JP2014028950A - Composition and color filter - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a composition that is good in hue as a green dye, and exhibits high luminance, and a color filter including the composition.SOLUTION: A composition includes a phthalocyanine compound (1) having a maximum absorption wavelength in the range of 600-700 nm and a phthalocyanine compound (2) having a maximum absorption wavelength in the range of more than 700 nm and 750 nm or less.

Description

  The present invention relates to a composition containing phthalocyanine compounds (1) and (2) having a maximum absorption wavelength in a specific wavelength region, and a color filter containing the composition. More specifically, the present invention relates to a composition used as a green colorant for a color filter having high luminance and good color, and a color filter including the composition.

  A color filter used for a liquid crystal display (LCD: Liquid Crystal Display), an imaging device, or the like is generally a substrate made of glass, plastic, an imaging device, a thin film transistor, or the like, and red (R) by a pattern arrangement of fine colored pixels on the substrate. ), Green (G), and blue (B) pixels, and a black matrix that is a light shielding layer provided between these pixels. 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 removed by alkali washing and further post-cured (post-baked).

  In addition to personal computer applications, LCDs using color filters have also been actively developed for large-sized liquid crystal televisions with further improved color reproducibility. The competition of LCD is intensifying, and there is a strong demand for improving the quality of color filters, such as good color, high brightness, and color reproducibility.

  For example, it has been proposed to use a green pigment colored resin composition containing a halogenated zinc phthalocyanine green pigment and a blue pigment (copper phthalocyanine pigment) for green (G) pixels of a color filter (Patent Document 1). In Patent Document 1, a blue dye (copper phthalocyanine pigment) suppresses pixel chipping of a halogenated zinc phthalocyanine green pigment, has excellent pattern linearity, no light leakage, high color purity, high luminance, and high contrast. Although it is described that a color filter can be obtained, the luminance actually decreased as the blending ratio of the blue pigment was increased.

JP 2012-72252 A

  Actually, even with the green pigment colored resin composition described in Patent Document 1, the brightness and color (color purity) cannot be said to be sufficient, and the brightness and color (color purity) can be further improved. Technology is desired.

  Accordingly, the present invention has been made in view of the above circumstances, and an object thereof is to provide a composition having a good color as a green pigment and exhibiting high luminance, and a color filter including the composition. .

  As a result of intensive studies to solve the above problems, the present inventors have found that a composition containing phthalocyanine compounds (1) and (2) having a maximum absorption wavelength in a specific wavelength region is a green pigment. It has been found that it has good color (color purity) and has high luminance, and has completed the present invention.

  That is, the above object is achieved by a composition comprising a phthalocyanine compound (1) having a maximum absorption wavelength at 600 to 700 nm and a phthalocyanine compound (2) having a maximum absorption wavelength exceeding 700 nm and not more than 750 nm.

  The composition of the present invention has good color (color purity) as a green pigment and exhibits high brightness. For this reason, the said composition can be used conveniently for a color filter.

  Embodiments of the present invention will be described below. In addition, although the structural requirement of this invention, embodiment, etc. are demonstrated in detail below, these are examples of the embodiment of this invention, and are not limited to these content.

  The first of the present invention is a composition comprising a phthalocyanine compound (1) having a maximum absorption wavelength at 600 to 700 nm and a phthalocyanine compound (2) having a maximum absorption wavelength exceeding 700 nm and not more than 750 nm.

  In the following, “phthalocyanine compound (1) having a maximum absorption wavelength in 600 to 700 nm” is simply referred to as “phthalocyanine compound (1)”, and “phthalocyanine compound (2) having a maximum absorption wavelength in excess of 700 nm to 750 nm or less” is simply “ Also referred to as “phthalocyanine compound (2)”.

  The composition of the present invention is obtained by adding the phthalocyanine compound (2) having the maximum absorption wavelength in the specific wavelength region to the phthalocyanine compound (1) having the maximum absorption wavelength in the specific wavelength region as described above. . By setting it as such a composition, the composition of this invention becomes favorable [the green color (color purity)], and when it is used as a color filter, the brightness | luminance improves. Hereinafter, the mechanism will be described, but the following mechanism is estimation and does not limit the scope of the present invention.

  The green (G) pixel of the color filter has an absorbance exceeding 600 nm in the red wavelength region, which is unnecessary light, and having a high absorbance of 700 nm or less (that is, low transmittance), and a low absorbance in the green wavelength region of 500 to 600 nm ( That is, a high transmittance is required. In addition to the phthalocyanine compound (1) having a maximum absorption wavelength at 600 to 700 nm, the composition of the present invention further contains a phthalocyanine compound (2) having a maximum absorption wavelength exceeding 700 nm and not more than 750 nm. The absorption band of such a phthalocyanine compound (2) has a spread around the maximum absorption wavelength, and has a second absorption peak (sub-peak) at 620 to 700 nm on the short wavelength side with respect to the maximum absorption wavelength. It is preferable. Further, the phthalocyanine compound (2) preferably has a feature that the absorbance at 530 to 600 nm is extremely low (that is, the transmittance is high). When the combination of the absorption wavelength of the short peak on the short wavelength side of the phthalocyanine compound (2) is close to the maximum absorption wavelength of the phthalocyanine compound (1), while maintaining the light absorption characteristics of the phthalocyanine compound (1), The entire absorption wavelength can be moved to the long wavelength side. For this reason, the absorbance in the red wavelength region (exceeding 600 nm and 700 nm or less) that is unnecessary for the green pixel is relatively larger than the absorbance in the green wavelength region (500 to 600 nm). That is, the absorbance at 500 to 600 nm, which is the green wavelength region, is relatively low (that is, the transmittance is high) compared to other wavelength regions such as the red wavelength region. As a result, the composition of the present invention has high luminance when used in a color filter, and can exhibit a good color as a green pigment.

  Moreover, the composition of this invention contains the phthalocyanine compound (2) which has a maximum absorption wavelength exceeding 700 nm and 750 nm or less. In recent years, LCDs increasingly use white LEDs (Light Emitting Diodes) as backlights, but white LEDs emit near-infrared light of 700 to 750 nm although it is weak light. In particular, a strong light emission is observed in the vicinity of 710 nm from an LED of a type that emits RGB phosphors with a short wavelength LED. When the composition of the present invention is used in an LCD using an LED as a backlight source, an effect of being able to cut a wavelength of 700 to 750 nm, which is an extra light emission of the LED, is also achieved. Regardless of the type of LED, when light in the above wavelength range is emitted from the backlight, peripheral devices such as remote controllers such as air conditioners and video decks that use light in the wavelength range as an optical communication means are used in the vicinity. Although there is a possibility of causing malfunction of the device, and further, the transmission optical communication device, the effect of preventing malfunction of the peripheral device can also be obtained by using the composition of the present invention.

  Therefore, when the composition of the present invention is used in a color filter, the color of green is good, the luminance is high, and the effects of being able to cut light having a wavelength of 700 to 750 nm are also exhibited.

  Furthermore, according to the present invention, the heat resistance of the composition containing the phthalocyanine compounds (1) and (2) can be improved by appropriately selecting the phthalocyanine compounds (1) and (2). Specific structures of the phthalocyanine compounds (1) and (2) for stabilizing the composition will be described in detail below. For example, when the composition of the present invention is used in an electronic device, the behavior is stabilized. Can be made.

  The ratio of the phthalocyanine compounds (1) and (2) contained in the composition of the present invention is not particularly limited as long as the above effects can be obtained, but the phthalocyanine compound (2) is 100 parts by weight of the phthalocyanine compound (1). The content is preferably 0.1 to 50 parts by weight, and more preferably 1 to 30 parts by weight. Furthermore, it is preferable that a phthalocyanine compound (2) is 5-20 weight part with respect to 100 weight part of phthalocyanine compounds (1). By setting the content of the phthalocyanine compound (2) to 0.1 parts by weight or more with respect to the content of the phthalocyanine compound (1), the transmittance of the green wavelength region (500 to 550 nm) of the composition is changed to the red wavelength region (600 It can be made sufficiently large compared to the transmittance of ˜700 nm). Furthermore, the said effect can be acquired more notably by making content of a phthalocyanine compound (2) with respect to content of a phthalocyanine compound (1) into 1 weight part or more. On the other hand, by setting the content of the phthalocyanine compound (2) to 50 parts by weight or less with respect to the content of the phthalocyanine compound (1), the effect of the phthalocyanine compound (1), particularly a sufficient color as a green colorant is achieved. Can do. Furthermore, the said effect can be acquired more notably by making content of a phthalocyanine compound (2) with respect to content of a phthalocyanine compound (1) into 30 weight part or less.

  The phthalocyanine compounds (1) and (2) contained in the composition of the present invention will be specifically described below.

[Phthalocyanine compound (1)]
The phthalocyanine compound (1) contained in the composition of the present invention is a phthalocyanine compound having a maximum absorption wavelength at 600 to 700 nm. Among the phthalocyanine compounds (1) having the maximum absorption wavelength in the above range, the structures shown in the following phthalocyanine compounds (1-1), (1-2), and (1-3) are particularly preferable. That is, the phthalocyanine compound (1) has the following formula (1):

In the above formula (1), Z _{1 to} Z ₁₆ are each independently a hydrogen atom, a halogen atom or the following formula (3):

In the above formula (3), R ₁ represents a halogen atom, an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, a cyano group, a nitro group, or an ester group (—COOR ₂ : R ₂ represents an alkyl group having 1 to 20 carbon atoms),
m is an integer from 0 to 5;
Represents a substituted phenoxy group (1) represented by:
M represents metal-free, metal, metal oxide or metal halide;
In this case, _{1 to} 5 of Z _{1 to} Z ₁₆ are substituted phenoxy groups (1), and the rest are hydrogen atoms or halogen atoms;
A phthalocyanine compound (1-1) represented by:
In the above formula (1), Z _{1 to} Z ₁₆ are each independently a hydrogen atom, a halogen atom or the following formula (4):

In the above formula (4), R ₃ represents an alkylene group having 1 to 5 carbon atoms,
R ₄ represents an alkyl group having 1 to 5 carbon atoms,
R ₅ is a halogen atom, an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, a cyano group, a nitro group, or an ester group (—COOR ₆ : R ₆ is the number of carbon atoms. 1-20 alkyl groups)
a is 1 or 2,
b is an integer from 0 to 4;
-COOR ₃ OR ₄ -containing phenoxy group represented by
M represents metal-free, metal, metal oxide or metal halide;
In this case, one or more and less than four of Z _{1 to} Z ₁₆ are —COOR ₃ OR ₄ -containing phenoxy groups, and the rest are hydrogen atoms or halogen atoms;
In the formula (1), Z _{1 to} Z ₁₆ each independently represent a halogen atom,
M represents metal-free, metal, metal oxide or metal halide;
It is preferable in it being a phthalocyanine compound (1-3) shown by these.

