JP2003176424A - Green coloring matter composition and color filter - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To obtain a green coloring matter composition providing excellent fluidity when added to a medium to be colored, and further to provide a color filter having sufficient Y-value in the chromaticity (x, y, Y) of the CIE colorimetric system, and excellent transparency. <P>SOLUTION: The green coloring matter composition contains a green organic coloring matter and a yellow organic coloring matter. The green organic coloring matter is a metal phthalocyanine halide represented by a specific formula, or a dissimilar metal phthalocyanine halide having a specified center metal except copper. The yellow organic coloring matter is a yellow condensed polycyclic compound having a sulfonic acid group or a sulfonic acid salt as a functional group. The color filter contains the green coloring matter composition. <P>COPYRIGHT: (C)2003,JPO

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a green colorant and a color filter using the same.

[0002]

2. Description of the Related Art A color filter used in a liquid crystal display device has three types of red, green and blue on a transparent substrate such as glass.
A color pattern is formed. As a backlight light source of such a liquid crystal display device, JIS Z871
A fluorescent lamp F10 light source of three-wavelength band emission type defined by 9 is the mainstream, and has a maximum intensity bright line at 545 nm. Therefore, in forming the green pattern of the color filter, it is preferable to select a colorant having a wavelength (Tmax) that maximizes the transmittance of the spectral transmission spectrum as close as possible to this bright line. Examples of such a coloring agent include halogenated copper phthalocyanine.

As a colorant for forming this green colored pattern, there are JP-A Nos. 11-72616, 11-256053, and 2001-4211.
7 and JP 2001-59906 A, for example, chlorinated copper phthalocyanine (C.I. Pig.
ment Green 7), chlorinated brominated copper phthalocyanine (CI Pigment Green 36) or total brominated copper phthalocyanine, and a quinophthalone-based pigment (CI Pigment Yellow).
A colorant composition is used in combination with a yellow organic colorant comprising a fused polycyclic compound such as w138).

[0004]

However, a colorant composition prepared by mixing the above-mentioned green organic colorant and yellow organic colorant into a medium to be colored (medium to be colored) such as a synthetic resin. There was a drawback that the fluidity when added was insufficient. In addition, the color filter produced by using such a colorant composition also does not satisfy the Y value in the CIE color system chromaticity (x, y, Y) as a result, and a larger Y value is obtained. Therefore, a color filter having excellent transparency is required. Moreover, there is a demand for a color filter that emits a brighter green color with a stronger yellow tint than that of a conventional green organic colorant composed of a halogenated copper phthalocyanine.

The present invention has been made in view of the above circumstances, and provides a green organic colorant composition which is excellent in fluidity when added to a medium to be colored and has a stronger yellowish color and a brighter green color. , And a larger Y value and excellent transparency,
An object of the present invention is to provide a color filter that produces a brighter green color with stronger yellowness.

[0006]

As a result of intensive studies to solve the above problems, the present inventors have found that as a yellow organic colorant to be combined with a conventional green organic colorant, a sulfonic acid group or a sulfonate group is used as a functional group. When the condensed polycyclic compound having as is used, the fluidity when added to the medium to be colored becomes more excellent than the case where the condensed polycyclic compound having no functional group is used. Found out.
Further, instead of a conventional green organic colorant such as a halogenated copper phthalocyanine, a halogenated metal-free phthalocyanine having no central metal, or a halogenated dissimilar metal phthalocyanine having a specific central metal other than copper is used. It has been found that the yellow color is stronger and produces a lighter green color. Based on these findings, the present inventors have completed the following present invention.

That is, the present invention provides a green colorant composition comprising a green organic colorant and a yellow organic colorant, wherein the green organic colorant is a halogenated phthalocyanine (A) represented by the following formula Provided are a green colorant composition characterized in that the agent is a yellow condensed polycyclic compound (B) having a sulfonic acid group or a sulfonate as a functional group, and a color filter containing the green colorant composition. The purpose is to

[0008]

[Chemical 3]

(In the formula, M is Al, Si, Sc, Ti,
V, Mg, Fe, Co, Ni, Zn, Ga, Ge, Y,
Represents Zr, Nb, In, Sn, Pb, 2H. X represents fluorine, chlorine, bromine and iodine, which may be the same or different, and m represents an integer of 8 to 16. Y is fluorine
It represents chlorine, bromine, iodine, oxygen, a hydroxyl group, or a sulfonic acid group, and n represents an integer of 0-2. )

[0010]

