JP2002121420A - Copper phthalocyanine pigment and method for producing the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a fine ε-type copper phthalocyanine pigment having excellent dispersibility. SOLUTION: An ε-type copper phthalocyanine crude, an ε-type copper phthalocyanine semi-crude containing an α-type copper phthalocyanine or an ε-type copper phthalocyanine pigment having <=90 m2/g BET specific surface area measured by a nitrogen adsorption method is subjected to solvent salt milling by using 8-20 pts.wt. of an inorganic salt based on 1 pts.wt. of the crude, the semi-crude or the pigment, and the organic solvent and the inorganic salt is removed from the product to provide the objective fine ε-type copper phthalocyanine pigment having 95-150 m2/g BET specific surface area measured by the nitrogen adsorption method.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

[0001] The present invention relates to an ε-type copper phthalocyanine fine pigment and a method for producing the same.

[0002]

2. Description of the Related Art An ε-type copper phthalocyanine pigment has a strongest peak at a Bragg angle 2θ (allowable range ± 0.2 °) = 9.2 ° in an X-ray diffraction spectrum (CuKα ray), It has an excellent property that it has a reddish color tone, is clear and has high coloring power, and is more stable against crystal transition than copper phthalocyanine.

A method for producing such an ε-type copper phthalocyanine pigment is disclosed in British Patent No. 141,880 (JP-A-48-1014) by a solvent treatment.
No. 19), dry milling with a ball mill for a long time, followed by solvent treatment, or ε-type copper phthalocyanine semi-crude containing α-type copper phthalocyanine in an organic solvent as disclosed in JP-A-4-252273. There is a method of performing heat treatment.

On the other hand, there is a method described in a reference example of Japanese Patent Application Laid-Open No. Sho 57-149358 as a method using a solvent salt milling treatment.

Japanese Patent Application Laid-Open No. 9-953838 discloses that
A blue color filter using an ε-type copper phthalocyanine pigment is described.

[0006]

However, in the above-mentioned conventional methods, there is a limit in making the pigment finer, and the obtained ε-type copper phthalocyanine pigment having a small specific surface area has a dispersibility in use. Was insufficient. As a result, when used for a color filter, there is also a disadvantage that sharpness and lightness are insufficient.

[0007]

The inventors of the present invention have conducted intensive studies in view of the above-mentioned situation, and as a result, have found that the above-mentioned problems can be solved by using an ε-type copper phthalocyanine pigment having a larger specific surface area than conventional ones. The invention has been completed.

That is, the present invention provides the following invention in order to solve the above problems. 1. BET specific surface area of 95 to 150 in nitrogen adsorption method
An ε-type copper phthalocyanine fine pigment having a m ² / g ratio.

[0009] 2. ε-type copper phthalocyanine crude, α
-Type copper phthalocyanine semi-crude containing copper phthalocyanine or a BET specific surface area of 90 m in nitrogen adsorption method
² / g or less ε-type copper phthalocyanine pigment, solvent salt milling the crude, semi-crude or pigment with 8 to 20 parts by weight of inorganic salt per 1 part by weight, and then removing the organic solvent and the inorganic salt, A method for producing an ε-type copper phthalocyanine fine pigment having a BET specific surface area of 95 to 150 m ² / g in a nitrogen adsorption method.

[0010]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in detail. The ε-type copper phthalocyanine fine pigment according to the present invention includes C.I. I. Pigment Blue 15: 6, which is characterized by having a larger specific surface area than before.

The ε-type copper phthalocyanine fine pigment of the present invention can be obtained, for example, by adding ε-type copper phthalocyanine crude or ε-type copper phthalocyanine semi-crude containing α-type copper phthalocyanine to crude or semi-crude under the condition that the ratio of inorganic salt to semi-crude is higher than before. And solvent salt milling.

The ε-type copper phthalocyanine crude used in the present invention is defined as having an average primary particle diameter of 50 to 0.1 μm.
Mean ε-type copper phthalocyanine, while ε-type copper phthalocyanine semi-crude containing α-type copper phthalocyanine is α-type copper phthalocyanine in which primary particles having an average particle diameter of 0.02 to 0.001 μm are aggregated with ε-type copper phthalocyanine. A mixture with type copper phthalocyanine.

