TWI419941B - Process for the production of an ε form phthalocyanine pigment - Google Patents

Description

Method for producing ε-type phthalocyanine pigment

The present invention relates to a process for producing an ε-type phthalocyanine pigment which has remarkably excellent dispersibility in a carrier and has fine powder particles for color development, which is sized to a uniform particle size. More specifically, the present invention relates to a process for producing an ε-type phthalocyanine pigment which can be provided when it is used to disperse colored particles of a powder in a carrier such as an aqueous flexographic printing ink, a colorant or an aqueous dispersion. Good gloss, high tinting strength and clarity and suitability for even applications where finer pigment particles are required, such as inks for ink jet printing or color filters.

The phthalocyanine pigment has a pleasant hue and high tinting strength, and its various properties such as weather resistance and heat resistance make it widely used in the field of the coloring material industry.

Various phthalocyanine pigments containing a central metal such as copper, zinc, nickel, cobalt or aluminum are known. Among these phthalocyanine pigments, copper phthalocyanine is the most clear and widely used. In addition, metal-free phthalocyanine and phthalocyanines containing different metals such as zinc phthalocyanine and cobalt phthalocyanine are also commercially practical.

Further, the phthalocyanine pigment has different crystal forms such as an α form, a β form, a δ form, and an ε form. In particular, the ε-type phthalocyanine pigment has a more reddish hue than α-type phthalocyanine and is clear, and has a high coloring power. Further, the ε-type phthalocyanine pigment has an excellent property in that it is more stable in crystal transformation. The ε-type phthalocyanine pigment is very useful in coloring materials, electronic materials, and the like.

The phthalocyanine obtained by the synthesis usually has a β form crystal form, and they contain coarse acicular particles having a size of about 10 to 200 μm and are called crude phthalocyanine. Therefore, as a coloring pigment for inks, paints or plastics, its value is very low.

In order to obtain an ε-type phthalocyanine pigment, conversion of the crystal form to the ε form is required and a treatment called pigmentation is also required. In the pigmentation treatment, the particles are subdivided to obtain a size of about 0.01 to 0.5 μm, which is valuable in terms of coloration.

Regarding a method for producing an ε-type phthalocyanine pigment, there is known a method based on a solvent treatment, a method disclosed in JP-A-48-101419, in which a ball mill is used for drying and milling for a long period of time, followed by solvent treatment. And a method disclosed in JP-A-4-252273, wherein a ε-type phthalocyanine semi-crude comprising α-type phthalocyanine is heat-treated in an organic solvent.

On the other hand, as a method based on a solvent salt milling treatment, a method is known in which a crude α-type phthalem blue (JP-A-57-149358) is kneaded by a kneading machine in the presence of a grinding aid and a binder. And another method in which a mixture of α-type phthalem blue and ε-form phthalocyanine is similarly kneaded by a kneader or the like in the presence of a pigment derivative. In addition, JP-A-2002-121420 discloses a technique for converting a ε-type phthalocyanine semi-crude containing α-type phthalocyanine into fine ε-type phthalocyanine by a solvent salt milling method.

Further, as a method based on dry milling, a method is known in which an epsilon type phthalocyanine pigment (JP) is produced by adjusting a balance between grinding by dry milling and crystal growth due to contact with an organic solvent. -A-2004-244563).

Among these methods, the solvent salt milling method using a batch type kneader is the most advantageous and most commonly used in the industry.

Solvent salt milling processes are industrially advantageous. However, due to their batch type form, quality changes between batches, due to the incorporation of foreign materials of their open type structure, and work environment pollution due to dust, conventional batch type kneaders are subject to production scale. Limitation issues. In addition, a large amount of energy is required for the subdivision of the ε-type phthalocyanine pigment, and there is also a limit to the level of subdivision. In addition, when the obtained ε-type phthalocyanine pigment is dispersed and used in a carrier such as an aqueous flexographic ink, a colorant or an aqueous dispersion, the gloss, tinting strength and transparency of the object to be coated are always required to be improved. In addition, finer pigment particles are required in applications such as inks for ink jet printing or color filters. However, it is difficult to obtain such pigment particles by the above method, and requires a large amount of energy and a large amount of time.

In view of the above circumstances, an object of the present invention is to provide a method for producing an ε-type phthalocyanine pigment which overcomes the problems of the conventional batch type kneader, such as the limitation of the production scale, the variation in quality between batches due to The incorporation of foreign materials caused by their open type structure and the pollution of the working environment due to dust.