BEST MODE FOR CARRYING OUT THE INVENTION The present invention will be described in detail below.
In the present invention, a halogenated metal phthalocyanine (hereinafter referred to as a halogenated dissimilar metal phthalocyanine) or a halogenated metal-free phthalocyanine represented by the above formula and having a specific central element other than copper is used. In the present invention, these are collectively referred to as a halogenated phthalocyanine (A). This halogenated phthalocyanine (A) is a conventionally used chlorinated copper phthalocyanine (CI Pigment).
As compared with Green 7), chlorinated brominated copper phthalocyanine (CI Pigment Green 36) or all brominated copper phthalocyanine, it is a preferable green organic colorant in that it has a stronger yellowish tint and produces a brighter green color. This halogenated phthalocyanine (A) used in the present invention has Al, Si, Sc, Ti, V, Mg, Fe and C as the central element M as shown in the above formula.
o, Ni, Zn, Ga, Ge, Y, Zr, Nb, In,
It has any one of Sn, Pb, and 2H (metal-free).

In the formula, X represents a halogen atom bonded to the aromatic ring, specifically fluorine, chlorine, bromine or iodine,
All may be the same or different, and m represents an integer of 8 to 16. When Y, n, and X, which will be described later, are the same, when m is less than 8, the color is blue, and when it is 8 or more, the color is darker. Y represents a halogen atom or an oxygen atom, specifically, fluorine, chlorine, bromine, iodine and oxygen, and n represents an integer of 0-2.

The valence of the central element M determines the number n of ligands Y bound to M. The valence of the central element M is
In the case of trivalence such as Al, Sc, Ga, Y and In, one fluorine, chlorine, bromine, iodine, hydroxyl group, sulfonic acid group and the like coordinate to the central element. Si, Ti, V, Ge, Zr,
When it is tetravalent like Sn, one oxygen, two fluorine,
Chlorine, bromine, iodine, hydroxyl group, sulfonic acid group, etc. coordinate to the central element. Mg, Fe, Co, Ni, Zn, Zr,
In the case of divalent compounds such as Sn and Pb, there is no coordination.

Since phthalocyanine has 16 hydrogen atoms in the phthalocyanine ring, these hydrogen atoms can be replaced with up to 16 halogen atoms X. m halogen atoms X are all the same,
Each may be different. When the number of m is constant, X has a deep green color in the order of iodine>bromine>chlorine> fluorine. When these hydrogen atoms are replaced with bromine atoms and chlorine atoms, for example, the number of bromine atoms is 0 to 16, the number of chlorine atoms is 0 to 16, the number of hydrogen atoms is 0 to 16, and theoretically. A total of 136 types of substitution products can be produced.

Here, 8 or more bromine atoms and 1 chlorine
It is preferable that the number of bromine atoms is 12 or more, and that the number of bromine atoms is 12 or more and the number of chlorine atoms is 2 or more. It is suitable for use in a green pattern of a color filter, which produces a yellowish green color with high brightness. Become.

The halogenated phthalocyanine (A) as described above can be used as a copper or copper compound in a method for producing a halogenated copper phthalocyanine, for example, a known production method such as a chlorosulfonic acid method, a halogenated phthalonitrile method or a melting method. It can be easily produced by using a different metal or a different metal compound instead of the compound and appropriately changing the reaction conditions.

The halogenated phthalocyanine (A) in the colorant of the present invention is, for example, M = Al and Y = C.
l and n = 1 halogenated chloroaluminum phthalocyanine, M = V and Y = O and n = 1 halogenated oxyvanadium phthalocyanine, M = Zn halogenated zinc phthalocyanine, M = Ti and Y = O and n = 1 Halogenated titanyl phthalocyanine, M = Sn halogenated tin phthalocyanine, M = 2H (metal-free) halogenated metal-free phthalocyanine, M = Al and Y = O and n =
1 halogenated μ-oxoaluminum phthalocyanine and the like.

In preparing the colorant of the present invention, the halogenated phthalocyanine (A) may be used alone or in combination of two or more different kinds. When the halogenated phthalocyanine (A) is used in a color filter, it is preferable to use primary particles having an average particle diameter of 0.01 to 0.10 μm.

There are two directions regarding the color gamut,
One of them is color reproduction conforming to sRGB / EBU (colorimetric color reproduction), and the other is "color appearance" (CIECA).
M97s) expansion of color reproduction range (equivalent color reproduction)
Is. The color filter along the former direction is C
It is a high transmission color filter for small screens such as mobile phones and small TVs that emphasizes compatibility with RT. The latter one is a high-quality image that requires higher contrast on large screens such as personal computers, displays and TVs. It is a color purity color filter.