Here, as a method for producing the ε-type copper phthalocyanine crude, any known and conventional production method for producing copper phthalocyanine in the presence or absence of a metal phthalocyanine derivative can be used. The method of producing copper phthalocyanine in the presence is preferred because the content of ε-type copper phthalocyanine increases. The phthalocyanine derivative will be described later in detail.

[0014] As such a production method, for example, phthalic anhydride, urea and a copper salt and a reaction catalyst are heated and stirred in a nitrobenzene solvent in the presence of a condensation reaction product of copper phthalocyanine sulfochloride and dehydroabiethylamine. The synthesis method (JP-A-53-39325) and the reaction of phthalic anhydride, urea and a copper salt and a reaction catalyst in an alkylbenzene solvent in the presence of a copper phthalocyanine sulfamide derivative and ε-type copper phthalocyanine as seed crystals. A method of synthesizing by heating and stirring (JP-A-57-149358) or the like can be used.

The ε-type copper phthalocyanine semi-crude containing the α-type copper phthalocyanine can be obtained, for example, by grinding the ε-type copper phthalocyanine crude. Usually, the ε-type copper phthalocyanine crude is obtained by grinding the ε-type copper phthalocyanine crude in the presence of a grinding medium. Obtained by dry grinding.

Examples of the dry milling device used for the milling include a ball mill device filled with a grinding medium and the like.
A vibration mill device, an attritor mill device, a cylindrical bead mill device, a horizontal double drum mill device and the like can be mentioned. Among these devices, a cylindrical grinding container having a longitudinal axis for putting powder to be ground, a rotating shaft arranged along this axis, and fixed to the rotating shaft, respectively Is a stirrer having two or more pairs of arms extending symmetrically outwardly toward the side wall of the milling vessel, and an attritor mill device filled with steel balls as a grinding medium is preferable (this is particularly preferred). No. 58-29861).

Examples of the grinding media used in the dry mill include, for example, balls and rods of iron, stainless steel, corundum, pottery, steatite, aluminum oxide, zirconium oxide, oxide mixture, quartz and the like. Its size is usually 1 to 50 mm in diameter.

This dry milling is usually carried out at a temperature of 100 ° C. or lower, preferably at a temperature of room temperature to 100 ° C. The dry milling time is determined by the type of milling equipment and the required pigment specific surface area, but is generally 0.1 to 36 hours. For example, when the above-mentioned suitable attritor mill is used as a grinding device, the dry grinding time is usually 0.1 to 10 times.
The time is preferably 0.5 to 5 hours, and the dry milling time when using a vibrating mill is usually 1 to 36 hours, preferably 2 to 12 hours.

When the ε-type copper phthalocyanine crude containing a metal phthalocyanine derivative is ground, ε-type copper phthalocyanine semi-crude containing α-type copper phthalocyanine and a phthalocyanine derivative is obtained. In the case of obtaining a semi-crude having a similar average particle diameter of primary particles, milling in the presence of the metal phthalocyanine derivative can shorten the milling time.

In the present invention, instead of the above crude or semi-crude, the BET specific surface area in the nitrogen adsorption method is 90%.
An ε-type copper phthalocyanine pigment of m ² / g or less can be used. This ε-type copper phthalocyanine pigment, for example,
It can be obtained according to GB 141118. In this method, α-type, γ-type or δ-type copper phthalocyanine or a mixture thereof is pulverized using a high degree of pulverization energy so as to essentially include ε-type, and the pulverized product is mixed with, for example, ethanol, propanol, butanol, With an organic solvent such as pentanone or tetrahydrofuran,
This is a method of heating at a temperature lower than the temperature (limit temperature) specific to the organic solvent which does not convert copper phthalocyanine into β-form (limit temperature) for 1 to 30 hours, stirring, removing the solvent, and drying. In order to prevent the crystal transition to β-form, water can be used in combination. If necessary, the above operation can be performed under pressure.

Hereinafter, ε-type copper phthalocyanine crude:
ε-type copper phthalocyanine semi-crude containing α-type copper phthalocyanine and BET specific surface area of 90 m in nitrogen adsorption method
The ε-type copper phthalocyanine pigment of ² / g or less is collectively referred to as a crude pigment for convenience.