  In addition, a phthalocyanine compound (1-1), (1-2), (1-3) may be used independently, or may be used in combination of 2 or more type.

Hereinafter, the phthalocyanine compounds (1-1), (1-2), and (1-3) will be specifically described. In the present specification, Z ₁ , Z ₄ , Z ₅ , Z ₈ , Z ₉ , Z ₁₂ , Z ₁₃ and Z ₁₆ in the formula (1) are each substituted with 8 α-positions of the phthalocyanine nucleus. These substituents are also referred to as α-position substituents. Similarly, in formula (1), Z ₂ , Z ₃ , Z ₆ , Z ₇ , Z ₁₀ , Z ₁₁ , Z ₁₄ and Z ₁₅ are each substituted with 8 β-positions of the phthalocyanine nucleus. In order to represent substituents, these substituents are also referred to as β-position substituents. The β-position substituent is effective in improving heat resistance, and the α-position substituent is effective in improving solvent solubility. Therefore, it is preferable to mix the two in a balanced manner.

(Phthalocyanine compound (1-1): phthalocyanine dye)
Hereinafter, the phthalocyanine compound (1-1) will be described.

In the above formula (1), Z _{1 to} Z ₁₆ which are substituents at the α-position and β-position of the phthalocyanine nucleus are each independently a hydrogen atom, a halogen atom or the following formula (3):

A substituted phenoxy group (1) represented by the formula (herein simply referred to as “substituted phenoxy group (1)”). At this time, Z _{1 to} Z ₁₆ may be the same or different. Further, the substituted phenoxy group (1) may be substituted at any position of Z _{1 to} Z ₁₆ . That is, the position where the hydrogen atom, halogen atom or substituted phenoxy group (1) occupies the α-position and β-position of the phthalocyanine nucleus is arbitrary and is not particularly limited.

Of Z _{1 to} Z _{16 in} the above formula (1), 1 to 5 are substituted with a substituted phenoxy group (1), and the rest are hydrogen atoms and / or halogen atoms. When the number of substituted phenoxy groups (1) introduced is outside the above range, the maximum absorption wavelength of the resulting phthalocyanine compound may be outside the range of 600 to 700 nm. Among Z _{1 to} Z _16, the number of substituted phenoxy groups (1) is preferably 1.5 to 4, and more preferably 2 to 3. At this time, it is preferable that all the remainders are halogen atoms.

As will be described in detail below, generally, when the number of substituted phenoxy groups (1) introduced is large, conjugation expands and the maximum absorption wavelength of the resulting phthalocyanine compound (1) shifts to the longer wavelength side. There is a tendency to shift to the longer wavelength side. Further, when the central metal M is a trivalent or higher metal, metal oxide or metal halide (for example, M is indium chloride), even if the number of substituted phenoxy groups (1) introduced is the same, three The maximum absorption wavelength of a phthalocyanine compound containing a trivalent or higher metal tends to move to the longer wavelength side as compared with a phthalocyanine compound containing a metal less than the valence. Therefore, when the central metal M is a trivalent or higher metal, metal oxide or metal halide, Z _{1 to} Z ₁₆ are substituted with 1 or more and less than 3 substituted phenoxy groups (1), and the rest It is preferably a hydrogen atom and / or a halogen atom. Further, it is more preferable that Z _{1 to} Z ₁₆ are substituted with 1 to 2 substituted phenoxy groups (1), and the remainder is a hydrogen atom and / or a halogen atom.

The phthalocyanine compound (1-1) contained in the composition of the present invention includes a case where a plurality of types of compounds are present in the form of a mixture, in addition to the case of being a type of compound. For example, the number of hydrogen atoms, halogen atoms or substituted phenoxy groups (1), which are the substituents of Z _{1 to} Z _{16 in} the above formula (1), is expressed as an average of the respective phthalocyanine compounds, and therefore is not necessarily an integer. do not become.

  Here, the halogen atom is not particularly limited, and any of a fluorine atom, a chlorine atom, a bromine atom and an iodine atom can be selected. Preferred are a fluorine atom, a chlorine atom and a bromine atom, and particularly preferred is a chlorine atom.

In the above formula (3) showing the substituted phenoxy group (1), R ₁ is a halogen atom, an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, a cyano group, a nitro group, Alternatively, it represents an ester group (—COOR ₂ : R ₂ is an alkyl group having 1 to 20 carbon atoms). R ₁ is preferably a halogen atom, an alkyl group having 1 to 8 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, or an ester group, and particularly preferably an ester group.

In the above formula represents a substituted phenoxy group (1) (3), m represents the number of -R ₁ is attached to the phenoxy group, an integer from 0 to 5, to improve the solubility in a solvent , M is preferably 1 to 3, and more preferably 1 to 2. Here, the bonding position of —R ₁ is not particularly limited. For example, when m is 1, the substitution position on the benzene ring of the —R ₁ group is not particularly limited, and is any one of the ortho position (second position), the meta position (third position), and the para position (fourth position). Can be placed in position. In consideration of color, luminance, solvent solubility, etc., the 2nd and 4th positions are preferable, and the 4th position is particularly preferable. When the relatively bulky substituent —R ₁ is arranged at the 4-position, the resulting phthalocyanine compound has a particularly high transmittance in the vicinity of 520 to 560 nm, which is a wavelength of strong backlight light. Moreover, when the relatively bulky substituent —R ₁ is arranged at the 4-position, the solvent solubility of the resulting phthalocyanine compound is improved. Moreover, when m is 2, the substitution position on the benzene ring of the —R ₁ group is not particularly limited. However, in consideration of color, luminance, solvent solubility, etc., the 2, 4th position, the 2, 5th position, the 2nd position, , 6th, 3rd, 4th, etc. are preferred, and 2nd, 4th, 2nd, 6th are more preferred. When m is 2 or more, R ₁ may be the same as or different from each other.

The halogen atom for R ₁ may be any of a fluorine atom, a chlorine atom, a bromine atom and an iodine atom. Preferred are a fluorine atom and a chlorine atom, and particularly preferred is a chlorine atom.

The alkyl group having 1 to 20 carbon atoms of R ₁ may be linear, branched or cyclic. Examples of the alkyl group for R ₁ 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, a tert-butyl group, an n-pentyl group, and an iso-amyl group. , A tert-pentyl group, a neopentyl group, an n-hexyl group, an n-octyl group, a 2-ethylhexyl group, an n-decyl group, and the like, and a cyclohexyl group, a cycloheptyl group, Examples thereof include cyclic alkyl groups such as a cyclooctyl group. Among these, in order to improve solubility in a solvent, an alkyl group having 1 to 8 carbon atoms is preferable, a methyl group, an ethyl group, an n-propyl group, and an isopropyl group are more preferable, and a methyl group and an ethyl group are further included. preferable.

Examples of the alkoxy group having 1 to 20 carbon atoms of R ₁ include methoxy group, ethoxy group, n-propoxy group, isopropoxy group, n-butoxy group, n-octyloxy group, and 2-ethylhexyloxy group. Can be mentioned. Among these, those having 1 to 8 carbon atoms are preferable, and in order to improve the solubility in a solvent, alkoxy groups having 1 to 5 carbon atoms are preferable, and a methoxy group, an ethoxy group, and an n-propoxy group. An isopropoxy group is more preferable, and a methoxy group and an ethoxy group are further preferable.

For R ₁ of the ester group (-COOR _2), R ₂ is the same as the description of the above-described alkyl group R _1, since the description thereof is omitted, improving the solubility in a solvent, R ₂ is An alkyl group having 1 to 8 carbon atoms is preferable, a methyl group, an ethyl group, an n-propyl group, and an isopropyl group are more preferable, and a methyl group and an ethyl group are further preferable.

  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, specifically copper, zinc, cobalt, nickel, iron, vanadyl, titanyl, tin (II) chloride, more preferably zinc and copper. . This is because zinc and copper are excellent in heat resistance and light resistance. In particular, when the composition of the present invention is used for an LCD filter, high optical properties (transparency) are required. Therefore, for the above-mentioned use, a phthalocyanine compound in which the central metal having excellent optical properties (transparency) is zinc is preferable.

  Accordingly, a preferred example of the phthalocyanine compound (1-1) of the present invention is the following compound (A). The following formula represents that two substituted phenoxy groups (1) and 14 chlorine atoms are bonded to the α-position and β-position, and this is the same for other examples of phthalocyanine compounds.

  In addition, the formula showing the following phthalocyanine compound (A) is described with the intention of a mixture in which an average of two substituted phenoxy groups (1) and an average of 14 chlorine atoms are bonded to a phthalocyanine nucleus. In the following, the maximum absorption wavelength (λmax) is shown in parentheses described with each exemplified compound. In the present specification, the “maximum absorption wavelength (λmax)” is measured by the method described in Examples described later. Moreover, in the following chemical formulas, the substituents with “*” written on the right side are bound to any position of “*” attached to the phthalocyanine nucleus.