When the colorant of the present invention is used in the production of a color filter, T of the green organic pigment is taken into consideration in relation to the kind of light source.
The closer max is to 545 nm, the more preferable it is, but for producing the former color filter, M = Al, which boasts high transmittance in a wider wavelength range than when the central element is copper, is preferable.
And Y = Cl and n = 1 halogenated chloroaluminum phthalocyanine.

On the other hand, preferred for producing the latter color filter is a halogenated zinc phthalocyanine of M = Zn, which transmits light only in a wavelength range narrower than that in the case where the central element is copper. This zinc halide phthalocyanine has Tmax when the average diameter of primary particles is reduced.
Can be higher and the transmittance at Tmax can also be higher. This halogenated zinc phthalocyanine has a higher Tmax than the conventional halogenated copper phthalocyanine even if the average diameter of the primary particles is large, and the transmission curve shows that the transmittance is half the transmittance at Tmax. When inserted, the distance (half-width) between two points on the curve is 90-110 nm
Since it is very sharp, it has a high color purity and is green even when mixed with a yellow organic colorant consisting of a yellow condensed polycyclic compound having a sulfonic acid group or a sulfonate as a functional group described later. The amount of light transmitted through the region is larger, a brighter screen can be obtained, the contrast of the image is good, and it can be suitably used for a high color purity color filter.

The halogenated zinc phthalocyanine is also characterized in that it has a coloring power higher than that of conventional halogenated copper phthalocyanine by 10% or more. This has an advantage that the content of the colorant can be reduced when a color filter having the same transmittance with the same colored resin film thickness is obtained. Conversely, it can be said that it is more suitable for thinning the color filter.

For color filter applications, 650-70
It is preferable that the region where the spectral transmittance at 0 nm is 5% or less is wider and the maximum transmittance (Tmax) is larger.

The halogenated phthalocyanine finely divided to have a smaller average primary particle diameter is often used when curing the resist ink for color filters.
The light-shielding property at 65 nm is decreased (that is, the transmittance is increased), the photocuring sensitivity of the resist is not decreased, and the film edge and the pattern flow during development are less likely to occur, which is preferable.

As a result, the wavelength at which the transmittance of the spectral transmission spectrum becomes maximum is on the longer wavelength side and is close to 545 nm, and the maximum transmittance value is also higher than the level, so that the conventional copper halide phthalocyanine It is possible to obtain a color filter having a green portion which has both a yellowish green color and an excellent brightness as compared with the pigment.

The spectral transmission spectrum in the present invention means
It is required in accordance with the first industrial spectrophotometer of Japanese Industrial Standard JIS Z 8722 (color measuring method-reflection and transmission object color), and the pigment composition is formed on a glass substrate or the like to the above-mentioned predetermined dry film thickness. It is a plot of light transmittance values at respective wavelengths obtained by scanning and irradiating a resin coating containing a substance with light in a predetermined wavelength region. The transmittance as a color filter can be obtained more accurately by correcting the spectral transmission spectrum obtained in the same manner for a coating film made of only resin and having the same dry film thickness (baseline correction, etc.).

The color filter of the present invention has the above-mentioned characteristics, and more preferably 380 to 7
The wavelength (Tmax) at which the transmittance of the spectral transmission spectrum at 80 nm is maximum is 520 to 590 nm, the transmittance at the Tmax is 70 to 99%, and the wavelength is 65.
The transmittance of the spectral transmission spectrum at 0 to 700 nm is 0 to 20%.

In the green colorant composition of the present invention, a specific yellow organic colorant is used in combination in order to develop a green color with a stronger yellowish tint and a brighter green color than in the case of using only the above green organic colorant. This specific yellow organic colorant is a yellow condensed polycyclic compound (B) having a sulfonic acid group or a sulfonate as a functional group. By using this together with a green organic colorant composed of a halogenated phthalocyanine, a wavelength of 400 to 500 nm can be obtained without impairing the fluidity of the medium to be colored.
It is possible to reduce the transmittance of the same spectral transmission spectrum in, for example, the transmittance in the wavelength range of 5
It can be set to 0% or less.

The yellow condensed polycyclic compound (B) having this sulfonic acid group or sulfonic acid salt as a functional group is
Well-known and commonly used ones can be mentioned, but the azo compounds and phthalocyanine compounds are not included in this condensed polycyclic compound as described in the Coloring Material Handbook (Asakura Shoten). Examples of the yellow condensed polycyclic compound (B) having a sulfonic acid group or a sulfonate as a functional group include, for example, a yellow quinophthalone compound having the sulfonic acid group or a sulfonate as a functional group, the same isoindolinone compound, Examples include isoindoline compounds. These are C.I. I. Pi
gment Yellow 138, 109, 11
No. 0, No. 173, No. 173, No. 139, No. 185, etc., to sulfonate a yellow condensed polycyclic compound to introduce a sulfonic acid group, or to neutralize the sulfonic acid group introduced by this sulfonation with a base to give a sulfonate. It can be obtained by

The most preferable yellow condensed polycyclic compound (B) having this sulfonic acid group or sulfonate as a functional group has a sulfonic acid group or sulfonate represented by the following formula as a functional group. It is a yellow quinophthalone compound.