The crude pigment thus obtained is then subjected to a pigmentation treatment. The pigmentation treatment method is not particularly limited, and various pigmentation treatment methods can be adopted, but the crystal growth is more easily suppressed than the solvent treatment in which the crude pigment is heated and stirred in a large amount of organic solvent. It is preferable to employ a solvent salt milling treatment from the viewpoint that pigment particles having a large specific surface area can be obtained.

The solvent salt milling means kneading and milling a crude pigment, an inorganic salt and an organic solvent. Specifically, a crude pigment, an inorganic salt, and an organic solvent that does not dissolve it are charged into a kneader, and kneading and milling are performed therein. As a kneader at this time, for example, a kneader or a mix muller can be used.

As the inorganic salt, a water-soluble inorganic salt can be suitably used, and for example, an inorganic salt such as sodium chloride, potassium chloride or sodium sulfate is preferably used. It is more preferable to use an inorganic salt having an average particle size of 0.5 to 50 μm. Such an inorganic salt can be easily obtained by pulverizing a usual inorganic salt.

Ε of the specific BET specific surface area specified in the present invention
In obtaining a fine copper phthalocyanine pigment, it is preferable that the amount of the inorganic salt used with respect to the amount of the crude pigment used in solvent salt milling be higher than before. That is, the amount of the inorganic salt used is 8 to 2 parts by weight per 1 part by weight of the crude pigment.
The amount is preferably 0 parts by weight, more preferably 10 to 15 parts by weight.

As the organic solvent, a water-soluble organic solvent as an organic solvent capable of suppressing crystal growth can be suitably used. For example, diethylene glycol, glycerin, ethylene glycol, propylene glycol, liquid polyethylene glycol, liquid polypropylene glycol, (Methoxymethoxy) ethanol, 2-butoxyethanol, 2
-(Isopentyloxy) ethanol, 2- (hexyloxy) ethanol, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether,
Diethylene glycol monobutyl ether, triethylene glycol, triethylene glycol monomethyl ether, 1-methoxy-2-propanol, 1-ethoxy-2-propanol, dipropylene glycol, dipropylene glycol monomethyl ether, dipropylene glycol monomethyl ether, dipropylene glycol, etc. Can be used.

The amount of the water-soluble organic solvent to be used is not particularly limited, but may be 0.0 to 1 part by weight of the crude pigment.
1 to 5 parts by weight is preferred.

In the production method of the present invention, only the crude pigment may be subjected to the solvent salt milling. However, the solvent salt milling using the crude pigment and the phthalocyanine derivative in combination is more effective for the pigment having the specific surface area defined in the present invention. This is preferable because it can be obtained in a short time. The crude pigment produced in the presence of the phthalocyanine derivative may be subjected to solvent salt milling as it is, or the phthalocyanine derivative may be added to the crude pigment produced in the absence of the phthalocyanine derivative for solvent salt milling. Of course, solvent salt milling may be performed by further adding a phthalocyanine derivative to the crude pigment produced in the presence of the phthalocyanine derivative.

When a fine pigment having the same specific surface area is obtained, it is more preferable to perform solvent salt milling in the presence of a phthalocyanine derivative than to perform solvent salt milling in the absence of the phthalocyanine derivative, even within the range specified in the present invention. The amount of the inorganic salt used can be further reduced.

As the phthalocyanine derivative that can be included in the crude pigment during the preparation of the crude pigment and / or during the solvent salt milling, any known and commonly used phthalocyanine derivative can be used, but a phthalocyanine derivative represented by the following general formula (I) is preferred.

[0031]

Embedded image P- (AY) _n (I)

(Wherein, P represents a phthalocyanine residue having no or having a central metal, A represents a direct bond or a divalent linking group, and Y represents a primary to primary amino group or a heterocyclic residue. And n represents ４4)

Specifically, phthalimidomethyl derivatives of the metal-free or metal phthalocyanines, sulfonic acid derivatives thereof,
The same N- (dialkylamino) methyl derivative and the same N- (dialkylaminoalkyl) sulfonic acid amide derivative are preferable. These phthalocyanine derivatives are preferably further used by adding an amine such as a primary amine, a secondary amine, a tertiary amine, a quaternary amine salt, and ethylenediamine.

The phthalocyanine derivative used in combination with the crude pigment is preferably a sulfonic acid derivative or a derivative composed of a sulfonic acid-aromatic amine condensate in that the yield of ε-type copper phthalocyanine is the highest. As the phthalocyanine derivative used in combination,
The phthalimidomethyl derivative is preferable in that the specific surface area can be further increased. As metal phthalocyanine derivatives,
It is preferable to use a copper phthalocyanine derivative corresponding to the central metal of the pigment.

