative synthesized in Comparative Reference Example 2). Although no superiority was observed in εg), the heat resistance improved more than twice as compared with the β-position 4-substituted phthalocyanine derivative having high heat resistance synthesized in Comparative Reference Example 1. Further, compared with Comparative Reference Examples 1 and 2, the phthalocyanine derivatives of Reference Examples 1 to 14 and 28 to 43 showed remarkably superior solvent solubility.

  Subsequently, an example of a color filter composition containing a phthalocyanine compound and a yellow pigment will be described.

[Synthesis Example of Azo Dye Intermediate (a)]
After thoroughly stirring 37.0 parts of sulfanilic acid with 150 parts of water and 32.0 parts of concentrated hydrochloric acid, it was diazotized at 5-10 ° C. with 25.0 parts of 4N sodium nitrite, then 1-ethyl-1, 370 parts of water was added to 42.0 parts of 2-dihydro-6-hydroxy-4-methyl-2-oxo-3-pyridinecarbonitrile, and a solution adjusted to pH 8 with 2N sodium hydroxide was added to the coupling component. The temperature was kept at a temperature of ℃ or less and added. The pH is adjusted to 5.0 with sodium hydroxide to complete the coupling reaction. After completion of the reaction, 100 parts of sodium chloride is used for salting out, and the precipitated product is filtered and dried to obtain an azo compound represented by the following formula. 60.4 parts (78%) of the dye intermediate (a) was obtained.

[Synthesis Example of Azo Dye (1)]
Azo dye (1):

Synthesis Example 5: 50.0 parts of the azo dye intermediate (a) was dissolved in 0.1N aqueous sodium hydroxide solution, 51.2 parts of trioctylamine and chloroform were added and stirred. Concentrated sulfuric acid was added to adjust to pH 1.0, and then the organic layer was separated and concentrated, followed by drying to obtain 77.0 parts (yield 78%) of azo dye (1).

[Synthesis Example of Azo Dye (2)]
Azo dye (2):

Example of Synthesis of Azo Dye Synthesis Example 1 The same procedure was followed except that trioctylamine in Example 1 was changed to tributylamine (26.9 parts) to obtain 54.4 parts of azo dye (2) (yield 72%). It was.

[Synthesis Example of Azo Dye (3)]
Azo dye (3):

Synthesis Example of Azo Dye Synthesis Example 1 was repeated except that the sulfanilic acid in Synthesis Example 1 was changed to 4-chloroaniline-3-sulfonic acid (33.8 parts), and 47.9 parts of azo dye (3) ( Yield 75%).

  [Synthesis Example of Sulfonate Compound (b)]

While 35.0 parts of the azo dye intermediate (a) was suspended in a mixed solvent of 15.6 parts of dimethylformamide and 215.5 parts of acetonitrile under ice-cooling, thionyl chloride was added dropwise. After a while, the temperature was raised to 40 ° C. and further stirred for 4 hours. The suspension was then poured into 525 parts of water with stirring and stirred for an additional 10 minutes. The resulting precipitate was collected by filtration and vacuum-dried at 60 ° C. for several hours to obtain 29.2 parts of sulfonic acid chloride (b) (80 mol% based on the azo dye intermediate (a)).
[Synthesis Example of Azo Dye (4)]
Azo dye (4):

  29.2 parts of the sulfonic acid chloride (b) was suspended in chloroform under ice-cooling, and a mixed solution of 14.9 parts of 2-ethylhexylamine and 38.9 parts of triethylamine was slowly added dropwise. After warming to room temperature and stirring for 10 minutes, the reaction solution was concentrated. The concentrate was dissolved in 150 parts of acetone, poured into 600 parts of 1M hydrochloric acid, and the resulting precipitate was collected by filtration. This precipitate was dissolved in 400 parts of methanol under heating and refluxing, and slowly cooled to room temperature. The resulting precipitate was collected by filtration and then vacuum-dried at 60 ° C. for several hours to obtain 28.4 parts of azo dye (3) (78 mol% with respect to sulfonic acid chloride (b)).

  Azo dye (5):

  Azo dye (6):

  The azo dyes (4) to (6) were synthesized by the same route as the azo dye (3).

[Synthesis Example of N, N-di (2-ethylhexyl) -4-nitrobenzoic acid amide]
10 parts of 4-nitrobenzoyl chloride was dissolved in 200 parts of chloroform, and a mixed solvent of 14.3 parts of di (2-ethylhexyl) amine and 16.4 parts of triethylamine was added. After stirring at room temperature for 30 minutes, water was added and separated. The organic layer was washed successively with 2M hydrochloric acid, saturated sodium bicarbonate and saturated brine, and dried over anhydrous sodium sulfate. Filtration, concentration and vacuum drying gave 16.8 parts (80 mol%) of N, N-di (2-ethylhexyl) -4-nitrobenzoic acid amide.