Another object of the present invention is to provide a process for producing a ε-type phthalocyanine pigment containing finer particles using a smaller amount of energy than a conventional batch type kneader, when the pigment is in a carrier such as an aqueous flexographic printing ink. When dispersed in a colorant or aqueous dispersion, it imparts good gloss and tinting strength and transparency improvement to the coated object, and also has applications for requiring finer pigment particles therein (eg, for inkjet printing or color filtration). The adaptability of the ink of the light sheet.

According to the present invention, there is provided a method for producing an ε-type phthalocyanine pigment, which comprises kneading a mixture comprising α-type phthalocyanine, ε-form phthalocyanine, a water-soluble inorganic salt and a water-soluble organic solvent by a continuous kneader. Kneading the mixture, the kneading machine comprising a cylindrical sleeve, a concentrically mounted annular fixed disc in the sleeve, a drive shaft, a rotating disc rotated by the drive shaft, and a smash formed in a gap between the fixed disc and the rotating disc space.

The α-type phthalem blue and ε-type phthalocyanine introduced in the gap between the fixed disk and the rotating disk are broken by the rotation of the rotating disk, thereby generating α-type phthalocyanine to ε-type benzoic acid. The crystal of the blue pigment changes and the particles are subdivided and homogenized.

In the method for producing an ε-type phthalocyanine pigment provided by the present invention, the above kneaded mixture preferably contains a phthalocyanine derivative.

Further, an ε-form metal phthalocyanine pigment or a metal-free ε-type phthalocyanine pigment containing a central metal selected from the group consisting of copper, zinc, nickel, and cobalt can be produced by the method for producing an ε-type phthalocyanine pigment provided by the present invention. .

According to the present invention, the production scale is less restrictive than the conventional batch type kneader, and it is possible to produce in a proper amount in time, and it is possible to produce ε-type phthalem blue with almost no quality change between batch products. pigment. Further, since the kneading machine used is a closed type kneader, the problem of contamination of the working environment due to dust and the incorporation of foreign materials is overcome. Further, an ε-type phthalocyanine pigment containing homogenized fine particles can be easily produced with a small amount of energy. When the epsilon type phthalocyanine pigment is dispersed in a carrier such as an aqueous flexographic ink, a colorant or an aqueous dispersion, the pigment imparts a good gloss and improvement in tinting strength and transparency to the coated object. In addition, ε-type phthalocyanine pigments have excellent suitability for applications requiring finer pigment particles, such as inks for ink jet printing or color filters.

According to the present invention, wherein the kneaded mixture further contains a phthalocyanine derivative, the crystal of the produced ε-type phthalocyanine pigment is stabilized to prevent the functional crystal of the phthalocyanine derivative from being converted into the β form or the α form. Crystals, and also prevent the growth of particles, so that a fine ε-type phthalocyanine pigment can be efficiently produced. Further, it has an effect of improving the adaptability of the obtained ε-type phthalocyanine pigment in various applications.

Further in accordance with the present invention, there is provided an ε-form metal phthalocyanine pigment or a metal-free ε-type phthalocyanine pigment containing a central metal selected from the group consisting of copper, zinc, nickel and cobalt, each of which is in various ε-type phthalonitriles. Blue pigments are significantly highly visible and very useful as coloring materials.

First, a continuous kneader used in the present invention will be explained with reference to Fig. 1 . Fig. 1 is a side sectional view showing a specific example of a continuous kneader used in the present invention. As a preferred example of the continuous kneader used in the present invention, a continuous kneader disclosed in JP-B-2-92 can be used. For example, a continuous kneader ("Miracle K.C.K.") supplied by Asada Iron Works Co., Ltd. is preferably used.

As shown in FIG. 1, the continuous kneader 10 has a basic structure including a feed section 1, a kneading section 2, a discharge section 3, and a metering feeder section 4. The feed section 1 includes a cylindrical sleeve 11 extending in the horizontal direction and a spiral rod 12 which is concentric with the sleeve 11 and assembled in a sliding contact state. The raw material inlet 111 for receiving the raw material from the metering feeder section 4 is opened on the upstream side at the upper surface of the sleeve 11. The start end (right side in FIG. 1) of the spiral wand 12 is concentrically fixed to the drive shaft 121 of the drive motor, and the motor is omitted in FIG. 1, driven by the drive motor, and the drive shaft 121 is used as a medium to make the spiral wand 12 Rotate about the axis of the drive shaft 121. A spiral fin 122 spirally formed in a predetermined direction is provided on the outer surface of the spiral wand 12. The raw material supplied from the metering feeder section 4 is forcibly sent to the kneading section 2 by the helical fins 122 rotating about the axis.