(Phthalocyanine compound (1-2): phthalocyanine dye)
Hereinafter, the phthalocyanine compound (1-2) will be described.

In the above formula (1), Z _{1 to} Z ₁₆ that are substituents at the α-position and β-position of the phthalocyanine nucleus are each independently a hydrogen atom, a halogen atom or the following formula (4):

-COOR ₃ OR ₄ -containing phenoxy group represented by the formula (herein, simply referred to as “—COOR ₃ OR ₄ -containing phenoxy group”). At this time, Z _{1 to} Z ₁₆ may be the same or different. In addition, the —COOR ₃ OR ₄ -containing phenoxy group may be substituted at any position of Z _{1 to} Z ₁₆ . That is, the position where the hydrogen atom, halogen atom, or —COOR ₃ OR ₄ -containing phenoxy group occupies the α-position and β-position of the phthalocyanine nucleus is arbitrary and is not particularly limited.

Among Z _{1 to} Z _{16 in} the above formula (1), 1 or more and less than 4 are substituted with a —COOR ₃ OR ₄ -containing phenoxy group, and the remainder is a hydrogen atom or a halogen atom. Among Z _{1 to} Z _16, the number of —COOR ₃ OR ₄ -containing phenoxy groups is preferably 1.5 to 3.5, and more preferably 2 to 3. At this time, it is preferable that all the remainders are halogen atoms.

The phthalocyanine compound (1-2) contained in the composition of the present invention includes a case where a plurality of types of compounds are present in the form of a mixture in addition to the case of being a type of compound. For this reason, in such a case, the number of —COOR ₃ OR ₄ -containing phenoxy groups in the α-position and β-position substituents in the above formula (1) is expressed as the average of each phthalocyanine compound. Therefore, it is not necessarily an integer.

  Here, the halogen atom is not particularly limited, and any of a fluorine atom, a chlorine atom, a bromine atom and an iodine atom can be selected. Preferred are a fluorine atom, a chlorine atom and a bromine atom, and particularly preferred is a chlorine atom.

In the above formula (4) showing a —COOR ₃ OR ₄ -containing phenoxy group, R ₃ represents an alkylene group having 1 to 5 carbon atoms. Examples of such groups include a methylene group (—CH ₂ —), an ethylene group (—CH ₂ CH ₂ —), a trimethylene group (—CH ₂ CH ₂ CH ₂ —), and a propylene group (—CH (CH ₃ ) CH. _2- ) and tetramethylene groups (—CH ₂ CH ₂ CH ₂ CH ₂ —) and the like include straight-chain and branched-chain groups. Among these, a methylene group, an ethylene group, and a propylene group are preferable, and an ethylene group is most preferable.

R ₄ represents an alkyl group having 1 to 5 carbon atoms, more preferably 1 to 3 carbon atoms. Examples of such alkyl groups include linear and branched alkyl groups such as methyl, ethyl, propyl, isopropyl, n-butyl, pentyl, neopentyl, sec-butyl, and tert-butyl. Is mentioned. Of these, a methyl group, an ethyl group, an n-propyl group, and an isopropyl group are preferable, and a methyl group is most preferable.

Further, R ₅ is a halogen atom, an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, a cyano group, a nitro group, or an ester group (—COOR ₆ : R ₆ is carbon R ₅ is a halogen atom, an alkyl group having 1 to 8 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, or an ester group. A halogen atom is preferable, and a halogen atom is particularly preferable.

Since the explanation of the halogen atom of R ₅ is the same as the explanation of R ₁ in the phthalocyanine compound (1-1), the explanation thereof is omitted, but a chlorine atom is particularly preferred.

The description of the alkyl group having 1 to 20 carbon atoms of R ₅ is the same as the description of R ₁ in the phthalocyanine compound (1-1), and thus the description thereof is omitted, but 1 to 8 carbon atoms. The alkyl group is preferably a methyl group, an ethyl group, an n-propyl group or an isopropyl group, more preferably a methyl group or an ethyl group.

The description of the alkoxy group having 1 to 20 carbon atoms of R ₅ is the same as the description of R ₁ in the phthalocyanine compound (1-1), and thus the description thereof is omitted, but the solubility in a solvent is improved. Therefore, an alkoxy group having 1 to 8 carbon atoms is preferable, and a methoxy group and an ethoxy group are particularly preferable.

The description of R ₆ in the ester group of R ₅ (—COOR ₆ : R ₆ is an alkyl group having 1 to 20 carbon atoms) is the R ₂ that uses R ₁ in the phthalocyanine compound (1-1). However, in order to improve solubility in a solvent, an alkyl group having 1 to 8 carbon atoms is preferable, and a methyl group, an ethyl group, an n-propyl group, an isopropyl group is preferable. R ₆ is more preferably a methyl group or an ethyl group.

In the above formula (4) showing a —COOR ₃ OR ₄ -containing phenoxy group, a represents the number of —COOR ₃ OR ₄ groups bonded to the phenoxy group, 1 or 2, and b represents the phenoxy group. It represents the number to which the R ₅ group is bonded, and is an integer of 0-4. a and b may be any combination as long as the relationship of a + b ≦ 5 is satisfied. However, a = 1 and b = 0 or 1 are preferable, and in particular, a = 1 and b = 0. It is preferable.

Here, the bonding position of the —COOR ₃ OR ₄ group is not particularly limited. For example, when a is 1, the substitution position on the benzene ring of the —COOR ₃ OR ₄ group is not particularly limited, and is in the ortho position (2nd position), meta position (3rd position) or para position (4th position). It can be arranged at any position. In consideration of color, luminance, solvent solubility, etc., the 2nd and 4th positions are preferable, and the 4th position is particularly preferable. When the relatively bulky substituent —COOR ₃ OR ₄ is arranged at the 4-position, the obtained phthalocyanine compound has a high transmittance in the vicinity of 520 to 545 nm, which is a green wavelength. Further, when the relatively bulky substituent —COOR ₃ OR ₄ is arranged at the 4-position, the solvent solubility of the resulting phthalocyanine compound is improved. When a is 2, the position of substitution on the benzene ring of the —COOR ₃ OR ₄ group is not particularly limited, but considering the color, brightness, solvent solubility, etc., the 2, 4th, 2, 5th, 2nd, , 6th, 3rd, 4th, etc. are preferred, and 2nd, 4th, 2,6th are more preferred. When a is 2, COOR ₃ OR ₄ may be the same as or different from each other. Further, when b is 1 or more, the substitution position on the benzene ring of the ₅ group -R is not particularly limited. For example, when a and b are 1, the —COOR ₃ OR ₄ group and R ₅ are 2, 4th, 2,5th, 2,6th, 3th, in consideration of color, brightness, solvent solubility and the like. , 4th and the like are preferable, and the 2nd, 4th and 2nd and 6th positions are more preferable. In this case, the —COOR ₃ OR ₄ group and R ₅ may be at the above substitution positions. Thus, for example, “-COOR ₃ OR ₄ group and R ₅ are substituted at the 2- and 4-positions” means “-COOR ₃ OR ₄ group is substituted at the 2-position and R ₅ is substituted at the 4-position. And the “-COOR ₃ OR ₄ group is substituted at the 4-position and R ₅ is substituted at the 2-position” form. When b is 2 or more, R ₅ may be the same as or different from each other.

  In the above formula (1), M represents a metal-free, metal, metal oxide or metal halide. Since the explanation about M is the same as that of the phthalocyanine compound (1-1), explanation thereof is omitted, but zinc and copper are preferable.

  Accordingly, a preferred example of the phthalocyanine compound (1-2) of the present invention is the following compound (B).

(Phthalocyanine compound (1-3): phthalocyanine pigment)
Hereinafter, the phthalocyanine compound (1-3) will be described.

In the above formula (1), Z _{1 to} Z ₁₆ each independently represent a halogen atom. Here, the halogen atom is not particularly limited, and any of a fluorine atom, a chlorine atom, a bromine atom and an iodine atom can be selected. Preferred are a fluorine atom, a chlorine atom and a bromine atom, and particularly preferred are a chlorine atom and a bromine atom.

At this time, the types of halogen atoms represented by Z _{1 to} Z ₁₆ may be the same or different, but the number of halogen atoms contained is preferably 3 or less, and preferably 2 or less. It is more preferable.

  The phthalocyanine compound (1-3) contained in the composition of the present invention includes not only a type of compound but also the presence of a plurality of types of compounds in the form of a mixture.

  In the above formula (1), M represents a metal-free, metal, metal oxide or metal halide. Since the explanation about M is the same as that of the phthalocyanine compound (1-1), explanation thereof is omitted, but zinc and copper are preferable.

  Accordingly, preferred examples of the phthalocyanine compound (1-3) of the present invention include brominated chlorinated copper phthalocyanine (CIPig. Green 36: λmax = 664 nm) and brominated chlorinated zinc phthalocyanine (CIPig. Green 58: λmax = 667 nm). ).

  The phthalocyanine compounds (1-1) and (1-2) are phthalocyanine dyes and the phthalocyanine compound (1-3) is a phthalocyanine pigment, both of which are green dyes. Among the phthalocyanine compounds (1) having a maximum absorption wavelength at 600 to 700 nm, the phthalocyanine compounds (1-1), (1-2) and (1-3) are the phthalocyanine compounds (2) described below. It is particularly suitable as a green dye to be combined with. Among these, phthalocyanine compounds (1-1) and (1-2), which are dyes, are preferable as green pigments to be combined with the phthalocyanine compound (2), and the phthalocyanine compound (1-2) is preferably a phthalocyanine compound (2). ) Is particularly preferable as a green colorant to be combined. In particular, among the phthalocyanine compounds (1-2), those having the structure of the compound (B) are particularly suitable.