[0030]

[Chemical 4]

However, in the above formula, X is a halogen atom, M is a hydrogen atom, a monovalent, divalent or trivalent metal atom, ammonia or an organic amine, and n is 1 to 3. ]

The halogen atom represented by X includes a chlorine atom and a bromine atom, and each X may be the same atom or different atoms. M is a hydrogen atom, ammonia, a monovalent, divalent or trivalent metal atom, or an organic amine. As these metal atoms, potassium atom, sodium atom, lithium atom, calcium atom, magnesium atom, strontium atom, Aluminum atom, as the organic amine, a monoalkylamine such as ethylamine and butylamine, a dialkylamine such as dimethylamine and diethylamine, trimethylamine,
Examples include trialkylamines such as triethylamine, alkanolamines such as monoethanolamine, diethanolamine and triethanolamine.

In the formula, n is derived from quinaldine described later.
Atomic group substituted on aromatic ring (SO _Three) Number
1-3. When n is 2 or more, each atomic group (SO
_Three) Are attached to different carbon atoms of the aromatic ring derived from quinaldine.
I am fit. In addition, sulfonic acid group or sulfonate
Equivalent atomic group (SO_Three) M is SO_ThreeNa and (S
O_Three)_ThreeIt is electrically neutral like Al. Sulfonic acid (S
O_ThreeH) is a monovalent acid, so this hydrogen atom
Substituting with an atomic group M other than an atom, when n = 1,
When M is a divalent metal atom, etc., 1/2 mol, trivalent metal
In the case of atoms and the like, the equivalent amount is 1/3 mol.

A preferred compound (B), a yellow quinophthalone compound having a sulfonic acid group or a sulfonate as a functional group, first comprises 1 mol of 8-aminoquinaldine and phthalic anhydride whose aromatic ring is halogenated. React, 4,
5,6,7-Tetrahalogeno-2- [2- (4,5,
6,7-Tetrahalogeno-2,3-dihydro-1,3-
Dioxo-1H-inden-2-yl) -8-quinolinyl] -1H-isoindole-1,3 (2H) -dione, which is sulfonated with a sulfonating agent such as sulfuric acid, or sulfonated and It can be obtained by further neutralizing the sulfonic acid group thus obtained.

When the compound (B) is used in a color filter, it is preferable to use a primary particle having an average particle diameter of 0.01 to 0.10 μm.

The proportion of the halogenated phthalocyanine (A) and the yellow condensed polycyclic compound (B) used in combination in preparing the green colorant composition of the present invention should be within the range in which the composition containing both is green. For example, in terms of mass, for example, 100 parts of the former (A) corresponding to the green organic colorant is 0.5 to 20 parts of the latter (B) corresponding to the yellow organic colorant.

The green colorant composition of the present invention may contain only the halogenated phthalocyanine (A) and the yellow condensed polycyclic compound (B), but in addition to these, a yellow color other than the compound (B) is used. Organic pigments (C) can be included. In this case, a yellow organic colorant containing at least compound (B) per 100 parts by weight of halogenated phthalocyanine (A) [that is, compound (B) alone or a mixture of compound (B) and pigment (C)] Means 1 to
It is preferably 70 parts. Further, the yellow organic pigment (C) is 10 parts per 100 parts of the halogenated phthalocyanine (A).
It is preferably about 60 parts. When the purpose is to form the green part of the color filter, such (A),
A three-component system of (B) and (C) is preferable.

In preparing the green colorant composition of the present invention, the halogenated phthalocyanine (A) and the yellow condensed polycyclic compound (B) may be mixed by an arbitrary method. For the purpose of forming the green portion of the color filter, it is preferable that the particles of (A) and (B) have approximately the same size.