A metering feeder section 4 is provided for adding a raw material to be subjected to a continuous kneading process (the present invention comprises α-type phthalocyanine, ε-form phthalocyanine, a mixture of a water-soluble inorganic salt and a water-soluble organic solvent) Go to feed section 1. The metering feeder section 4 includes a raw material hopper 41 containing raw materials, a raw material supplied from the bottom of the raw material hopper 41 is fed to the screw feeder 42 of the feed section 1, and a raw material inlet from the casing 11 A connecting cylinder 43 is vertically provided around the periphery of 111 to cover the downstream end of the screw feeder 42.

The screw feeder 42 is mounted such that its spiral fins are in sliding contact with the intermediate cylindrical body 44 provided between the bottom hole of the raw material hopper 41 and the upper hole of the connecting cylinder 43. The start end (right side in Fig. 1) of the screw feeder 42 is concentrically connected to the drive shaft of the feed motor omitted in Fig. 1. Therefore, due to the driving of the feed motor, the rotation of the screw feeder 42 about the axis, by the intermediate cylinder 44 and the connecting cylinder 43, the material in the raw material hopper 41 is spiraled into the predetermined amount. The hopper 42 is added to the sleeve 11.

The kneading section 2 includes a plurality of fixed disks 21, an annular kneading cylinder 22 provided between the fixed disks 21, the fixed disk 21 and the annular kneading cylinder 22 are alternately arranged, and the rotating disk 23, the front and rear surfaces of the rotating disk 23 (Right and left surfaces in Fig. 1) are opposed to the fixed disk 21 and are fitted concentrically into the kneading cylinder 22. The coupling rod omitted in Fig. 1 is inserted through the above plurality of fixed disks 21 and the kneading cylinder 22. The beginning end of the coupling rod is fixed to the sleeve 11 of the feed section 1. Thereby, the fixed disk 21 and the kneading cylinder 22 are integrated with the feed section 1.

Each of the rotary disks 23 is fitted on a spline shaft omitted in FIG. 1, which is concentrically protruded from the foremost surface of the spiral wand 12. A cylindrical intermediate screw 24 is provided between each two adjacent rotating disks 23. Thereby, the rotary disk 23 and the intermediate screw 24 are alternately mounted on the spline shaft. The outer diameter of the rotary disk 23 is slightly smaller than the inner diameter of the kneading cylinder 22, and the outer diameter of the intermediate screw 24 is slightly smaller than the inner diameter of the fixed disk 21. For this reason, in a state in which the rotary disk 23 and the intermediate screw 24 are alternately assembled on the spline shaft, the outer circumferential surface of each of the rotary disk 23 and each intermediate screw 24 is passed through the gap between the raw material and each of the kneading circles. The cylindrical body 22 is opposed to the inner circumferential surface of the fixed disk 21.

Due to the above configuration of the continuous kneading machine 10, the raw material carried in the raw material hopper 41 is discharged from the bottom of the raw material hopper 41 by the driving of the screw feeder 42, and then passes through the intermediate cylindrical body 44 and the connecting cylindrical body 43. The sleeve 11 is introduced into the feed section 1. Due to the driving of the spiral rod 12, the raw material introduced into the sleeve 11 is sequentially conveyed to the downstream kneading section 2 by the rotation of the spiral fins 122.

Then, the raw material conveyed to the kneading section 2 is first passed between the outer circumferential surface of the intermediate screw 24 which is rotated about the axis on the most upstream side (the right side in FIG. 1) and the inner circumferential surface of the fixed disk 21 which is the most upstream. Clearance. Then, the raw material passes through the gap between the left side surface of the fixed disk 21 on the most upstream side in Fig. 1 and the right side surface of the rotary disk 23 which is rotated around the axis on the most upstream side. The raw materials are kneaded as they pass through these gaps. The above kneading operation for the raw material is repeated in a plurality of stages in accordance with the number of the fixed disk 21, the kneading cylinder 22, the rotating disk 23 and the intermediate screw 24 which are mounted. Thereby, various components of the raw material (α-type phthalocyanine, ε-formaldehyde blue, water-soluble inorganic salt and water-soluble organic solvent in the present invention) are subjected to kneading treatment. The product obtained by the completion of the kneading process is separated from the outer circumferential surface of the rotary disk 23 disposed on the most downstream side and the inner circumferential surface of the kneading cylinder 22 disposed on the most downstream side, that is, the discharge section 3 discharge.