  The phthalocyanine compound (1) may be a dye that dissolves in a solvent or may be a pigment that is atomized to such an extent that haze does not become a problem. However, in order to improve light transmittance, A dye that dissolves is preferred.

[Phthalocyanine compound (2)]
The phthalocyanine compound (2) contained in the composition of the present invention is a phthalocyanine compound having a maximum absorption wavelength exceeding 700 nm and not more than 750 nm. Therefore, the composition of the present invention contains phthalocyanine compounds (1) and (2), and these phthalocyanine compounds (1) and (2) have structures different from each other, and phthalocyanine compound (1) and phthalocyanine compound (2) is distinguished from each other by its maximum absorption wavelength. And among the phthalocyanine compounds (2) having the maximum absorption wavelength in the above range, it has a second absorption peak (sub peak) at 620 to 700 nm which is a short wavelength side with respect to the maximum absorption wavelength of the phthalocyanine compound (2). It is preferable. When a combination of wavelengths in which the absorption wavelength of the sub-peak of the phthalocyanine compound (2) is close to the maximum absorption wavelength of the phthalocyanine compound (1) is used, the light absorption characteristics of the phthalocyanine compound (1) are maintained while being used alone. The entire absorption wavelength can be moved to the long wavelength side. Furthermore, the phthalocyanine compound (2) has a feature that the absorbance at 530 to 600 nm is extremely low (that is, the transmittance is high). For this reason, the absorbance in the red wavelength region (exceeding 600 nm and 700 nm or less) that is unnecessary for the green pixel is relatively larger than the absorbance in the green wavelength region (500 to 600 nm). That is, the absorbance at 500 to 600 nm, which is the green wavelength region, is relatively low (that is, the transmittance is high) compared to other wavelength regions such as the red wavelength region. As a result, the composition of the present invention has high luminance when used in a color filter, and can exhibit a good color as a green pigment.

  The phthalocyanine compound (2) preferably has a structure shown in the following phthalocyanine compound (2-1). That is, the phthalocyanine compound (2) has the following formula (2):

In the above formula (2), Z ₁ ′ to Z ₁₆ ′ are each independently a halogen atom or the following formula (5):

In the above formula (5), R ₇ represents a halogen atom, an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, a cyano group, a nitro group, or an ester group (—COOR ₈ : R ₈ represents an alkyl group having 1 to 20 carbon atoms),
n is an integer from 0 to 5;
Represents a substituted phenoxy group (2) represented by:
M represents metal-free, metal, metal oxide or metal halide;
In this case, 3 to _{16 of} Z ₁ ′ to Z ₁₆ ′ are substituted phenoxy groups (2), and the rest are halogen atoms;
It is preferable in it being a phthalocyanine compound (2-1) shown by these.

Hereinafter, the phthalocyanine compound (2-1) will be specifically described. In the present specification, in formula (2), Z ₁ ′, Z ₄ ′, Z ₅ ′, Z ₈ ′, Z ₉ ′, Z ₁₂ ′, Z ₁₃ ′ and Z ₁₆ ′ are each a phthalocyanine nucleus. These eight substituents are also referred to as α-position substituents. Similarly, Z ₂ ′, Z ₃ ′, Z ₆ ′, Z ₇ ′, Z ₁₀ ′, Z ₁₁ ′, Z ₁₄ ′ and Z ₁₅ ′ in the formula (2) are respectively phthalocyanine nuclei. These substituents are also referred to as β-position substituents because they represent eight substituents at the β-position. The β-position substituent is effective in improving heat resistance, and the α-position substituent is effective in improving solvent solubility. Therefore, it is preferable to mix the two in a balanced manner.

(Phthalocyanine compound (2-1))
Hereinafter, the phthalocyanine compound (2-1) will be described.

In the above formula (2), Z ₁ ′ to Z ₁₆ ′ are each independently a halogen atom or the following formula (5):

And a substituted phenoxy group (2) (also simply referred to as “substituted phenoxy group (2)” in the present specification). At this time, Z ₁ ′ to Z ₁₆ ′ may be the same or different.

Of Z ₁ ′ to Z ₁₆ ′ in the above formula (2), 3 to ₁₆ are substituted with the substituted phenoxy group (2), and the rest are halogen atoms. Of Z ₁ ′ to Z ₁₆ ′, the substituted phenoxy group (2) is preferably the following number depending on the valence of the central metal M.

That is, when M is a divalent metal (for example, copper, zinc, etc.), the greater the number of substituted phenoxy groups (2), the greater the conjugation, and the maximum absorption wavelength of the phthalocyanine compound moves to the longer wavelength side. because, it is possible to obtain a composition suitable for the green color filter applications, among Z ₁ '~Z _16', substituted phenoxy group (2) is more preferably to be 10 to 16 pieces, 11 More preferably, the number is 15, and particularly preferably 12 to 14.

Further, when the central metal M is a trivalent or higher metal (for example, indium chloride), the maximum absorption wavelength of the phthalocyanine compound tends to be increased by the central metal, so that the substituted phenoxy group (2) Even if the number is small, a composition suitable for a green color filter can be obtained. Therefore, it is preferable that the number of substituted phenoxy groups is smaller than that in the case where the central metal is a divalent metal. Specifically, among Z ₁ ′ to Z ₁₆ ′, the number of substituted phenoxy groups (2) is preferably 3 to 12, and more preferably 4 to 10. If it is such a range, the composition suitable for a green color filter use can be obtained.

  The phthalocyanine compound (2) contained in the composition of the present invention includes a case where a plurality of types of compounds are present in the form of a mixture, in addition to the case of being a type of compound. For this reason, in such a case, the number of substituted phenoxy groups (2) in the above formula (2) is not necessarily an integer because it is expressed as the average of each phthalocyanine compound.

  Here, the halogen atom is not particularly limited, and any of a fluorine atom, a chlorine atom, a bromine atom and an iodine atom can be selected. Preferred are a fluorine atom, a chlorine atom and a bromine atom, and particularly preferred are a fluorine atom and a chlorine atom.

In the above formula (5) showing the substituted phenoxy group (2), R ₇ is a halogen atom, an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, a cyano group, a nitro group, Or an ester group (—COOR ₈ : R ₈ is an alkyl group having 1 to 20 carbon atoms), and R ₇ is particularly preferably a halogen atom or an alkyl group having 1 to 20 carbon atoms. .

In the above formula represents a substituted phenoxy group (2) (5), n represents the number of -R ₇ is attached to the phenoxy group, an integer from 0 to 5, to improve the solubility in a solvent , N is preferably 1 to 3, and more preferably 1 to 2. Here, the substitution position on the benzene ring of the -R ₇ group is not particularly limited. For example, when n is 1, the substitution position on the benzene ring of the —R ₇ group is located at any position of the ortho position (2 position), meta position (3 position) or para position (4 position). However, considering the solvent solubility, the maximum absorption wavelength, the sharpness of the absorption wavelength, etc., the 2nd and 4th positions are preferable, and the 4th position is particularly preferable. Further, when n is 2, the substitution position on the benzene ring of the —R ₇ group is not particularly limited, but considering the solvent solubility, the maximum absorption wavelength, etc., the 2, 4th, 2,5th, 2, 6th, 3rd, 4th, etc. are preferred, and 2nd, 5th, 2nd, 6th are more preferred. When n is 2 or more, R ₇ may be the same as or different from each other.

Since the explanation of the halogen atom of R ₇ is the same as the explanation of R ₁ in the phthalocyanine compound (1-1), its explanation is omitted, but a chlorine atom is particularly preferred.

The description of the alkyl group having 1 to 20 carbon atoms of R ₇ is the same as the description of R ₁ in the phthalocyanine compound (1-1), and thus the description thereof is omitted, but the solubility in a solvent is improved. Therefore, an alkyl group having 1 to 8 carbon atoms is preferable, a methyl group, an ethyl group, an n-propyl group, and an isopropyl group are more preferable, and a methyl group and an ethyl group are particularly preferable.

The description of the alkoxy group having 1 to 20 carbon atoms of R ₇ is the same as the description of R ₁ in the phthalocyanine compound (1-1), and thus the description thereof is omitted, but the solubility in a solvent is improved. Therefore, an alkoxy group having 1 to 8 carbon atoms is preferable, and a methoxy group and an ethoxy group are particularly preferable.

The description of R ₈ in the ester group of R ₇ (—COOR ₈ : R ₈ is an alkyl group having 1 to 20 carbon atoms) is the R ₂ that uses R ₁ in the phthalocyanine compound (1-1). However, in order to improve solubility in a solvent, an alkyl group having 1 to 8 carbon atoms is preferable, and a methyl group, an ethyl group, an n-propyl group, an isopropyl group is preferable. R ₈ is more preferably a methyl group or an ethyl group.

  In the above formula (2), 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, specifically copper, zinc, cobalt, nickel, iron, vanadyl, titanyl, indium chloride, tin (II) chloride, zinc, copper and chloride. Indium is more preferred.

  As described above, when the number of substituted phenoxy groups (2) is increased in order to shift the maximum absorption wavelength of the phthalocyanine compound to the longer wavelength side and obtain a composition suitable for green color filter application, Metals are preferred, and zinc and copper are particularly preferred. On the other hand, in view of the Gram extinction coefficient, when the number of substituted phenoxy groups (2) is reduced, trivalent metals are preferable, and indium, indium oxides and chlorides are particularly preferable. In particular, indium halide is preferable, and indium chloride is particularly preferable from the viewpoint of increasing the maximum absorption wavelength of the phthalocyanine compound and obtaining suitable absorption characteristics as a composition for use in green color filter applications.

  Accordingly, preferred examples of the phthalocyanine compound (2-1) of the present invention include the following compounds (a) to (co).