Examples of this mixing method include the following. 1) A dry powder of a halogenated phthalocyanine (A) pigment obtained by pigmenting a crude pigment by an arbitrary method and a compound (B) are thoroughly mixed (treatment by a powder method). 2) A slurry or wet cake containing a pigment of a halogenated phthalocyanine (A) obtained by pigmenting a crude pigment by an arbitrary method, and a compound (B) are thoroughly mixed and dried to remove water ( Treatment by slurry method). 3) A crude pigment of halogenated phthalocyanine (A), a compound (B), a water-soluble inorganic salt, and a water-soluble organic solvent in which the inorganic salt is insoluble are added, and the water-soluble inorganic salt / crude pigment (mass ratio) = 0.
5 to 20, water-soluble organic solvent / crude pigment = 0.5 to 2 (mass ratio), at an appropriate temperature, for example 60 to 120 ° C., for 30 minutes to
Solvent salt milling is performed for 15 hours to make the crude pigment into a halogenated phthalocyanine (A) pigment, which is washed with water and dried (treatment by the solvent salt milling method). 4) mixing the crude pigment of halogenated phthalocyanine (A), the compound (B) and a large excess of organic solvent with respect to them,
Organic solvent / crude pigment (mass ratio) = 3 to 20, and pressurizing as necessary, at an appropriate temperature, for example, 60 to 120 ° C.,
After heating for 30 minutes to 15 hours, the crude pigment is used as a pigment of a halogenated dissimilar metal phthalocyanine (A), the organic solvent is filtered, washed with water and dried (treatment by a solvent method).

However, among the above methods 1) to 4), the treatment by the slurry method of 2) or the solvent salt milling method of 3) is performed by using a halogenated phthalocyanine (A).
On the particle surface of the primary particles before agglomeration of the compound (B)
Is preferable in that it is possible to obtain a colorant composition sufficiently adhered, and a green organic colorant having excellent dispersibility in a medium to be colored can be obtained as compared with other methods. Regardless of whether it is the powder method of 1) or the solvent method of 4), uniform treatment cannot be performed without stirring and mixing for a longer period of time with the treatment by these, and the treatment by the slurry method of 2) or the solvent salt milling method of 3) In order to obtain the same effect, a larger amount of compound (B) is used as compared with them, which is not economical. The difference between these effects is
In the preparation of the color filter, the high and low Y values are affected.

The halogenated phthalocyanine (A) and the yellow condensed polycyclic compound (B) are mixed and then milled by a solvent salt milling method to form a pigment (this operation is referred to as co-milling). As a result, it is possible to obtain a colorant composition in which the yellow condensed polycyclic compound (B) is more sufficiently adhered to the surface of the halogenated phthalocyanine (A) particles, and the pigmented compounds are mixed separately. It is possible to obtain a colorant composition in which color separation is less likely to occur than in the colorant composition prepared as described above and which has improved dispersibility and coloring power.

When a color filter is produced, the halogenated phthalocyanine (A) and the yellow condensed polycyclic compound (B) are pigmented as described above, and the average primary particle diameter is 0.01. It is preferable to use a green colorant composition of ˜0.10 μm. Moreover, it is preferable that the aspect ratio of the primary particles in the vertical and horizontal directions is 1 to 3 because the viscosity characteristics are improved and the fluidity is further increased.

The average particle size of the primary particles in the present invention means the particles in the visual field with a transmission electron microscope JEM-2010 (manufactured by JEOL Ltd.) to form an aggregate on a two-dimensional image. For each of the 50 primary particles of each colorant, the longer diameter (major axis) is determined, and the average value is obtained. The aspect ratio of particles in the vertical and horizontal directions can be obtained by similarly obtaining the shorter diameter (shorter diameter) together with the long diameter described above. At this time, each colorant as a sample is photographed with a microscope after ultrasonically dispersing it in a solvent. A scanning electron microscope may be used instead of the transmission electron microscope.

The colorant composition of the present invention may be prepared from only the halogenated phthalocyanine (A) and the yellow condensed polycyclic compound (B), but in the color filter application, the yellow condensed polycyclic compound (B) is used. The Y value can be further improved by using a known and commonly used yellow organic colorant such as a yellow organic pigment (C) other than the above).

The yellow organic pigment (B) is preferably a quinophthalone type pigment, and the yellow organic pigments (B) and (C) can be contained in the halogenated phthalocyanine (A) in a mass ratio of 1% to 70%. .

The colorant composition of the present invention can be used for forming a green pattern of a color filter by a known method. Typically, it is possible to obtain a photosensitive composition for a green portion of a color filter, which contains the colorant composition of the present invention and a photosensitive compound as essential components. As a method for producing a color filter, for example, the colorant composition of the present invention is dispersed in a dispersion medium containing a photosensitive compound, and then a transparent substrate such as glass is formed by a spin coating method, a roll coating method, an inkjet method, or the like. There is a method called photolithography, in which a green pattern is obtained by applying an overcoat, and then subjecting this coating film to pattern exposure with ultraviolet light through a photomask, and then washing the unexposed portion with a solvent or the like to obtain a green pattern. .