Fig. 2 shows a front view (viewed from the right side of Fig. 1) or a rear view (viewed from the left side of Fig. 1) of the fixed disk and the rotary disk in the specific example of the continuous kneading shown in Fig. 1. In Fig. 2, (a) is a cavity-magnetic area-shape fixing disk 21a, (b) is a cavity-magnetic area-shaped rotating disk 23b, and (c) is a cavity-rose-shaped fixed disk 21c, ( d) is a cavity-rose-shaped rotating disk 23d, (e) is a cavity-mortar-shape fixing disk 21e, and (f) is a cavity-mortar-shaped rotating disk 23f.

As shown in Fig. 2, each of the fixed disks 21 has a movable fitting hole 211 concentric with the intermediate screw 24, in which the intermediate screw 24 is to be movably assembled. On the front and rear surfaces (front side and rear side) of each of the fixed disks 21, a plurality of recesses (cavities (shredding spaces) 212) are dug in the radial direction from the movable fitting hole 211, and these notches are in the circumference The directions are set at regular intervals. On the other hand, each of the rotary disks 23 has a fitting hole 231 concentric with the spline shaft, and the spline shaft omitted in Fig. 1 is to be fitted therein in a state of close contact. A cavity (shredding space) 232 corresponding to the cavity 212 of the fixed disk 21 is dug on the front and rear surfaces of each of the rotary disks 23. The edge of each cavity 232 of the rotating disk 23 is open.

Due to the driving of the spiral rod 12, the raw materials introduced into the gap between the fixed disk 21 and the rotary disk 23 are pushed into the respective cavities 212 and 232, respectively. In this state, the rotation of the rotary disk 23 about the axis exerts a shearing force on the raw materials in the cavities 212 and 232 at the boundary surface between the cavities 212 and 232. That is, the cavity 212 of the fixed disk 21 and the original material in the cavity 232 of the rotary disk 23, which are opposed to each other, are cut by the ridges of the mountain portions of the cavities 212 and 232, so that shearing force and substitution act on the original material. Thereby the raw material is kneaded and dispersed. In the above alternative, the sheared raw material exits cavities 212 and 232, while the new raw material enters the same cavities 212 and 232.

Depending on the shape of the cavities 212 and 232, the fixed disk 21 and the rotating disk 23 are divided into a plurality of different kinds of fixed disks and rotating disks. That is, they are divided into a cavity-magnetic-shape-fixing disk 21a and a cavity-magnetic-shape-shaped rotating disk 23b shown by (a) and (b) of Fig. 2, by (c) and (d) of Fig. 2. The cavity-rose-shaped fixed disk 21c and the cavity-rose-shaped rotating disk 23d are shown, and the cavity-mortar-shape fixing disk 21e and cavity-showed by (e) and (f) in Fig. 2钵-shape rotating disk 23f. These different kinds of fixed discs and rotating discs are used to increase the shearing force acting on the raw materials according to the progress of the kneading and dispersing treatment.

That is, from highest to lowest, the porosity of the cavity 212 or 232 (the area percentage (%) of the cavity 212 of the fixed disk 21 or the cavity 232 of the rotating disk 23, based on the surface area of the fixed disk 21 or the rotating disk 23) The arrangement is a magnetic zone-shaped cavity 212 or 232, a rose-shaped cavity 212 or 232, and a mortar-shaped cavity 212 or 232. The shear force acting on the raw material increases as the porosity decreases.

In this embodiment, the fixed disk 21 containing the magnetic zone-shaped cavity 212 or the rotating disk 23 containing the magnetic zone-shaped cavity 232; the fixed disk 21 containing the rose-shaped cavity 212 or containing a rose-shaped cavity a rotating disk 23 of 232; and a fixed disk 21 containing a mortar-shaped cavity 212 or a rotating disk 23 containing a mortar-shaped cavity 232 arranged in order from the upstream side to the downstream side, so that shearing of the original material is performed The force is increased in accordance with the progress of the kneading and dispersion treatment of the raw materials.

In this way, instead of suddenly applying a large shear force to the raw material, the shearing force on the raw material increases sequentially as the kneading and dispersing treatment of the raw material proceeds. Therefore, the kneading and dispersing treatment is applied to the raw material smoothly without any additional stress. Therefore, a mixture of α-type phthalene blue, ε-form phthalocyanine, a water-soluble inorganic salt and a water-soluble organic solvent (each of which is a component of a raw material) can be kneaded and dispersed without any trouble.