  In addition, the said phthalocyanine compound (I) was described following the description of the said phthalocyanine compound (a), and takes the same substitution form.

  The phthalocyanine compounds (e) to (c) are described following the description of the phthalocyanine compound (c), and take the same substitution form.

  In addition, the said phthalocyanine compound (co) is described according to description of the said phthalocyanine compound (ke), and takes the same substitution form.

  The phthalocyanine compound having the specific structure as described above exhibits a maximum absorption wavelength in a specific wavelength range of more than 700 nm and 750 nm or less. Therefore, it is possible to cut a wavelength of 700 to 750 nm which is an extra light emission in an LCD using a specific LED as a backlight. As a result, when the composition of the present invention is applied to a color filter, it is possible to block light in a wavelength region that causes a malfunction of a communication device.

  Then, by adding the phthalocyanine compound (2) to the phthalocyanine compound (1) which is a green pigment, the phthalocyanine compounds (1) and (2) interact with each other, and light having a preferable color tone in a green pixel The absorbance of light having a wavelength exceeding 600 nm and not exceeding 700 nm can be relatively increased as compared with the absorbance in the green wavelength region (500 to 600 nm). That is, by using a composition containing the phthalocyanine compounds (1) and (2), the light transmittance in the green wavelength region can be selectively increased. As a result, since the composition of the present invention exhibits a good color and high brightness as a green colorant compared with only the phthalocyanine compound (1) which is a green colorant, the filter using the composition of the present invention is It can be suitably used for an LCD that reproduces pure green.

  Furthermore, the phthalocyanine compound (2) having the above structure has a relatively high solubility in an organic solvent among general phthalocyanine compounds, and by interacting with the phthalocyanine compound (1), the solubility of the entire composition is increased. There is also an effect that it can be increased. Therefore, when manufacturing a color filter or the like, application becomes easy, and the color filter or the like can be manufactured at a low cost.

  Among the phthalocyanine compounds (2), in particular, the phthalocyanine compounds having the structures of the above phthalocyanine compounds (a) to (co) have a maximum absorption wavelength exceeding 700 nm and 750 nm or less, and are combined with the phthalocyanine compound (1). Suitable as a compound. Of the phthalocyanine compounds (a) to (co), phthalocyanine compounds (e), (f), (g), and (co) are preferable. When the phthalocyanine compounds (e), (f), (g), and (co) are used, not only the color and luminance can be improved, but also the heat resistance of the composition can be improved.

  Furthermore, as the phthalocyanine compound (2), among the above phthalocyanine compounds, those having a maximum absorption wavelength of more than 700 nm and not more than 730 nm are preferable. That is, as the phthalocyanine compound (2), phthalocyanine compounds (e), (f), and (g) are preferable.

  The phthalocyanine compounds (1) and (2) of the present invention have good solubility in ether solvents. This is due to the presence of substituents substituted on the phthalocyanine nucleus and the number of substitutions. When applying the phthalocyanine compound, the solubility of the phthalocyanine compound 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. The phthalocyanine compounds (1) and (2) having an appropriate absorption wavelength can be obtained by selecting the type, number and central metal of the 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 color filter applications. The phthalocyanine compounds (1) and (2) of the present invention each preferably have a solubility in PGMEA, which is an ether solvent, of 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.

[Method for Producing Phthalocyanine Compounds (1) and (2)]
The production method of the phthalocyanine compounds (1) and (2) of the present invention is not particularly limited, and a conventionally known method can be appropriately used. Preferably, the phthalocyanine compounds (1) and (2) are preferably used in a molten state or in an organic solvent. A method of cyclizing a nitrile compound and a metal salt is particularly preferably used. Hereinafter, a particularly preferred embodiment of the production method will be described by taking the phthalocyanine compound (1-1) of the present invention as an example. However, the present invention is not limited to the following preferred embodiments.

  That is, the following formula (I):

A phthalonitrile compound (1) represented by the following formula (II):

A phthalonitrile compound (2) represented by the following formula (III):

A phthalonitrile compound (3) represented by formula (IV):

And a phthalonitrile compound (4) represented by formula (1) selected from the group consisting of metal oxides, metal carbonyls, metal halides, and organic acid metals (also collectively referred to as “metal salts” in the present specification) By carrying out the cyclization reaction, the phthalocyanine compound of the present invention can be produced.

In the above formulas (I) to (IV), Z _{1 to} Z ₁₆ are defined by the structure of the desired phthalocyanine compound (1-1). Specifically, in the above formula (I) ~ (IV), Z 1 ~Z 16 , respectively, Z ₁ of Z ₁ to Z ₁₆ in the formula (1), the formula (2) 'to Z _Since it is the same as the definition of ₁₆ ', explanation is omitted here.

  In the above embodiment, the starting phthalonitrile compounds of formulas (I) to (IV) can be synthesized by a conventionally known method such as the method disclosed in JP-A No. 64-45474, or commercially available. Can be used, but preferably, the following formula (V):

In the formula, X ₁ , X ₂ , X ₃ and X ₄ are each independently halogen atoms such as fluorine atom, chlorine atom, bromine atom and iodine atom, preferably fluorine atom, chlorine atom and bromine atom, particularly preferably Represents a fluorine atom or a chlorine atom,
Is obtained by reacting with a HOX. Specifically, the substituent “OX” in the above formula corresponds to the substituted phenoxy group (1) represented by the above formula (3) in the above formula (1) representing the phthalocyanine compound (1-1). In the above formula (1) showing the phthalocyanine compound (1-2), it corresponds to the —COOR ₃ OR ₄ -containing phenoxy group represented by the above formula (4) and represents the phthalocyanine compound (2-1) ( In 2), it corresponds to the substituted phenoxy group (2) represented by the above formula (5). In the phthalocyanine compound (1-3), it is not necessary to specifically react the phthalonitrile derivative with HOX, and a phthalonitrile derivative having an appropriate halogen atom may be used as it is.

  In particular, when tetrafluorophthalonitrile (hereinafter abbreviated as TFPN), tetrachlorophthalonitrile (hereinafter abbreviated as TCPN) or tetrabromophthalonitrile (hereinafter abbreviated as TBPN) is used as a starting material, HOX In the case of TFPN, the fluorine atoms at the 4th and 5th positions preferentially, and in the case of TCPN or TBPN, they react with the 3rd or 6th position chlorine atoms or bromine atoms randomly. Therefore, when TFPN is used as the starting material, the substitution position is controlled to some extent, and when TCPN or TBPN is used as the starting material, the substituted phenoxy group (1) is randomly placed at the α-position and β-position of the phthalocyanine skeleton. Can be introduced. For this reason, when TCPN or TBPN is used as a starting material for a phthalonitrile derivative, the phthalonitrile derivative is in the form of a mixture in which four chlorine atoms or bromine atoms of TCPN or TBPN are optionally substituted with a precursor. can get.

  The ratio of HOX is appropriately selected depending on the structure of the target phthalonitrile compound. Further, the amount of HOX used is not particularly limited as long as these reactions can proceed to produce a desired phthalonitrile compound. For example, in the phthalocyanine compound (A), 4-hydroxy-ethyl benzoate is Usually, it is used in an amount of 0.5 to 0.55 mol with respect to 1 mol of the phthalonitrile derivative. These ratios are defined by the structures of the desired phthalocyanine compounds (1) and (2).

  In the above preferred embodiment, the reaction between the phthalonitrile derivative and HOX 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 (w / v)%, preferably 10 to 30 (w / v)%. . Further, in the reaction of this phthalonitrile derivative and HOX, it is preferable to use these trapping agents in order to remove hydrogen halide generated during the reaction. Specific examples of the trapping agent when using the trapping agent include calcium carbonate, calcium hydroxide, magnesium hydroxide, magnesium chloride and magnesium carbonate. Among these, calcium carbonate and calcium hydroxide are preferable. . The amount of the trapping agent used when using the trapping agent is not particularly limited as long as it is an amount capable of efficiently removing hydrogen halide and the like generated during the reaction, but is usually 1 with respect to 1 mol of the phthalonitrile derivative. 0.0 to 4.0 moles.

  Alternatively, the phthalonitrile compounds of the formulas (I) to (IV) as starting materials are converted into the following formula (VI):

The nitrophthalonitrile compound (hereinafter, also simply referred to as “nitrophthalonitrile compound”) may be obtained by reacting with HOX. Specifically, the substituent “OX” in the above formula corresponds to the substituted phenoxy group (1) represented by the above formula (3) in the above formula (1) representing the phthalocyanine compound (1-1). In the above formula (1) showing the phthalocyanine compound (1-2), it corresponds to the —COOR ₃ OR ₄ -containing phenoxy group represented by the above formula (4) and represents the phthalocyanine compound (2-1) ( In 2), it corresponds to the substituted phenoxy group (2) represented by the above formula (5). For the phthalocyanine compound (1-3), the halogenated phthalonitrile derivative represented by the above formula (V) may be used instead of the nitrophthalonitrile compound of the formula (VI).

Thus, when the nitrophthalonitrile compound of the formula (VI) is reacted with HOX, the nitro group (—NO ₂ ) in the nitrophthalonitrile compound reacts with HOX preferentially, and the nitro group (—NO ₂ ) may be selectively substituted with -X. Therefore, according to this method, the phthalocyanine compound of the substituted phenoxy group (1) in the above formula (1) showing the phthalocyanine compound (1-1) by selecting the substitution position of the nitro group in the nitrophthalonitrile compound The introduction position can be easily defined. Similarly, a —COOR ₃ OR ₄ -containing phenoxy group in the above formula (1) representing the phthalocyanine compound (1-2) and a substituted phenoxy group in the above formula (2) representing the phthalocyanine compound (2-1) ( The position of introduction of 2) into the phthalocyanine compound can be easily assumed. That is, the substituted phenoxy group (1), the —COOR ₃ OR ₄ -containing phenoxy group, and the substituted phenoxy group (2) can be selectively introduced into the α-position or β-position of the phthalocyanine skeleton.