[Synthesis Example of 4-Amino-N, N-di (2-ethylhexyl) benzoic acid amide]
7.22 parts of reduced iron was suspended in a mixed solvent of 11.6 parts of acetic acid and 29.6 parts of water, and stirred at 80 ° C. for 1 hour. To this suspension, a solution of 12.6 parts of N, N-di (2-ethylhexyl) -4-nitrobenzoic acid amide in ethanol (29.2 parts) was added dropwise, and stirring was continued for 10 minutes, followed by cooling to room temperature. . Next, a solution of 9.38 parts of water (50 parts) in sodium carbonate was added and filtered. The filtrate was concentrated, acetone was added and stirred. Thereafter, the mixture was filtered again, dried over anhydrous sodium sulfate, filtered, concentrated and dried to obtain 10.6 parts (91 mol%) of 4-amino-N, N-di (2-ethylhexyl) benzoic acid amide.

[Synthesis Example of Azo Dye (7)]
Azo dye (7):

  4-Amino-N, N-di (2-ethylhexyl) benzoic acid amide (2.70 parts) is dissolved in 6.5 wt% hydrochloric acid (45 parts), and sodium nitrite (0.57 parts) water (6.70 parts) at 0 ° C. ) The solution was added dropwise and stirred for 1 hour. Thereafter, at 0 ° C., the solution was dissolved in 1.47 parts of 1-ethyl-1,2-dihydro-6-hydroxy-4-methyl-2-oxo-3-pyridinecarbonitrile and 0.56 parts of sodium hydroxide ( 13.9 parts) The solution was added dropwise and stirred for 30 minutes. The precipitate was collected by filtration, washed with stirring with 50 g of methanol and 70 g of water, and vacuum-dried to obtain 3.12 parts (78%) of azo dye (7).

[Synthesis Example of 4-Nitrophthalate Di (2-methoxyethyl)]
4-Nitrophthalic acid (50.0 g) was dissolved in a mixed solution of toluene (294 g) and 2-methoxyethanol (108 g). Further, 9.95 g of sulfuric acid was added, and the mixture was heated to reflux while removing water using a Dean-Stark trap. After 5.5 hours, the reaction solution was poured into water to separate two layers, and the aqueous layer was extracted with ethyl acetate. The combined organic layers were washed successively with saturated sodium bicarbonate and saturated brine, and then dried over anhydrous sodium sulfate. After filtration, the filtrate was concentrated and dried under reduced pressure to obtain 78.5 g (corresponding to 101 mol%) of 4-nitrophthalic acid di (2-methoxyethyl).

[Synthesis example of di (2-methoxyethyl) 4-aminophthalate]
31.2 g of reduced iron was suspended in a mixed solvent of 50 g of acetic acid and 132 g of water and stirred at 80 ° C. for 1 hour. To this suspension was added dropwise a solution of 73.2 g of di (2-methoxyethyl) 4-nitrophthalate in ethanol (104 g), and the mixture was stirred for 40 minutes and then cooled to room temperature. The reaction solution was cooled to 0 ° C., and an aqueous sodium carbonate solution was slowly added dropwise to adjust the pH to 7-8. After the suspension was concentrated, acetone was added and stirred, and the solution obtained by filtration was dried over anhydrous magnesium sulfate. After filtration, it was concentrated and dried under reduced pressure to obtain 59.9 g (90 mol%) of bis (2-methoxyethyl) 4-aminophthalate.

[Synthesis Example of Azo Dye (8)]
Azo dye (8):

  25.0 g of di (2-methoxyethyl) 4-aminophthalate was dissolved in 160 g of 9 wt% hydrochloric acid and stirred at 0 ° C. To this solution, a solution of 6.38 g of sodium nitrite in water (13 g) was slowly added dropwise, stirred at 0 ° C. for 1 hour, and 1.63 g of sulfamic acid was added (solution 1-A). Separately, a solution obtained by dissolving 4.14 g of sodium hydroxide in 108 g of methanol was treated with 1-ethyl-1,2-dihydro-6-hydroxy-4-methyl-2-oxo-3-pyridinecarbonitrile. Solution 1-B was prepared in addition to 15.0 g. Solution 1-B was added dropwise to Solution 1-A cooled to 0 ° C. After stirring for 20 minutes, the precipitate was collected by filtration, washed with water, and vacuum-dried at 60 ° C. overnight to obtain 39.1 g of azo dye (8) based on di (2-methoxyethyl) 4-aminophthalate. : 96 mol%).

Example 1
(1) Preparation of dye resist solution A dye resist solution was prepared by mixing and dissolving in the following composition.

(2) Preparation of coating film plate Using a spin coater so that the film thickness after drying the dye resist solution obtained in (1) above is about 2 μm against a glass substrate whose surface has been wiped with acetone in advance. It was applied under the conditions of 25 drops, 1500 rpm and 1 second, and prebaked at 80 ° C. for 30 minutes. Thereafter, the resin was cured by UV irradiation, and then post-baked at 220 ° C. for 20 minutes.

(3) Evaluation of filter The chromaticity coordinate value, heat resistance, light resistance and contrast ratio of the colored filter obtained above were evaluated. The results are shown in Table 5 below. The chromaticity coordinate values, heat resistance, light resistance and contrast ratio shown in the following table were measured as follows.