According to the continuous kneader 10 having such a structure, a mixture of α-type phthalocyanine blue and ε-type phthalocyanine (which are components of the raw materials) is introduced into the gap between the fixed disk 21 and the rotary disk 23 (especially Ground, cavities 212 and 232), and thus shear forces are applied to the pigment particles by the rotation of the rotating disk 23. Due to the above application of the shearing force, the above α-type phthalocyanine crystal is converted into ε-type phthalocyanine and at the same time the particles can be divided into fine particles.

Then, the kneaded mixture to be kneaded and dispersed by the continuous kneading machine 10 will be described in detail.

The α-type phthalocyanine blue and ε-type phthalocyanine used for kneading the mixture are metal phthalocyanine or metal-free phthalocyanine containing a central metal, and can be produced by a known method. When using each of the α form and ε type phthalocyanine or the α form and the ε form metal-free phthalocyanine containing copper, zinc, nickel or cobalt as a central metal, it can be obtained as a coloring material which is particularly highly clear and Very useful ε form metal phthalocyanine pigment or copper ε-free phthalocyanine pigment containing copper, zinc, nickel or cobalt as the central metal.

The alpha form of xylylene blue can be produced by acid gelatinization of, for example, crude phthalocyanine. Ε-type phthalocyanine can be produced by milling a solvent salt of α-type phthalocyanine. Further, a mixture of alpha-formaldehyde blue and epsilon-type phthalocyanine can be produced by dry milling a crude alpha-formaldehyde blue in the presence of a milling medium.

The α-type phthalocyanine blue and the ε-type phthalocyanine are preferably contained in the kneaded mixture in a certain ratio such that the ε type is contained per 100 parts by weight of the total amount of the α-type phthalocyanine blue and the ε-type phthalocyanine blue. The amount of the phthalocyanine is 2 to 40 parts by weight, more preferably 5 to 30 parts by weight. The above content of ε-formaldehyde blue is less than 2 parts by weight, and the crystal transition speed of α-phthalic blue to ε-type phthalocyanine is low. When it is more than 30 parts by weight, the overall production efficiency from crude phthalocyanine is lowered. Every situation is industrially unfavorable.

Further, the water-soluble inorganic salt used for kneading the mixture is not particularly limited. Examples thereof include common salts (sodium chloride), potassium chloride, sodium sulfate, zinc chloride, calcium chloride, and mixtures of these.

The amount of the water-soluble inorganic salt in the kneaded mixture is not particularly limited. When it is too small, crystal transformation of the ε-type phthalocyanine pigment or subdivision and homogenization of the particles is difficult. When it is too large, the amount of treated α-type phthalocyanine blue and ε-type phthalocyanine becomes small, so that the productivity is unfavorably lowered industrially. Therefore, the amount of the water-soluble inorganic salt is preferably from 1 to 20 times by weight based on the total weight of the α-type phthalem blue and the ε-type phthalocyanine. The amount of water-soluble inorganic salts can be selected according to the desired particle size.

Further, the addition of a water-soluble organic solvent for kneading the mixture causes α-type phthalocyanine, ε-type phthalocyanine and a water-soluble inorganic salt to form a uniform kneaded body. The water-soluble organic solvent is not particularly limited as long as it can be freely mixed with water, or even if it is not freely mixed with water, and it allows the pigment particles to grow as long as it has solubility to enable industrial washing by water. Remove. The solvent easily evaporates easily due to an increase in temperature during kneading. For this reason, a high boiling point solvent is preferred in view of safety.

The amount of the water-soluble organic solvent in the kneaded mixture is not particularly limited. When it is too small, the kneading mixture is too hard to make stable operation difficult. When it is too large, the kneading mixture is too soft so that the degree of subdivision and homogenization of the particles is lowered. Therefore, the amount of the water-soluble organic solvent is preferably from 0.3 to 5 times by weight based on the total weight of the α-type phthalem blue and the ε-type phthalocyanine. The amount of the water-soluble organic solvent can be selected in accordance with the amount of the water-soluble inorganic salt and the hardness of the kneaded mixture.