  The ratio of HOX is appropriately selected depending on the structure of the target phthalonitrile compound. Further, the amount of HOX used is not particularly limited as long as these reactions can proceed to produce a desired phthalonitrile compound. For example, in the phthalocyanine compound (A), 4-hydroxy-ethyl benzoate is It is usually used in an amount of 0.5 to 5 mol, preferably 0.8 to 3 mol, per 1 mol of the nitrophthalonitrile compound of the formula (VI). Defined by the structure of the desired phthalocyanine compounds (1) and (2).

  In addition, in the above formula (VI), the bonding position of the nitro group to phthalonitrile is appropriately selected depending on the structure of the target phthalonitrile compound, and is any one of the 2, 3, 4, and 5 positions, A combination of these may be used, but in consideration of solubility in a solvent, cost, and the like, it is preferable that it is in the 3rd or 4th position.

In the above method, the reaction between the nitrophthalonitrile compound and HOX may be carried out in the absence of a solvent or in an organic solvent, but is preferably carried out in an organic solvent. Examples of organic solvents that can be used include amides such as formamide, N-methylformamide, N, N-dimethylformamide, acetamide, N-methylacetamide, N, N-dimethylacetamide, N-methylpropionamide, and N-methylpyrrolidone. And nitriles such as acetonitrile and benzonitrile. Of these, dimethylformamide, acetonitrile, and benzonitrile are preferable. The amount of the organic solvent used when using the solvent is such an amount that the concentration of the nitrophthalonitrile compound is usually 10 to 80 (w / v)%, preferably 20 to 50 (w / v)%. is there. In addition, the reaction of this nitrophthalonitrile compound with HOX is carried out by using 1,8-diazabicyclo [5.4.0] -7-undecene (DBU), potassium fluoride (KF), potassium carbonate (K ₂ CO ₃ ), etc. It is preferable to be carried out in the presence of the catalyst. At this time, the amount of the catalyst used is not particularly limited as long as the above reaction proceeds satisfactorily. Specifically, the catalyst is preferably added in an amount of usually 1.0 to 4.0 mol with respect to 1 mol of the nitrophthalonitrile compound.

  Moreover, the reaction conditions of the said nitrophthalonitrile compound and HOX will not be restrict | limited especially if the said reaction advances favorably. Specifically, the nitrophthalonitrile compound and HOX are preferably reacted at a temperature of 30 to 150 ° C., more preferably 40 to 100 ° C., preferably 2 to 12 hours, more preferably 3 to 8 hours.

  In the above embodiment, the cyclization reaction is carried out by melting one kind selected from the group consisting of phthalonitrile compounds (1) to (4) and metal, metal oxide, metal carbonyl, metal halide, and organic acid metal in a molten state or in an organic solvent. It is preferable to make it react with. Examples of the metal, metal oxide, metal carbonyl, metal halide, and organic acid metal (hereinafter collectively referred to as “metal compound”) that can be used at this time include phthalocyanine compounds of formula (1) (1- There is no particular limitation as long as one corresponding to M in 1) can be obtained. For example, iron, copper, zinc, vanadium, titanium, indium listed in the item M in the above formula (1). And metals such as tin, metal halides such as chloride, bromide, and iodide, metal oxides such as vanadium oxide, titanyl oxide and copper oxide, organic acid metals such as acetate, and acetylacetonate, etc. And metal carbonyls such as carbonyl iron. Of these, metals, metal oxides and metal halides are preferred.

  In the above embodiment, the cyclization reaction can be carried out in the absence of a solvent, but is preferably carried out using an organic solvent. The organic solvent may be any inert solvent that has a low reactivity with the phthalonitrile compound as a starting material, and preferably does not exhibit any reactivity. For example, benzene, toluene, xylene, nitrobenzene, monochlorobenzene, dioxybenzene, Inert solvents such as chlorobenzene, trichlorobenzene, 1-chloronaphthalene, 1-methylnaphthalene, ethylene glycol, and benzonitrile; and pyridine, N, N-dimethylformamide, N-methyl-2-pyrrolidinone, N, N-dimethyl Examples include aprotic polar solvents such as acetophenone, triethylamine, tri-n-butylamine, dimethyl sulfoxide, and sulfolane. Of these, 1-chloronaphthalene, 1-methylnaphthalene and benzonitrile are preferably used, and benzonitrile is more preferably used.

  The reaction conditions of the phthalonitrile compounds (1) to (4) and the metal compound in the above embodiment are not particularly limited as long as the reaction proceeds. For example, for 100 parts by mass of the organic solvent The total amount of the phthalonitrile compound is 2 to 40 parts by mass, preferably 20 to 35 parts by mass, and the metal compound is 1 to 2 mols, preferably 1.1 to 1 mol per 4 mols of the phthalonitrile compound. The reaction is carried out at a reaction temperature of 30 to 250 ° C, preferably 80 to 200 ° C. After the reaction, a phthalocyanine derivative that can be used in the next step can be efficiently and highly purified by filtration, washing, and drying according to a conventionally known method for synthesizing phthalocyanine compounds.

  In addition, the phthalocyanine compound contained in the composition of the present invention includes the case where a plurality of types of compounds are present in the form of a mixture in addition to the case of being one type of compound. In such a case, such a phthalocyanine compound can be produced by cyclizing a metal salt with a mixture of a plurality of phthalonitrile compounds as raw materials.

[Color filter]
The color filter according to the present invention includes a composition containing the phthalocyanine compounds (1) and (2) described above.

  Moreover, it is preferable that the color filter pigment | dye 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 (registered trademark) series manufactured by Avicia, Disperbyk (registered trademark) series manufactured by BYK Chemie, Efka (registered trademark) series manufactured by Efka, and the like. . The acid value is preferably 20 to 170 mgKOH / g, more preferably 100 to 150 mgKOH / g, or the amine value is 1 to 100 mgKOH / g, more preferably 30 to 90 mgKOH / g. The amount of the dispersing agent is usually 3 to 80 parts by mass with respect to 100 parts by mass of the composition 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 described in the Background Art section, a color filter used in an LCD or an imaging device is generally 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 color filter of the present invention is characterized in that it contains a composition containing the phthalocyanine compounds (1) and (2), the method for producing the color filter is applied with reference to known knowledge as appropriate or in combination. can do. 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 composition of the present invention 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, a method for preparing a resist preparation solution using the composition of the present invention will be described more specifically.

  The resist preparation liquid contains a composition containing the phthalocyanine compounds (1) and (2) of the present invention, but preferably further contains a solvent, a photosensitive resin composition, a dispersant, or the like.

  Examples of the solvent that can be used in the production of the color filter of the present invention include toluene, xylene, benzene, ethylbenzene, tetralin, styrene, cyclohexane, dichloromethane, chloroform, ethyl chloride, 1,1,1-trichloroethane, and 1-chlorobutane. , Cyclohexyl chloride, 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, Run, β-β-dichloroethyl ether, dioxane, tetrahydrofuran, ethyl acetate, n-butyl acetate, amyl acetate, n-butyl acetate, cyclohexylamine, ethanolamine, dimethylformamide, acetonitrile, nitromethane, nitroethane, 2-nitropropane, Examples thereof include nitrobenzene, dimethyl sulfoxide, diethylene glycol dimethyl ether, diethylene glycol monomethyl ether, propylene glycol monomethyl ether acetate (PGMEA), ethylene glycol monomethyl ether acetate, cyclohexanone, and N-methylpyrrolidone. Of these, diethylene glycol dimethyl ether, propylene glycol monomethyl ether acetate, cyclohexanone, N-methylpyrrolidone and the like are preferable from the viewpoint of boiling point and viscosity.

  The composition containing the phthalocyanine compounds (1) and (2) with respect to the solvent is preferably 2 to 20% by mass, more preferably 8 to 12% by mass, and the mass ratio of the phthalocyanine compound (1) alone is Preferably it is 0.01-15 mass%, More preferably, it is 0.02-10 mass%.

  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 or maleimide resin is used as a binder resin (base polymer), and photosensitive monomers (photopolymerizable monomers) and photopolymerization initiators made of various acrylic esters or methacrylic esters are added thereto. Photopolymerization type photosensitive resin composition, or photodimerization type photosensitive resin composition using an acrylic resin liquid to be photodimerized, and the like. 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 it has an appropriate viscosity as a resist preparation solution. 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.

  As the acrylic or maleimide resin, at least 10% by mass of monomers and oligomers constituting the acrylic resin or maleimide resin are selected from compounds having acrylic acid, methacrylic acid, acrylic acid ester, methacrylic acid ester and maleimide group. The compound having an acrylic acid, methacrylic acid or maleimide group is preferably 1 to 50% by mass, more preferably 5 to 35% by mass, and the compound having an acrylic acid, methacrylic acid or maleimide group is preferably 10 to 90% by mass. Part, more preferably 30 to 80 parts by weight.

  As monomers and oligomers constituting the acrylic resin, (meth) acrylic acid, methyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, octyl (meth) acrylate, Benzyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, (meth) acrylamide, N-hydroxymethylacrylamide, acrylonitrile, styrene, vinyl acetate, maleic acid, fumaric acid, polyethylene glycol Di (meth) acrylate, trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, dipentaerythritol hexa (meth) acrylate, dipenta Examples include hexa (meth) acrylate, melamine (meth) acrylate, and epoxy (meth) acrylate prepolymers of caprolactone adducts of thrisitol hexa (meth) acrylate. Examples of acrylic resins include (meth) acrylic acid, hydroxyalkyl ( Polymerized with (meth) acrylate, acrylic resin obtained by polymerizing various alkyl (meth) acrylates, (meth) acrylic acid, hydroxyalkyl (meth) acrylate, various alkyl (meth) acrylates, benzyl (meth) acrylate, and styrene. An acrylic resin obtained by polymerizing an acrylic resin, (meth) acrylic acid, and various alkyl (meth) acrylates is preferable.