The phthalocyanine derivative which can be contained in the crude pigment during the preparation of the crude pigment and / or during the solvent salt milling is usually 0.01 to 0.1 part by weight per part of the crude pigment.
0.3 parts by weight. When the phthalocyanine derivative is used at the time of preparing the crude pigment and / or at the time of solvent salt milling, the total amount of the crude pigment and the phthalocyanine derivative is regarded as the usage amount of the crude pigment, and the usage amount of the inorganic salt is as described above. Select from a range.

The temperature during solvent salt milling is 3
0 to 150 ° C is preferable, and 80 to 100 ° C is more preferable. Solvent salt milling time from 5 hours to 2 hours
0 hours is preferable, and 8 to 18 hours is more preferable.

In this way, a mixture containing the ε-type copper phthalocyanine pigment of the present invention having a BET specific surface area of 95 to 150 m ² / g in the nitrogen adsorption method, an inorganic salt and an organic solvent as main components is obtained. And inorganic salts are removed, and if necessary, a solid substance mainly composed of fine ε-type copper phthalocyanine pigment is washed, filtered, dried, pulverized, etc. to obtain fine ε-type copper phthalocyanine pigment powder. . As the washing, any of water washing and hot water washing can be adopted. The number of times of washing can be repeated in the range of 1 to 5 times. In the case of the mixture using a water-soluble inorganic salt and a water-soluble organic solvent, the organic solvent and the inorganic salt can be easily removed by washing with water.

As the above-mentioned filtration and drying after washing, for example, a batch type or continuous type in which the pigment is dehydrated and / or desolvented by heating at 80 to 120 ° C. by a heating source installed in a dryer or the like is used. Drying and the like can be mentioned, and examples of the dryer generally include a box dryer, a band dryer, a spray dryer and the like. In addition, the pulverization after drying is not an operation for increasing the specific surface area or reducing the average particle diameter of the primary particles, but, for example, the pigment is ramped as in the case of drying using a box dryer or a band dryer. It is performed to dissolve the pigment when it becomes in a state such as a powder, for example, a mortar,
Pulverization by a hammer mill, a disc mill, a pin mill, a jet mill, or the like can be given.

Thus, a pigment powder containing as a main component the fine ε-type copper phthalocyanine pigment of the present invention having a BET specific surface area of 95 to 150 m ² / g in the nitrogen adsorption method is obtained. The ε-type copper phthalocyanine pigment of the specific specific surface area of the present invention can be used for any of known and commonly used applications, but by achieving this specific surface area, the dispersibility in a synthetic resin or the like to be colored becomes better. .

In the field of color filters,
Light-shielding properties at 365 nm, which are frequently used when curing a resist ink for a color filter, are reduced, so that the photocuring sensitivity of the resist is not reduced and a film edge and a pattern flow during development are less likely to occur.

In the present invention, B in the nitrogen adsorption method
The ET specific surface area is measured according to JIS Z 8830-1990 (method for measuring specific surface area of powder by gas adsorption).

In the case of producing a color filter, the fine pigment of the present invention has a BET specific surface area of 9 in a nitrogen adsorption method.
It is preferable that the average particle diameter of the primary particles is 5 to 150 m ² / g and the average particle diameter of the primary particles is 0.01 to 0.06 μm. When the average particle diameter of the primary particles of the fine pigment is within the above particle diameter range,
Pigment aggregation is relatively weak, the pigment can be easily dispersed in the resist ink for a color filter, and a color filter that has high sharpness and high brightness required in recent years can be obtained more easily.

The fine pigment of the present invention preferably has an aspect ratio of 4 or less in the vertical and horizontal directions, because it also contributes to the improvement of the viscosity characteristics of inks and paints, and has a higher fluidity.

The average particle diameter and the aspect ratio of the primary particles of the pigment can be measured by a transmission electron microscope or a scanning electron microscope. The average particle size of the primary particles of the pigment in the present invention is determined by a transmission electron microscope JEM.
-2010 (manufactured by JEOL Ltd.) takes a picture of the pigment in the field of view and finds the longer diameter (major axis) of each of the 50 primary pigment particles constituting the aggregate on the two-dimensional image,
It is the average value.