Examples of the water-soluble organic solvent include 2-(methoxymethoxy)ethanol, 2-butoxyethanol, 2-(isopentyloxy)ethanol, 2-(hexyloxy)ethanol, diethylene glycol, and two. Glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, triethylene glycol, triethylene glycol monoethyl ether, liquid polyethylene glycol, 1-methoxy-2-propanol, 1-B Oxy-2-propanol, dipropylene glycol, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, low molecular weight polypropylene glycol, aniline, pyridine, tetrahydrofuran, dioxane, methanol, ethanol, isopropanol, n-propanol, iso Butanol, n-butanol, ethylene glycol, propylene glycol, propylene glycol monomethyl ether acetate, ethyl acetate, isopropyl acetate, acetone, methyl ethyl ketone, dimethylformamide, dimethyl hydrazine and N-methylpyrrolidone . A mixture of at least two organic solvents can be used as required.

It is preferred to introduce a phthalocyanine derivative in the kneaded mixture for the purpose of efficiently producing a fine ε-type phthalocyanine pigment, which is a ε-type phthalocyanine pigment which is stably produced by the introduction of the phthalocyanine derivative. The crystals and thus the crystals are prevented from being converted into beta-form crystals or alpha-form crystals, and also prevent particle growth. The xylylene blue derivative is a metal-free or metal phthalocyanine derivative containing at least one substituent represented by the general formula (1), -X-Y (1)

Wherein X is a single bond or a divalent bonding group which is chemically composed of 2 to 50 atoms selected from a hydrogen atom, a carbon atom, a nitrogen atom, an oxygen atom and a sulfur atom, and Y is a nitro group or a halogen Atom, -NR ₁ R ₂ , -SO ₃ . M/m or -COO. M/m substituted phthalimido iminomethyl, wherein R ₁ and R ₂ each independently represent a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkenyl group or a substituted or unsubstituted phenyl group or R ₁ and R ₂ together form a substituted or unsubstituted heterocyclic ring which may further contain a nitrogen atom, an oxygen atom or a sulfur atom, M represents a hydrogen ion, a metal ion having a valence of 1 to 3 or consists of at least one alkyl group Substituted ammonium ion, and m is the valence of M.

Specific examples of the substituent represented by the general formula (1) include o-phthalimidomethylamino group, 4-nitrophthalimidoiminomethyl group, 4-chlorophthalic acid imidomethyl group. , tetrachlorophthalic iminomethyl, carbachol, amisulpht, aminomethyl, dimethylaminomethyl, diethylaminomethyl, dibutylaminomethyl, piperidine Methyl, dimethylaminopropylaminosulfonyl, diethylaminopropylaminosulfonyl, dibutylaminopropylaminosulfonyl, morpholinoethylaminosulfonyl, dimethylamino Propylaminocarbonyl, 4-(diethylaminopropylaminocarbonyl)phenylaminocarbonyl, dimethylaminomethylcarbonylaminomethyl, diethylaminopropylaminomethylcarbonylaminomethyl, dibutyl Aminopropylaminomethylcarbonylaminomethyl, sulfonate, sodium sulfonate, calcium sulfonate, aluminum sulfonate, dodecyl ammonium sulfonate, octadecyl ammonium sulfonate, trimethyl ten Octaalkylammonium sulfonate, dimethyldistenyl ammonium sulfonate, carboxylic acid group and 2-aluminumcarboxylate-5-nitrobenzimidylaminomethyl.

The phthalocyanine derivative containing these substituents can be disclosed, for example, in JP-B-39-28884, JP-B-57-15620, JP-B-58-28303, and JP-B-64-5070. Manufacturing.

The operating conditions of the continuous kneader in the present invention are not particularly limited. Crystallization of α-type phthalocyanine to ε-type phthalocyanine and the addition of particles in contact with water-soluble organic solvents are effective for the sliding of α-type phthalocyanine and ε-type phthalocyanine, respectively. The kneading temperature is preferably from 50 to 210 ° C, particularly preferably from 80 to 130 ° C. An increase in the kneading temperature promotes the crystal transition and the growth rate of the pigment particles. The ε-type phthalic acid to be obtained can be controlled by adjusting the mixing ratio of the kneading mixture, the kneading temperature, and the input quantity of mechanical energy (the number of revolutions of the main shaft (the drive shaft 121), the supply amount of the raw material, the power load of the main shaft, and the like). The amount or quality of blue pigment. When the kneading temperature is higher than 130 ° C, the growth of the particles is considerable, and thus, in view of the quality in some uses, it is not desirable that the kneading temperature is higher than 130 °C.