  Examples of monomers constituting the maleimide resin include fragrances such as N-phenylmaleimide, N-benzylmaleimide, N-hydroxyphenylmaleimide, N-methylphenylmaleimide, N-methoxyphenylmaleimide, N-chlorophenylmaleimide, and N-naphthylmaleimide. In addition to group-substituted maleimides, alkyl-substituted maleimides such as N-methylmaleimide, N-ethylmaleimide, N-propylmaleimide, and N-cyclohexylmaleimide can be exemplified.

  Examples of the photosensitive monomer that can be a component of the photosensitive resin composition include monomers constituting the acrylic resin, preferably trimethylolpropane trimethacrylate, dipentaerythritol hexaacrylate, pentaerythritol triacrylate, Polyfunctional (meth) acrylates such as pentaerythritol tetraacrylate are exemplified.

  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, acetophenone compounds such as IRGACURE (registered trademark) 369, IRGACURE (registered trademark) 907 (both are trade names, manufactured by Ciba Geigica Co., Ltd.) and the like can be mentioned. Among these, acetophenone compounds such as IRGACURE (registered trademark) 369 and IRGACURE (registered trademark) 907 are preferable.

  The addition amount of the photopolymerization initiator is not particularly limited, but for acetophenone compounds (IRGACURE 369, etc.), 100 mass of a photosensitive monomer (photopolymerizable monomer; for example, dipentaerythritol hexaacrylate, etc.). When it is made a part, it is preferably added in a proportion of 1 to 30 parts by mass, more preferably 5 to 15 parts by mass.

  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-tert-butylphenol), 2,2′-methylene (4-methyl-6-tert-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.

Synthesis Example 1: Synthesis of Phthalocyanine Compound (A): (Ethoxycarbonylphenoxy) _2.0 Cl _14.0 ZnPc In a 100 ml three-necked flask, 7.98 g (0.03 mol) of tetrachlorophthalonitrile (TCPN) and ethyl 4-hydroxybenzoate 2.49 g (0.015 mol), 2.44 g of potassium carbonate, and 32 g of benzonitrile (BN) were added and reacted at 100 ° C. for about 2 hours with stirring. After completion of the reaction, inorganic salts were removed by filtration, and concentrated until BN was about 6.7 g. After concentration, 2.63 g of zinc iodide was added, and the mixture was reacted at 160 ° C. for about 16 hours with stirring. After the reaction, about 14 g of methyl cellosolve was charged, and then charged into a mixed solution of 100 g of methanol and 35 g of water to obtain crystals. The crystals were subjected to suction filtration, once again put into a mixed solution of 50 g of methanol and 17.5 g of water, washed with stirring, and then suction filtered. The crystals after filtration were vacuum-dried at 70 ° C. overnight to obtain about 10.34 g (yield 99.3%) of a phthalocyanine compound (ethoxycarbonylphenoxy) _2.0 Cl _14.0 ZnPc.

Synthesis Example 2: Synthesis of Phthalocyanine Compound (B): (Methoxyethoxycarbonylphenoxy) _2.6 Cl _13.4 ZnPc Ethyl 4-hydroxybenzoate of Synthesis Example 1 above was changed to 3.83 g of methoxyethyl 4-hydroxybenzoate, and the amount of potassium carbonate Was changed to 3.32 g in the same manner as in Synthesis Example 1 to obtain 10.96 g (yield 94.7%) of a phthalocyanine compound (methoxyethoxycarbonylphenoxy) _2.6 Cl _13.4 ZnPc.

Synthesis Example 3: Synthesis of phthalocyanine compound (A): β-position (2,5-dichlorophenoxy) ₈ , α-position (2,6-dimethylphenoxy) ₄ F ₄ ZnPc Example 1 of JP 2002-302477 A 3- (2,6-Dimethylphenoxy) -4,5-bis (2,5-dichlorophenoxy) -6-fluorophthalonitrile was synthesized from tetrafluorophthalonitrile (TFPN) by the described method. 15 g, zinc iodide 2.23 g, and BN 30 g were put into a 100 ml three-necked flask and reacted at 180 ° C. for about 9 hours with stirring. After cooling to below 60 ° C., it was poured into about 450 ml of methanol and crystallized. After filtering the crystals, they were again put into 225 ml of methanol, separated after stirring and washing, and vacuum dried at 70 ° C. overnight to obtain about 13.4 g of phthalocyanine compound (A) (yield: 87.1%).

Synthesis Example 4: Synthesis of phthalocyanine compound (a): β-position (2,5-dimethylphenoxy) ₈ , α-position (2,6-dimethylphenoxy) ₄ F ₄ CuPc According to the method of Synthesis Example 3 above, 3- ( 2,6-dimethylphenoxy) -4,5-bis (2,5-dimethylphenoxy) -6-fluorophthalonitrile was synthesized, and 15 g of this nitrile, 0.77 g of copper (I) chloride, and 30 g of 1-octanol were synthesized. The mixture was put into a 100 ml three-necked flask and reacted at 150 ° C. with stirring for about 2 hours. After cooling to below 60 ° C., it was poured into about 450 ml of methanol and crystallized. After filtering the crystals, they were again poured into 225 ml of methanol, separated by stirring and washing, and vacuum-dried at 70 ° C. overnight to obtain about 12.4 g of phthalocyanine compound (I) (yield 80.0%).

Synthesis Example 5: Phthalocyanine Compound (U): (Phenoxy) _11.45 Cl _4.55 Synthesis of ZnPc Except that ethyl 4-hydroxybenzoate in Synthesis Example 1 above was changed to 8.02 g of phenol and the amount of potassium carbonate was changed to 13.7 g. Were operated in the same manner as in Synthesis Example 1 to obtain 11.3 g (yield: 88.9%) of the phthalocyanine compound (U).

Synthesis Example 6: Phthalocyanine Compound (D): (Phenoxy) _13.33 Cl _2.67 Synthesis of ZnPc Ethyl 4-hydroxybenzoate of Synthesis Example 1 above was 9.4 g of phenol, and the amount of potassium carbonate was 15.2 g, and a phenol substitution reaction. Except having changed the temperature of this to 120 degreeC, it operated similarly to the synthesis example 1, and obtained 12.9 g (yield 91.1%) of the phthalocyanine compound (d).

Synthesis Example 7 Synthesis of Phthalocyanine Compound (e): (2,5-Dichlorophenoxy) ₈ (2,6-Dimethylphenoxy) ₄ Cl ₄ ZnPc Ethyl 4-hydroxybenzoate of Synthesis Example 1 was converted to 2,5-dichloro The procedure was the same as in Synthesis Example 1 except that 9.78 g of phenol and 3.67 g of 2,6-dimethylphenol were used, the amount of potassium carbonate was 13.7 g, and the substitution reaction temperature of the substituted phenol was changed to 125 ° C. Thus, 17.07 g (yield 91.8%) of the phthalocyanine compound (v) was obtained.

Synthesis Example 8 Synthesis of Phthalocyanine Compound (F): (4-Cyanophenoxy) ₁₅ ClZnPc Ethyl 4-hydroxybenzoate in Synthesis Example 1 was 13.4 g of 4-cyanophenol, and the amount of potassium carbonate was 17.1 g. Except that the temperature of the 4-cyanophenol substitution reaction was changed to 130 ° C., the same operation as in Synthesis Example 1 was performed to obtain 17.1 g (yield 96.3%) of the phthalocyanine compound (F).

Synthesis Example 9 Synthesis of Phthalocyanine Compound (g): (2-Methylphenoxy) ₁₅ ClZnPc Ethyl 4-hydroxybenzoate of Synthesis Example 1 above was 12.2 g of 2-methylphenol, and the amount of potassium carbonate was 17.1 g Except having changed, it operated similarly to the synthesis example 1, and obtained 14.1 g (yield 85.7%) of phthalocyanine compounds (ki).

Synthesis Example 10 Synthesis of Phthalocyanine Compound (H): (4-Methylcarbonylphenoxy) ₁₆ ZnPc The starting material of Synthesis Example 1 above was converted from TCPN to 6.0 g of TFPN, and ethyl 4-hydroxybenzoate was converted to methyl 4-hydroxybenzoate 18 0.71 g, except that the amount of potassium carbonate was changed to 18.7 g, the same operation as in Synthesis Example 1 was carried out to obtain 17.2 g (yield 83.2%) of the phthalocyanine compound (C).

Synthesis Example 11 Synthesis of Phthalocyanine Compound (I): (2,6-Dichlorophenoxy) ₅ Cl ₁₁ InClPc In a 100 ml three-necked flask, 6.65 g (0.025 mol) of tetrachlorophthalonitrile (TCPN) and 2,6 -5.09 g (0.031 mol) of dichlorophenol, 4.75 g of potassium carbonate and 33 g of benzonitrile (BN) were added and reacted at 100 ° C. for about 3 hours with stirring. After completion of the reaction, inorganic salts were removed by filtration, and concentrated until BN became about 2.7 g. After concentration, 8 g of octanol and 2.02 g of indium (III) chloride tetrahydrate were added and reacted at 160 ° C. for about 8 hours with stirring. After the reaction, it was poured into 115 g of methanol to obtain crystals. The crystals were subjected to suction filtration, then once again put into 50 g of methanol, washed with stirring and suction filtered. The crystals after filtration were vacuum-dried at 70 ° C. overnight to obtain about 5.74 g of phthalocyanine compound (ke) (yield 49.7%).