(Dye coordinate value)
The absorption waveform was measured using a Hitachi spectrophotometer U-2910, and the chromaticity (x, Y) was determined so that the chromaticity coordinate value y = 0.600 by further multiplying this waveform by a constant. . Calculation was performed assuming that a C light source was used for illumination.

(Heat-resistant)
The absorption spectrum of the coated glass plate obtained by prebaking at 80 ° C. was measured with a spectrophotometer (manufactured by Hitachi, Ltd .: U-2910), and this was used as the spectrum before heating. Next, this coated glass plate was photocrosslinked and post-baked at 220 ° C. for 20 minutes, and then the absorption spectrum was measured with a spectrophotometer, and this was used as a spectrum after heating. In each spectrum before and after heating measured in this way, the absorbance from 380 nm to 780 nm 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.

  In this way, the heat resistance was measured.

(Light resistance)
The post-baked coating glass was irradiated with 130,000 lux of light using a xenon light resistance tester (Suntest CPS + manufactured by ATLAS), and the following three stages of evaluation were performed based on the residual ratio of absorbance over time.

A: When the ΔE value before and after light irradiation after 10 hours is less than 5 ○: When the ΔE value before and after light irradiation after 10 hours is 5 to 30 ×: The ΔE value before and after light irradiation after 10 hours is 30 When exceeding (contrast ratio)
The post-baked coating glass was sandwiched between two deflection plates, and the ratio of transmitted light amount (contrast ratio) when the deflection axes of the two deflection plates were parallel and orthogonal was measured. The following three stages of evaluation were performed based on the measurement results.

◎: When the contrast ratio exceeds 12,000 times ○: When the contrast ratio is 10,000 to 12,000 times ×: When the contrast ratio is less than 10,000 (Example 2)
All operations were performed in the same manner as in Example 1 except that the compounding ratio of the dye resist was changed as follows, and the results are shown in Table 5.

(Example 3)
All operations were performed in the same manner as in Example 1 except that the compounding ratio of the dye resist was changed as follows, and the results are shown in Table 5.

Example 4
All operations were performed in the same manner as in Example 1 except that the compounding ratio of the dye resist was changed as follows, and the results are shown in Table 5.

(Example 5)
All operations were performed in the same manner as in Example 1 except that the compounding ratio of the dye resist was changed as follows, and the results are shown in Table 5.

(Example 6)
All operations were performed in the same manner as in Example 1 except that the compounding ratio of the dye resist was changed as follows, and the results are shown in Table 5.

(Example 7)
All operations were performed in the same manner as in Example 1 except that the compounding ratio of the dye resist was changed as follows, and the results are shown in Table 5.

(Example 8)
All operations were performed in the same manner as in Example 1 except that the compounding ratio of the dye resist was changed as follows, and the results are shown in Table 5.

Example 9
All operations were performed in the same manner as in Example 1 except that the compounding ratio of the dye resist was changed as follows, and the results are shown in Table 5.

  Usually, since the dye is dissolved in the polymer resin, the dispersant is not essential. However, in the color filter, it may become a high concentration (about 30 wt%). In some cases, the contrast ratio was better in Example 3 to which the dispersant was added than in Example 4.

Claims (5)

A color filter composition comprising a phthalocyanine derivative and a yellow pigment,
The phthalocyanine derivative is
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. 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 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 a halogen atom:
A color filter composition represented by:   The color filter composition according to claim 1, wherein 1 to 6 of the substituents (a) are the substituents (a).   The color filter composition according to claim 2, wherein 1 to 4 of the substituents (a) are the substituents (a). The color filter composition according to any one of claims 1 to 3, wherein the yellow dye is an azo dye or a salt thereof represented by the following formula (A) or the following formula (I):

In the above formula,
Q is a substituted or unsubstituted alkyl group having 1 to 5 carbon atoms, a substituted or unsubstituted alkoxy group having 1 to 5 carbon atoms, a halogen atom, a nitro group, a sulfo group, a sulfamoyl group, an N-substituted sulfamoyl group, an alkoxy group. An aryl group having at least one group selected from the group consisting of a carbonyl group and an N-substituted carbamoyl group, or a substituted or unsubstituted heteroaryl group,
D ¹ is a hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 12 carbon atoms, a substituted or unsubstituted aralkyl group having 7 to 20 carbon atoms, — (R ₅ O) _r R ₆ , —COR ₇ , or A substituted or unsubstituted aryl group having 6 to 20 carbon atoms, wherein R ₅ is an alkylene group having 1 to 3 carbon atoms, and R ₆ is a hydrogen atom or an alkyl group having 1 to 8 carbon atoms. , R is an integer of 0-4, R ₇ is a substituted or unsubstituted alkyl group of 1-8,
D ² is a substituted or unsubstituted alkyl group having 1 to 5 carbon atoms, a substituted or unsubstituted amino group,
D ³ is a hydrogen atom, a -CN or -CONH _2,
D ⁴ and D ⁵ are each independently a substituted or unsubstituted amino group.   Furthermore, the color filter composition of any one of Claims 1-4 containing a dispersing agent.