If necessary, it is also possible to perform crystal transformation and finening and homogenization of the particles more efficiently by adjusting the temperature of the continuous kneader 10 to two stages, kneading at a high temperature in the preceding stage and at a low stage in the subsequent stage. Further, it is also possible to carry out the treatment by passing the kneaded mixture at least twice through a continuous kneader at different temperatures.

The kneaded mixture after kneading was treated according to a usual method. That is, the kneaded mixture is treated with water or an aqueous solution of an inorganic acid, followed by filtration and washing with water to remove the water-soluble inorganic salt and the water-soluble organic solvent and separate the ε-type phthalocyanine pigment. The ε-type phthalocyanine pigment can be used directly in this wet state. Further, the ε-type phthalocyanine pigment can also be used in a state in which it can be obtained by drying and pulverizing the powder. Resins, surfactants and/or other additives may be added after kneading if desired.

The use of the ε-type phthalocyanine pigment produced by the method of the present invention is not particularly limited. In addition to the use of coloring materials commonly used for ε-type phthalocyanine pigments, ε-type phthalocyanine pigments can be used in applications where high gloss, tinting strength and transparency are required. It can also be used for inkjet printing and color filters. In particular, an ε-type metal phthalocyanine pigment or a metal-free ε-type phthalocyanine pigment containing copper, zinc, nickel or cobalt as a central metal has high definition and is therefore very useful as a coloring material.

(Example)

The invention is explained in detail with reference to examples and comparative examples based on the above conventional methods, and the invention is not limited to the examples. In the examples, "parts" means "parts by weight" and "%" means "percent by weight".

In the examples and comparative examples, the crystal form of the crystal was measured by X-ray diffraction measurement (CuKα 1 ray). Further, the particle diameter was measured by a particle observation device using a transmission microscope and its image analysis.

(Example 1)

65 parts of α-type copper phthalocyanine, 35 parts of ε-type copper phthalocyanine, 1000 parts of sodium chloride and 200 parts of diethylene glycol were uniformly pre-prepared using a conversion mixer (provided by Asada Iron Works Co., Ltd.) Mix for 5 minutes. The obtained mixture was supplied to a continuous kneader 10 ("Miracle KCK-type 42" supplied by Asada Iron Works Co., Ltd.) through a screw type feeder (metering feeder section 4 (Fig. 1)), and ground. The mixture is used to produce an epsilon type copper phthalocyanine pigment. The feed section of the continuous kneading machine 10 has a screw diameter of 120 mmφ and has eight sets of kneading sections composed of a fixed disc and a rotating disc. The continuous kneader 10 was operated at a kneading mixture of 24 kg/hr, at a retention time of 8 minutes, at a spindle rotation speed of 50 rpm and at a kneading temperature of 110 °C. The kneaded composition thus obtained was taken out and poured into 3500 parts of a 1% aqueous sulfuric acid solution having a temperature of 70 °C. The mixture was stirred for 1 hour while maintaining the temperature, followed by filtration, washing with water and drying, thus obtaining a pigment. The pigment thus obtained was an ε-type copper phthalocyanine pigment having the strongest peak at X-ray diffraction measurement (CuKα1 ray) at a Bragg angle of 2θ (tolerance ± 0.2 deg.) = 9.2 degrees. The specific surface area of the ε-type copper phthalocyanine pigment according to the BET method was 91 m ² /g. The ε-type copper phthalocyanine pigment was observed by TEM (electron microscopy) and the photograph was subjected to image analysis to measure the particle diameter. The particle diameter was 36 nm as an average diameter. Further, the above ε-type copper phthalocyanine pigment was more subdivided than the ε-type copper phthalocyanine pigment obtained by the method of Comparative Example 1 described later. In addition, the amount of electric energy input per 1 kg of pigment is 2.5 kwh/kg. The above amount is based on 48% of the amount in Comparative Example 1.

(Comparative Example 1)

65 parts of α-type copper phthalocyanine, 35 parts of ε-type copper phthalocyanine, 1000 parts of sodium chloride and 200 parts of diethylene glycol were placed in a two-arm kneader having a volume of 1500 parts. The mixture was kneaded at 110 ° C for 14 hours while maintaining the mixture in a state of a thick kneaded body. The kneaded composition thus obtained was taken out and poured into 3500 parts of a 1% aqueous sulfuric acid solution having a temperature of 70 °C. The mixture was stirred for 1 hour while maintaining the temperature, followed by filtration, washing with water and drying, thus obtaining a pigment. The pigment thus obtained was an ε-type copper phthalocyanine pigment having the strongest peak at X-ray diffraction measurement (CuKα1 ray) at a Bragg angle of 2θ (tolerance ± 0.2 deg.) = 9.2 degrees. The specific surface area of the ε-type copper phthalocyanine pigment according to the BET method was 78 m ² /g. The ε-type copper phthalocyanine pigment was observed by TEM (electron microscopy) and the photograph was subjected to image analysis to measure the particle diameter. The particle size is 47 nm as the average diameter. In addition, the amount of electric energy input per 1 kg of pigment is 5.2 kwh/kg.