The aspect ratio of the primary particles in the vertical and horizontal directions of the pigment in the present invention can be obtained from the minor axis and the major axis. For the minor axis, the pigment in the field of view is photographed with a transmission electron microscope, and the shorter diameter (minor axis) of each of the 50 primary pigment particles constituting the aggregate on the two-dimensional image is determined. Is the average value of

In the present invention, a dioxazine-based compound pigment may be used in combination with a blue color filter for reddish coloring. Examples of the dioxazine compound pigment include C.I. I. Pigment Vio
let 23 and 37. In the present invention, when a conventional small specific surface area ε-type copper phthalocyanine pigment is used in combination with a dioxazine-based compound pigment, a decrease in brightness when a liquid crystal display is formed is reduced, and a light transmission amount in a blue region is reduced. Will be larger.

The ε-type copper phthalocyanine fine pigment of the present invention can be used for forming a blue pattern of a color filter by a known method. As a method for producing a color filter, for example, after dispersing this pigment in a dispersion medium made of a photosensitive resin, spin coating, roll coating,
Apply on a transparent substrate such as glass by ink jet method, etc.
Next, a method called photolithography is used in which a pattern exposure using ultraviolet rays is performed on the coating film through a photomask, and then the unexposed portion is washed with a solvent or the like to obtain a blue pattern.

In addition, a color filter may be manufactured by forming a blue pattern by an electrodeposition method or a transfer method.
In addition, a red pattern and a green pattern can be formed by a similar method using a known pigment.

To prepare a resist ink for a color filter, a pigment, a photosensitive resin, a photopolymerization initiator, and an organic solvent dissolving the resin are mixed as essential components. As a method for producing the resist ink, a method is generally used in which a pigment dispersion is prepared using a pigment, an organic solvent, and a dispersant if necessary, and then a photosensitive resin or the like is added thereto to form a resist ink.

Here, as the pigment, an ε-type copper phthalocyanine pigment which may or may not contain a phthalocyanine derivative, and a dioxazine compound pigment can be used if necessary.

Examples of the dispersing agent to be used if necessary include, for example, Dispervic 130, Dispervik 161, Dispervik 162, Dispervik 163, Dispervik 170 manufactured by Big Chemie, and Efka 46 and Efka 47 manufactured by Efka. . Further, a Leven rig agent, a coupling agent, a cationic surfactant, and the like can be used together.

As the organic solvent, toluene, xylene,
Aromatic solvents such as methoxybenzene, ethyl acetate and butyl acetate, acetate solvents such as propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propionate solvents such as ethoxyethyl propionate, methanol, ethanol, etc. Alcohol solvents, butyl cellosolve, propylene glycol monomethyl ether, ether solvents such as diethylene glycol ethyl ether, diethylene glycol dimethyl ether, ketone solvents such as methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, aliphatic hydrocarbon solvents such as hexane, N, N- Nitrogen compound solvents such as dimethylformamide, γ-butyrolactam, N-methyl-2-pyrrolidone, aniline, pyridine, γ-butyrol Lactone solvents such as lactone; carbamates such as a 48:52 mixture of methyl carbamate and ethyl carbamate; water; As the organic solvent, in particular, propionate type, alcohol type,
Water-soluble polar solvents such as ethers, ketones, nitrogen compounds, lactones, and water are suitable.

300-100 parts by weight per 100 parts by weight of pigment
A pigment dispersion can be obtained by stirring and dispersing 0 parts by weight of an organic solvent and, if necessary, 0 to 80 parts by weight of a dispersant so as to be uniform. Next, 3 to 20 parts by weight of a photosensitive resin per 1 part by weight of the pigment dispersion, 0.05 to 3 parts by weight of a photopolymerization initiator per 1 part by weight of the photosensitive resin,
If necessary, an organic solvent is further added, and the mixture is stirred and dispersed so as to be uniform to obtain a resist ink.