Synthesis Example 12 Synthesis of Phthalocyanine Compound (Co): (2,6-Dimethylphenoxy) ₇ Cl ₉ InClPc 2,6-Dimethylphenol of Synthesis Example 11 was changed to 5.34 g of 2,6-dimethylphenol, and potassium carbonate The procedure was the same as in Synthesis Example 11 except that the amount was changed to 6.65 g, to obtain 5.80 g of phthalocyanine compound (co) (yield 51.2%).

<Maximum absorption wavelength (λmax)>
The maximum absorption wavelength (λmax) of the obtained phthalocyanine compound was measured as follows.

  A sample of 40 mg was accurately weighed and dissolved in PGMEA in a volumetric flask to a volume of 50 mL. The resulting solution was diluted 50 times with PGMEA using a 1 mL whole pipette and a 50 mL volumetric flask. The absorption of the diluted liquid was measured using a spectrophotometer (spectrophotometer (manufactured by Hitachi, Ltd .: U-2910), and the wavelength with the maximum absorption was defined as the maximum absorption wavelength (λmax). The maximum absorption wavelength (λmax) measured by the above method is as described in the description of the phthalocyanine compounds (1) and (2).

<Color filter evaluation>
Example 1
(1) Preparation of dye resist solution (hereinafter also referred to as “colorant composition”) After preparing a dispersion solution by the following formulation, it is stirred and mixed for 2 hours using a bead mill, and then a green dispersion liquid (colorant composition) is prepared. )

  The yellow dye compound (1) in the present specification is represented by the following chemical formula (a).

(2) Preparation of coating film plate The thickness of the dye resist solution (colorant composition) obtained in (1) above after drying is about 2 μm on a glass substrate whose surface has been wiped with acetone in advance. The film was applied using a spin coater and pre-baked 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, transmittance, discoloration resistance and contrast ratio of the colored filter obtained above were evaluated. The results are shown in Table 4 below. The chromaticity coordinate values, transmittance, discoloration resistance (heat 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.

(Transmittance)
Measure the absorption waveform using a Hitachi spectrophotometer U-2910, further multiply by a constant such that the absorbance value of the maximum absorption wavelength of this waveform is 2.5, and further convert the waveform into a transmittance waveform. Thus, transmittance values of 710 nm and 720 nm were calculated.

(Discoloration resistance (heat resistance))
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. The absorbance up to 380 to 780 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, in the absorption spectrum of the colorant composition, the change before and after heating of the ratio of the absorbance at the wavelength of 520 nm to the absorbance at the maximum absorption wavelength at a wavelength of 630 to 670 nm was determined. That is, the color change resistance index ΔAbs represented by the following formula (I) was calculated by the following formula to evaluate the color change resistance.

In the formula, U ₁ and U ₂ represent the absorbance of the absorption spectrum before heating, where U ₁ represents the absorbance at a wavelength of 520 nm and U ₂ represents the absorbance at a wavelength of 630 to 670 nm, and E ₁ and E ₂ represents the absorbance of the absorption spectrum after heating, where E ₁ represents the absorbance at a wavelength of 520 nm and E ₂ represents the absorbance at the maximum absorption wavelength at a wavelength of 630 to 670 nm.

(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.

A: When the contrast ratio exceeds 12000 times. O: When the contrast ratio is 10,000 to 12000 times.

(Example 2)
In Example 1, the colorant composition was evaluated in the same manner except that (1) the preparation of the dye resist solution was changed as follows. The results are shown in Table 4.

  In Example 2, a dispersion solution was prepared according to the formulation shown below, and then stirred and mixed for 2 hours using a bead mill to obtain a green dispersion (colorant composition).

(Example 3)
In Example 1, the colorant composition was evaluated in the same manner except that (1) the preparation of the dye resist solution was changed as follows. The results are shown in Table 4.

  In Example 3, a dye resist solution (colorant composition) was prepared by mixing and dissolving the following composition.

Example 4
Evaluation was conducted in the same manner as in Example 3 except that the phthalocyanine compound (A) in Example 3 was changed to the phthalocyanine compound (U). The results are shown in Table 4.

(Example 5)
Evaluation was conducted in the same manner as in Example 3 except that the phthalocyanine compound (A) in Example 3 was changed to the phthalocyanine compound (D). The results are shown in Table 4.

(Example 6)
Evaluation was performed in the same manner as in Example 3 except that the phthalocyanine compound (A) in Example 3 was changed to the phthalocyanine compound (B) and the phthalocyanine compound (A) was changed to the phthalocyanine compound (e). The results are shown in Table 4.

(Example 7)
Evaluation was performed in the same manner as in Example 6 except that the phthalocyanine compound (e) in Example 6 was changed to the phthalocyanine compound (f). The results are shown in Table 4.

(Example 8)
Evaluation was performed in the same manner as in Example 6 except that the phthalocyanine compound (e) in Example 6 was changed to the phthalocyanine compound (g). The results are shown in Table 4.

Example 9
Evaluation was performed in the same manner as in Example 6 except that 4.5 parts by mass of the phthalocyanine compound (e) in Example 6 was changed to 10 parts by mass of the phthalocyanine compound (g). The results are shown in Table 4.

(Example 10)
Evaluation was conducted in the same manner as in Example 3 except that the phthalocyanine compound (A) in Example 3 was changed to the phthalocyanine compound (K). The results are shown in Table 4.

(Example 11)
Evaluation was performed in the same manner as in Example 2 except that the phthalocyanine compound (A) in Example 2 was changed to the phthalocyanine compound (CO). The results are shown in Table 4.

(Comparative Example 1)
The phthalocyanine compound (A) 30.0 parts by mass and the phthalocyanine compound (a) 4.5 parts by mass were changed to only the phthalocyanine compound (a) 30.0 parts by mass (that is, the phthalocyanine compound (1)). Evaluation was made in the same manner as in Example 3, except that The results are shown in Table 4. In addition, "-" in a table | surface shows that the said compound is not added (hereinafter the same).

(Comparative Example 2)
In Example 3, the evaluation was made in the same manner as in Example 3 except that the phthalocyanine compound (a) was not added (that is, only the phthalocyanine compound (1) was used). The results are shown in Table 4.

(Comparative Example 3)
In Example 2, the evaluation was performed in the same manner as in Example 2 except that the phthalocyanine compound (a) was not added (that is, only the phthalocyanine compound (1) was used). The results are shown in Table 4.

  As described above, the composition of the present invention (color filter colorant composition) improves the luminance Y value by appropriately blending two types of phthalocyanine compounds (1) and (2) having different wavelengths. The transmittance in the vicinity of the wavelength of 710 to 720 nm can be suppressed to a low value of 2% or less. At the same time, the value of the color change resistance index ΔAbs is 1.35 or less, the change before and after heating is small, and the contrast ratio can be improved as compared with the case where it is used alone.

  It can be seen that the color filter colorant composition of the present invention has a synergistic effect by appropriately blending two types of phthalocyanine compounds having different wavelengths, and is superior in performance in all characteristics than when used alone.

Claims (5)

  A composition comprising a phthalocyanine compound (1) having a maximum absorption wavelength at 600 to 700 nm and a phthalocyanine compound (2) having a maximum absorption wavelength of more than 700 nm and 750 nm or less.   The said phthalocyanine compound (2) is a composition of Claim 1 contained 0.1-50 weight part with respect to 100 weight part of said phthalocyanine compound (1). The phthalocyanine compound (1) has the following formula (1):

In the above formula (1), Z _{1 to} Z ₁₆ are each independently a hydrogen atom, a halogen atom or the following formula (3):

In the above formula (3), R ₁ represents a halogen atom, an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, a cyano group, a nitro group, or an ester group (—COOR ₂ : R ₂ represents an alkyl group having 1 to 20 carbon atoms),
m is an integer from 0 to 5;
Represents a substituted phenoxy group (1) represented by:
M represents metal-free, metal, metal oxide or metal halide;
In this case, _{1 to} 5 of Z _{1 to} Z ₁₆ are substituted phenoxy groups (1), and the rest are hydrogen atoms or halogen atoms;
A phthalocyanine compound (1-1) represented by:
In the above formula (1), Z _{1 to} Z ₁₆ are each independently a hydrogen atom, a halogen atom or the following formula (4):

In the above formula (4), R ₃ represents an alkylene group having 1 to 5 carbon atoms,
R ₄ represents an alkyl group having 1 to 5 carbon atoms,
R ₅ is a halogen atom, an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, a cyano group, a nitro group, or an ester group (—COOR ₆ : R ₆ is the number of carbon atoms. 1-20 alkyl groups)
a is 1 or 2,
b is an integer from 0 to 4;
-COOR ₃ OR ₄ -containing phenoxy group represented by
M represents metal-free, metal, metal oxide or metal halide;
In this case, one or more and less than four of Z _{1 to} Z ₁₆ are —COOR ₃ OR ₄ -containing phenoxy groups, and the rest are hydrogen atoms or halogen atoms;
In the formula (1), Z _{1 to} Z ₁₆ each independently represent a halogen atom,
M represents metal-free, metal, metal oxide or metal halide;
The composition of Claim 1 or 2 which is a phthalocyanine compound (1-3) shown by these. The phthalocyanine compound (2) has the following formula (2):

In the above formula (2), Z ₁ ′ to Z ₁₆ ′ are each independently a halogen atom or the following formula (5):

In the above formula (5), R ₇ represents a halogen atom, an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, a cyano group, a nitro group, or an ester group (—COOR ₈ : R ₈ represents an alkyl group having 1 to 20 carbon atoms),
n is an integer from 0 to 5;
Represents a substituted phenoxy group (2) represented by:
M represents metal-free, metal, metal oxide or metal halide;
In this case, 3 to _{16 of} Z ₁ ′ to Z ₁₆ ′ are substituted phenoxy groups (2), and the rest are halogen atoms;
The composition of any one of Claims 1-3 which is a phthalocyanine compound (2-1) shown by these.   The color filter containing the composition of any one of Claims 1-4.