In addition, electrodeposition method, transfer method, micelle electrolysis method,
PVED (Photovoltaic Electro)
A color filter may be manufactured by forming a green pattern by a deposition method. In addition, using a known pigment for the red pattern and the blue pattern,
It can be formed by a similar method.

In order to prepare the photosensitive composition for the green portion of the color filter, the colorant composition of the present invention, the photosensitive compound, the photopolymerization initiator, and the organic solvent that dissolves the resin are essential components. Mix. The production method is generally a method in which a dispersion liquid is prepared using the colorant of the present invention, an organic solvent and, if necessary, a dispersant, and then a photosensitive resin or the like is added to form a resist ink. is there.

Examples of the photosensitive compound used at this time include various mono- and trifunctional acrylates such as methyl (meth) acrylate, ethylene glycol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, styrene, and the like. Other monomers such as vinyl acetate and N-vinylpyrrolidone, and various alkali-soluble resins can be used.

The color filter resist ink thus prepared can be used as a color filter by performing pattern exposure with ultraviolet rays through a photomask and then washing the unexposed portion with an organic solvent or alkaline water. .

The colorant composition of the present invention has a yellowish green color and is used for paints, plastics, printing inks, rubbers, leathers, textile printing, electronic toners, jet inks, and thermal transfer, in addition to the detailed color filters. Suitable for coloring ink.

[0052]

EXAMPLES The present invention will now be specifically described with reference to examples. Hereinafter, unless otherwise specified,% and parts are converted into mass.

[Production Example 1] Chloroaluminum phthalocyanine was produced from phthalic anhydride, urea and aluminum chloride as raw materials. The 1-chloronaphthalene solution of this is
It had light absorption at 750 to 850 nm. The halogenation was carried out by mixing 3.2 parts of thionyl chloride, 3.8 parts of anhydrous aluminum chloride and 0.5 part of sodium chloride at 40 ° C.
2.7 parts of bromine are added dropwise. To this, 1 part of chloroaluminum phthalocyanine is added and reacted at 90 ° C. for 15 hours, after which the reaction mixture is poured into water to precipitate a halogenated chloroaluminum phthalocyanine crude pigment. The aqueous slurry was filtered, washed with hot water at 60 ° C., washed with 1% sodium hydrogensulfate water, washed with hot water at 60 ° C., dried at 90 ° C., and 2.7 parts of purified halogenated chloroaluminum phthalocyanine crude pigment. Got This halogenated chloroaluminum phthalocyanine crude pigment had an average composition of AlClPcBr ₁₄ Cl ₁ H based on a halogen content analysis by a flask combustion ion chromatograph (M = Al,
Y = Cl and n = 1, m = 15).

[Production Example 2] Zinc phthalocyanine was produced using phthalodinitrile and zinc chloride as raw materials. One of this
The chloronaphthalene solution had absorption of light at 750 to 850 nm. Halogenated thionyl chloride 3.1
Parts, 3.7 parts of anhydrous aluminum chloride and 0.5 parts of sodium chloride are mixed at 40 ° C., and 2.6 parts of bromine is added dropwise. Add 1 part of zinc phthalocyanine and add 1 part at 90 ℃.
After reacting for 5 hours, the reaction mixture is poured into water to precipitate a zinc halide phthalocyanine crude pigment. The aqueous slurry was filtered, washed with hot water at 60 ° C., washed with 1% sodium hydrogen sulfate aqueous solution, washed with acetone containing 7% toluene,
It was washed with hot water at 60 ° C. and dried at 90 ° C. to obtain 2.6 parts of purified zinc halide phthalocyanine crude pigment. The halogenated zinc phthalocyanine crude pigment has an average composition of ZnPcBr ₁₄ Cl from the halogen content analysis by mass spectrometry.
It was ₁ H (M = Zn, n = 0, m = 15).

[Production Example 3] 4,5,6,7-tetrachloro-2- [2- (4,5,6,7-tetrachloro-2,
3-dihydro-1,3-dioxo-1H-indene-2
-Yl) -8-quinolinyl] -1H-isoindole-
Made by BASF of Germany, consisting of 1,3 (2H) -dione Pa
liotol Gelb K0961HD (CI Pigment Ye
20 parts of low 138) and 300 parts of 98% sulfuric acid were placed in a 500 ml separable flask and reacted at 120 ° C. for 5 hours to sulfonate the quinophthalone compound. Then, the reaction mixture was taken out into 3000 parts of water to precipitate a quinophthalone sulfonic acid derivative, which was stirred and aged for 30 minutes, and then filtered and washed with water three times. Then, 1% of the wet cake obtained above
It was washed with 300 parts of dilute hydrochloric acid, filtered, and washed with water until the filtrate became colored. After that, it is dried with a hot air dryer,
Part (yield 95.9%) of solid was obtained. This solid was a quinophthalone-based sulfonic acid derivative in which X was a chlorine atom, m was 4, M was a hydrogen atom, and n = 1 in the general formula. The content rate (average number of substituents) of sulfonic acid groups contained in the whole solid was 0.9.