The photosensitive resin that can be used at this time includes:
For example, urethane-based resin, acrylic resin, polyamic acid-based resin, polyimide-based resin, styrene-maleic acid-based resin, thermoplastic resin such as styrene-maleic anhydride-based resin and the like, for example, 1,6-hexanediol diacrylate,
Bifunctional monomers such as ethylene glycol diacrylate, neopentyl glycol diacrylate, triethylene glycol diacrylate, bis (acryloxyethoxy) bisphenol A, 3-methylpentanediol diacrylate, etc., trimethylol propaton triacrylate, pentaerythritol Triacrylate, tris (2-hydroxyethyl) isocyanate,
Examples include photopolymerizable monomers such as polyfunctional monomers such as dipentaerythritol hexaacrylate and dipentaerythritol pentaacrylate.

Examples of the photopolymerization initiator include acetophenone, benzophenone, benzyldimethylketanol,
Benzoyl peroxide, 2-chlorothioxanthone, 1,3-bis (4′-azidobenzal) -2-propane, 1,3-bis (4′-azidobenzal) -2-propane-2′-sulfonic acid, 4,4 And '-diazidostilbene-2,2'-disulfonic acid.

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

The pigment of the present invention is a fine pigment having high clarity.
Suitable for coloring of paint, plastic, printing ink, rubber, leather, textile printing, electronic toner, jet ink, thermal transfer ink, etc.

[0058]

Next, the present invention will be described in detail with reference to Production Examples, Examples and Comparative Examples. Note that “parts” and “%” are based on weight.

Production Example 1 "Fast Gen" manufactured by Dainippon Ink and Chemicals, Inc.
Blue EPC ”(ε-type copper phthalocyanine blue crude. The average particle diameter of primary particles is 0.1 to 10 μm, the specific surface area is 5 m ² / g. It contains a derivative composed of a trace amount of copper phthalocyanine sulfonic acid-aromatic amine condensate.) 1 Parts, ground sodium chloride 10 parts, diethylene glycol 1 part,
0.05 parts of a copper phthalocyanine phthalimide methyl derivative was charged into a double-arm kneader and kneaded at 80 ° C to 90 ° C for 10 hours. After kneading, the mixture was taken out into 100 parts by weight of a 1% hydrochloric acid aqueous solution at 80 ° C., stirred for 1 hour, filtered, washed with hot water, dried and pulverized to obtain a fine ε-type copper phthalocyanine pigment (a).

The BET specific surface area of the obtained fine pigment (a) by a nitrogen adsorption method was measured using Microsoap 4232II manufactured by Micro Data Co., Ltd., and the specific surface area was 110 m ² / g. The company's NI
MO-206-11 of ST (specific surface area 110 ± 7 m ² /
The result of calibration using g) was 112.34 m ² / g. The average particle diameter was measured with a transmission electron microscope JEM-2010 (manufactured by JEOL Ltd.).
The average particle size was 0.02 μm. The vertical and horizontal aspect ratio was 2.

Production Example 2 "Fast Gen" manufactured by Dainippon Ink and Chemicals, Inc.
Blue EPC ”using an attritor mill
Dry milling was performed at a power density of 0.4 KW per liter of milling space to obtain semi-crude (a mixture of α-type and ε-type, specific surface area 3 m ² / g) having an average primary particle diameter of 0.02 μm. In addition, the attritor mill device used here has a cylindrical grinding container having a longitudinal axis for putting powder to be ground, a rotating shaft arranged along this axis, and a rotating shaft. An attritor mill device fixed to a shaft and having two or more pairs of arms each extending outward and symmetrically toward the side wall of the milling vessel, and filled with steel balls as grinding media. is there.

1 part of this semi-crude, 10 parts of ground sodium chloride, 1 part of diethylene glycol, and 0.10 part of copper phthalocyanine N- (dimethylaminopropyl) sulfonic acid amide derivative were charged into a double-arm kneader, and the mixture was heated to 80 ° C.
Kneaded at ~ 90 ° C for 7 hours. After kneading, the mixture is taken out into 100 parts by weight of a 1% aqueous hydrochloric acid solution at 80 ° C., stirred for 1 hour, filtered, washed with hot water, dried and pulverized to obtain a fine pigment of ε-type copper phthalocyanine (b).
I got

The specific surface area of the obtained fine pigment (b) was 130 m ² / g by the above instrument, and the average particle diameter by the above instrument was 0.01 μm. The vertical and horizontal aspect ratio was 1.5.

Production Example 3 According to Example 1 of JP-A-48-101419, first, crude β-type copper phthalocyanine was dissolved in concentrated sulfuric acid, and this sulfuric acid solution was poured into a large amount of water to be converted to α-type copper phthalocyanine. The mixture was filtered, washed with water until neutral, and dried. Next, 10 g of this α-type copper phthalocyanine was placed in a planet ball mill (volume: 0.2 liter, ball diameter: 3c) containing steel balls.
m, sphere volume of 28 cm ³ ) for 16 hours at 20 ° C. to obtain a dry milled product containing α-type and ε-type copper phthalocyanine, which is then milled in a 20-fold amount of ethanol at 78 ° C. for 8 hours. The mixture was stirred under reflux to produce an ε-type copper phthalocyanine pigment. This was filtered, washed with water and dried. This ε-type copper phthalocyanine blue pigment had an average primary particle diameter of 0.1 μm and a specific surface area of 50 m ² / g. One part of the ε-type copper phthalocyanine blue pigment, 10 parts of ground sodium chloride, 1 part of diethylene glycol, and 0.05 part of a copper phthalocyanine phthalimide methyl derivative were charged into a double-arm kneader and kneaded at 80 ° C to 90 ° C for 8 hours. After kneading, take out 100 parts by weight of 1% hydrochloric acid aqueous solution at 80 ° C.
After stirring for an hour, the mixture was filtered, washed with hot water, dried and pulverized to obtain an ε-type copper phthalocyanine fine pigment (c).

The specific surface area of the obtained fine pigment (c) determined by the above-mentioned equipment was 110 m ² / g, and the average particle diameter measured by the above-mentioned equipment was 0.02 μm. Vertical and horizontal aspect ratio is 2
Met.

Production Example 4 1 part of semicrude obtained in Production Example 2, 3 parts of toluene, n-
After pouring into a mixed solvent consisting of 1.5 parts of butanol and 6.7 parts of water and heating at an azeotropic temperature for 4 hours, the solvent was distilled and recovered, filtered and pulverized to obtain an ε-type copper phthalocyanine pigment.

The pigment (d) obtained had a specific surface area of 70 m ² / g by the above instrument and an average particle diameter of 0.10 μm by the above instrument. The aspect ratio in the vertical and horizontal directions was 4.

Production Example 5 The ε-type copper phthalocyanine pigment was obtained by changing the kneading temperature from 80 ° C. to 90 ° C. from 120 ° C. to 130 ° C. by changing 10 parts of the crushed sodium chloride of Production Example 1 to 7 parts.

The pigment (e) obtained had a specific surface area of 70 m 2 / g by the above equipment and an average particle diameter of 0.07 μm by the above equipment. The vertical and horizontal aspect ratio was 2.

Example 1 Using the fine pigment (a) obtained in the above Production Example as a blue pigment, anthraquinone red as a red pigment, and brominated phthalocyanine green as a blue pigment, the following photolithography was used. A color filter was manufactured.

The method for producing the color filter is as follows: 10 parts of the fine pigment (a), 2.5 parts of N, N'-dimethylformamide, 6.78 parts of Dispervic 161 (manufactured by BYK Chemie), and Eucherester EEP (Union
80.80 parts of Carbide Co., Ltd. was added with 0.5 mmφ seple beads and dispersed for 1 hour with a paint conditioner (manufactured by Toyo Seiki Co., Ltd.) to obtain a pigment dispersion. 75.00 parts of this pigment dispersion, 5.50 parts of a polyester acrylate resin (Aronix M7100, manufactured by Toagosei Chemical Industry Co., Ltd.), 5.00 pentaerythrate hexaacrylate (KAYARAD DPHA, manufactured by Nippon Kayaku Co., Ltd.) Part, benzophenone (KAYACURE
BP-100, manufactured by Nippon Kayaku Co., Ltd.) 1.00 part, Eucerester EFP 13.5 parts were stirred with a dispersion stirrer,
A color resist was obtained. The color resist was applied to a 1 mm thick glass so as to have a dry film thickness of 1 μm.

Next, after performing pattern exposure with ultraviolet rays through a photomask, the unexposed portions were washed with an organic solvent to obtain color filters.

Example 2 A color filter was produced in the same manner as in Example 1 except that the pigment composition (b) obtained in the above Production Example was used as a blue pigment.

Example 3 A color filter was produced in the same manner as in Example 1 except that the pigment composition (c) obtained in the above Production Example was used as a blue pigment.