Example 1 95 parts of the halogenated chloroaluminum phthalocyanine crude pigment of Production Example 1, 5 parts of the quinophthalone compound having a sulfonic acid group as a functional group of Production Example 3, 700 parts of ground sodium chloride, 200 parts of diethylene glycol. , 5 parts of xylene were charged into a double-arm kneader and kneaded (co-milled) at 100 ° C. for 6 hours. After kneading, the product was taken out in 5000 parts of water at 80 ° C., stirred for 1 hour, filtered, washed with hot water, dried and pulverized to obtain a green colorant composition (hereinafter, composition). The average particle size of the primary particles is 0.03μ
m, and the aspect ratio in the vertical and horizontal directions was 3.3. The average particle diameter and the aspect ratio of the primary particles were determined from the results of measurement with a transmission electron microscope JEM-2010 (manufactured by JEOL Ltd.).

[Example 2] 75 parts of zinc halide phthalocyanine crude pigment of Production Example 2, 5 parts of quinophthalone compound having a sulfonic acid group as a functional group of Production Example 3, Germany B
ASF Paliotol Gelb K0961HD (CI Pig
The same procedure as in Example 1 was carried out except that 20 parts of ment Yellow 138) was used to obtain a green colorant composition (hereinafter, referred to as a composition). The average particle size of the primary particles is
The aspect ratio was 0.04 μm and the aspect ratio was 3.6.

[Example 3] The same operation as in Example 1 was carried out except that the halogenated chloroaluminum phthalocyanine crude pigment of Production Example 1 was replaced with the same amount of the zinc halide phthalocyanine crude pigment of Production Example 2. A colorant composition was obtained (hereinafter, composition). The average particle size of the primary particles is
The aspect ratio was 0.05 μm and the aspect ratio was 2.8.

[Comparative Example 1] 80 parts of 9YC (chlorinated brominated copper phthalocyanine pigment) manufactured by Avicia and Paliot manufactured by BASF of Germany were used so that the same mass composition as in Example 1 was obtained.
ol Gelb K0961HD (C.I. Pigment Yell
ow 138) and 20 parts of ow 138) were evenly mixed for 1 hour at room temperature with a shaking mixer to obtain 100 parts of a green colorant composition (hereinafter, referred to as composition). The average particle size of the primary particles was 0.08 μm, and the aspect ratio in the vertical and horizontal directions was 6.3.

[Examples 4 to 6 and Comparative Example 2] Using the compositions obtained in the above Examples or Comparative Examples as a green colorant composition, color filters were produced by photolithography. did. As a method for producing a color filter, 17 parts of each green colorant composition,
2.5 parts of N, N'-dimethylformamide, Disperbic 161 (manufactured by Big Chemie) 17.0 parts, Eucherester EEP (manufactured by Union Carbide) 63.
Add 5 parts of 0.5 mmφ sepul beads and disperse with a paint conditioner (manufactured by Toyo Seiki Co., Ltd.) for 1 hour.
A pigment dispersion was obtained. 75.00 parts of this pigment dispersion and a polyester acrylate resin (Aronix M7100,
5.50 parts, manufactured by Toagosei Kagaku Kogyo Co., Ltd., dipentaerythrate hexaacrylate (KAYARAD DP)
HA, manufactured by Nippon Kayaku Co., Ltd.), 5.00 parts, benzophenone (KAYACURE BP-100, manufactured by Nippon Kayaku Co., Ltd.), 1.00 parts, and Eukerester EFP, 13.5 parts were stirred with a dispersion stirrer to obtain a color resist. It was The color resist was applied to a glass having a thickness of 1 mm so that the dry film thickness was 1 μm. Next, after pattern exposure with ultraviolet rays was performed through a photomask, the unexposed portion was washed with an organic solvent to obtain a color filter.

The viscosities of the respective color resists produced from these compositions were determined by VISCOMTE manufactured by Toki Sangyo Co., Ltd.
It was measured by R MODEL RL. The color tone and brightness of the green patterns of the color filters manufactured from these compositions were visually evaluated. Also,
Using a first-class spectrophotometer (spectrophotometer) specified in JIS Z 8722, a spectral transmission spectrum at 380 to 780 nm is measured, and the wavelength at which the transmittance becomes maximum (λma
x), and the transmittance (Tmax) at λmax was measured.
About the cured color resist coating film on this color filter, microscopic photometer OSP manufactured by Olympus Corporation
With -SP-200, the color coordinate x and y values were combined to measure the Y value in the CIE color system chromaticity. The results are summarized in Table 1.