The clarity and lightness of the blue pattern of the color filters of Examples 1, 2 and 3 were visually evaluated. Table 1 shows the results.

Comparative Example 1 A color filter was produced in the same manner as in Example 1 except that the pigment composition (d) obtained in the above Production Example was used as a blue pigment.

Comparative Example 2 A color filter was produced in the same manner as in Example 1 except that the pigment composition (e) obtained in the above Production Example was used as a blue pigment.

Further, the clarity and lightness of the blue pattern of the color filter manufactured in the same manner as in Example 1 were visually evaluated. Table 1 shows the results.

[0079]

[Table 1] Table 1

The BET specific surface area in the nitrogen adsorption method is 11
The fine ε-type copper phthalocyanine pigments (a), (b), and (c) of Examples 1 to 3 having 0, 130 m 2 / g have excellent pigment dispersibility and extremely little pigment aggregation. The blue pattern that could be prepared in a short time and obtained therefrom had high sharpness and lightness, as is clear from Table 1. On the other hand, the color filters using the ε-type copper phthalocyanine pigments (d) and (e) having a BET specific surface area of 70 m 2 / g in the nitrogen adsorption method of Comparative Examples 1 and 2 had low sharpness and lightness. Pigment aggregation was larger than in the resist inks of Examples 1, 2 and 3, and the dispersibility and fluidity were somewhat poor. The photocuring sensitivity was lower than that of the example.

The fine pigments (a) of Examples 1 to 3,
(B) and (c) as C.I. I. Pigment Viol
A color filter obtained in the same manner as described above using the pigment composition used in combination with et 23 was prepared by converting pigments (d) and (e) of Comparative Example 1 to C.I. I. Pigment Violet 2
The sharpness and lightness were higher than those of the color filters obtained in the same manner as above using the pigment composition used in combination with 3.

[0082]

The ε-type copper phthalocyanine fine pigment of the present invention has a BET specific surface area of 95 to 150 m in a nitrogen adsorption method.
Since the pigment has a ratio of ² / g, it has a particularly remarkable effect of being excellent in dispersibility as compared with the conventional pigment having a smaller specific surface area. When this fine pigment is used for a color filter, a particularly remarkable effect is obtained in that a color filter that emits a clear and high-blue color and has a larger light transmission amount can be obtained. In the production method of the present invention, the proportion of the inorganic salt used relative to the crude pigment is larger than that of the conventional method, so that there is an extremely remarkable effect that an ε-type copper phthalocyanine fine pigment having a large specific surface area can be easily produced.

──────────────────────────────────────────────────続 き Continuation of the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat 参考 (Reference) G03F 7/004 505 G03F 7/004 505 (72) Inventor Hiroshi Katsube 3-14-17 Nakazato, Kita-ku, Tokyo F-term (reference) 2H025 AA04 AB13 AC01 AD01 BC13 BC42 CA00 CC12 2H048 BA02 BA45 BA48 BB02 BB14 BB42 BB46

Claims (6)

[Claims] 1. A BET specific surface area of 95 in a nitrogen adsorption method.
Ε-type copper phthalocyanine fine pigment characterized by having a particle size of １５０150 m ² / g. 2. The average particle size of the primary particles is from 0.01 to 0.1.
The ε-type copper phthalocyanine fine pigment according to claim 1, which has a thickness of 06 µm. 3. The ε-type copper phthalocyanine fine pigment according to claim 1, further comprising a phthalocyanine derivative. 4. The ε-type copper phthalocyanine fine pigment for a color filter according to any one of claims 1 to 3. 5. A ε-type copper phthalocyanine crude containing an ε-type copper phthalocyanine, an α-type copper phthalocyanine containing an α-type copper phthalocyanine, or a BET specific surface area of 90 m ² / in a nitrogen adsorption method.
g or less of the ε-type copper phthalocyanine pigment,
Solvent salt milling of semi-crude or pigment with 8 to 20 parts by weight of inorganic salt per 1 part by weight, and then removing organic solvent and inorganic salt, having a BET specific surface area of 95 to 150 m ² / g in nitrogen adsorption method A method for producing an ε-type copper phthalocyanine fine pigment. 6. The method for producing an ε-type copper phthalocyanine fine pigment according to claim 5, wherein solvent salt milling is further performed in the presence of a phthalocyanine derivative.