[0062]

[Table 1]

In Table 1, the abbreviations indicate the following contents. Color ○… Green with a fairly yellowish color ×: Yellowish green Brightness ○… very bright △… Slightly dark

As is apparent from Table 1, a green colorant composition containing a halogenated metal phthalocyanine using Al and Zn as a central metal and a quinophthalone compound having a sulfonic acid group as a functional group, and a color prepared from the green colorant composition Since the viscosity of the resist is relatively low and the flowability is excellent, the color filter manufactured using them and the green pattern have a higher Y value in comparison with the same x and y values, and have a good transparency. It was more yellowish and brighter, which was closer to the bright line of the backlight light source of the liquid crystal display device. On the other hand, the viscosity of the color resist was high from a green colorant composition containing a halogenated copper phthalocyanine using copper as a central metal and a quinophthalone compound having no sulfonic acid group as a functional group, and was manufactured using them. The produced color filter also had a small Y value and was inferior in transparency. Compared to the examples, the yellowness was weaker and the color was a little dark green.

[0065]

The green colorant crude composition of the present invention comprises a halogen-free metal-free phthalocyanine or a specific halogenated dissimilar metal phthalocyanine having a central element other than copper and a yellow color containing a sulfonic acid group or a sulfonate as a functional group. Since it contains a condensed polycyclic compound, it is more fluid and more yellowish than a conventional green colorant composition comprising a halogenated copper phthalocyanine and a yellow condensed polycyclic compound containing no sulfonic acid group or the like. It produces a brighter greenish color. Therefore, the colorant of the present invention is most suitable for forming the green pattern of the color filter.

─────────────────────────────────────────────────── ─── Continuation of front page (51) Int.Cl. ⁷ Identification code FI theme code (reference) G02B 5/20 101 G02B 5/20 101 5/22 5/22 (72) Inventor Shin Kudo Kashima-gun, Ibaraki Prefecture 3428-1 Chite, Kamisu-cho (72) Inventor Shoji Funakura 3-4-1-302 Misatodai, Narita-shi, Chiba F-term (reference) 2H048 BA02 BA45 BA47 BB02 BB42

Claims (6)

[Claims] 1. A green colorant composition comprising a green organic colorant and a yellow organic colorant, wherein the green organic colorant is a halogenated phthalocyanine represented by the following formula, and the yellow organic colorant is a sulfonic acid. A green colorant composition, which is a yellow condensed polycyclic compound having a group or a sulfonate as a functional group. [Chemical 1] (In the formula, M is Al, Si, Sc, Ti, V, Mg, F
e, Co, Ni, Zn, Ga, Ge, Y, Zr, Nb,
It represents In, Sn, Pb, and 2H. X represents fluorine, chlorine, bromine, iodine, which may be the same or different,
m represents an integer of 8 to 16. Y is fluorine, chlorine, bromine,
Represents iodine, oxygen, hydroxyl group, sulfonic acid group, n is 0 to
Represents an integer of 2. ) 2. A yellow organic colorant containing at least a yellow condensed polycyclic compound having a sulfonic acid group or a sulfonate as a functional group is 1 to 70 per 100 parts by weight of the halogenated phthalocyanine represented by the above formula. The green colorant composition according to claim 1, which is a part. 3. The green colorant composition according to claim 1, wherein the condensed polycyclic compound is a yellow quinophthalone compound having a sulfonic acid group or a sulfonic acid metal salt as a functional group. 4. The green color according to claim 1, further comprising a quinophthalone-based pigment other than a yellow quinophthalone-based compound having a sulfonic acid group or a metal salt of sulfonic acid as a functional group, as the yellow organic colorant. Colorant composition. 5. A color filter comprising the green colorant composition according to any one of claims 1, 2, 3 and 4. 6. A green organic colorant comprising a halogenated phthalocyanine represented by the following formula and a yellow organic colorant comprising a yellow condensed polycyclic compound having a sulfonic acid group or a sulfonate as a functional group. Color filter. [Chemical 2] (In the formula, M is Al, Si, Sc, Ti, V, Mg, F
e, Co, Ni, Zn, Ga, Ge, Y, Zr, Nb,
It represents In, Sn, Pb, and 2H. X represents fluorine, chlorine, bromine, iodine, which may be the same or different,
m represents an integer of 8 to 16. Y is fluorine, chlorine, bromine,
Represents iodine, oxygen, hydroxyl group, sulfonic acid group, n is 0 to
Represents an integer of 2. )