(Example 2)

75 parts of α-type copper phthalocyanine, 17 parts of ε-type copper phthalocyanine, 8 parts of phthalocyanine containing phthalimido iminomethyl (derived from phthalocyanine), 800 parts of chlorine Sodium hydride and 150 parts of diethylene glycol were premixed almost uniformly for 5 minutes using a conversion mixer (supplied by Asada Iron Works Co., Ltd.). The obtained mixture was supplied to a continuous kneader 10 ("Miracle KCK-type 42" supplied by Asada Iron Works Co., Ltd.) through a screw type feeder (metering feeder section 4 (Fig. 1)), and ground. The mixture is used to produce an epsilon type copper phthalocyanine pigment. The feed section of the continuous kneading machine 10 has a screw diameter of 120 mmφ and has eight sets of kneading sections composed of a fixed disc and a rotating disc. The continuous kneader 10 was operated at a kneading mixture of 20 kg/hr, at a retention time of 10 minutes, at a spindle rotation speed of 50 rpm and at a kneading temperature of 120 °C. The kneaded composition thus obtained was taken out and poured into 3000 parts of a 1% aqueous sulfuric acid solution having a temperature of 70 °C. The mixture was stirred for 1 hour while maintaining the temperature, followed by filtration, washing with water and drying, thus obtaining a pigment. The pigment thus obtained was an ε-type copper phthalocyanine pigment having the strongest peak at X-ray diffraction measurement (CuKα1 ray) at a Bragg angle of 2θ (tolerance ± 0.2 deg.) = 9.2 degrees. The specific surface area of the ε-type copper phthalocyanine pigment according to the BET method was 105 m ² /g. The ε-type copper phthalocyanine pigment was observed by TEM (electron microscopy) and the photograph was subjected to image analysis to measure the particle diameter. The particle size is 32 nm as the average diameter. Further, the above ε-type copper phthalocyanine pigment was more subdivided than the ε-type copper phthalocyanine pigment obtained by the method of Comparative Example 2 described later. In addition, the amount of electric energy input per 1 kg of pigment is 2.8 kwh/kg. The above amount is based on 56% of the amount in Comparative Example 2.

(Comparative Example 2)

75 parts of α-type copper phthalocyanine, 17 parts of ε-type copper phthalocyanine, 8 parts of phthalocyanine containing phthalimido iminomethyl (derived from phthalocyanine), 800 parts of chlorine Sodium hydride and 150 parts of diethylene glycol were placed in a two-arm kneader having a volume of 1500 parts. The mixture was kneaded at 120 ° C for 10 hours while maintaining the mixture in a state of a thick kneaded body. The kneaded composition thus obtained was taken out and poured into 3000 parts of a 1% aqueous sulfuric acid solution having a temperature of 70 °C. The mixture was stirred for 1 hour while maintaining the temperature, followed by filtration, washing with water and drying, thus obtaining a pigment. The pigment thus obtained was an ε-type copper phthalocyanine pigment having the strongest peak at X-ray diffraction measurement (CuKα1 ray) at a Bragg angle of 2θ (tolerance ± 0.2 deg.) = 9.2 degrees. The specific surface area of the epsilon type phthalocyanine pigment according to the BET method was 89 m ² /g. The ε-type copper phthalocyanine pigment was observed by TEM (electron microscopy) and the photograph was subjected to image analysis to measure the particle diameter. The particle size is 39 nm as the average diameter. In addition, the amount of electric energy input per 1 kg of pigment is 5.0 kwh/kg.

1. . . Feed section

2. . . Kneading section

3. . . Draw section

4. . . Metering feeder section

10. . . Continuous kneading machine

11. . . casing

12. . . Spiral stick

twenty one. . . Fixed disk

21a. . . Cavity-magnetic area-shaped fixed disk

21c. . . Cavity-rose-shaped fixed plate

21e. . . Cavity - mortar - shape fixing plate

twenty two. . . Kneading cylinder

twenty three. . . Rotating disk

23b. . . Cavity-magnetic zone-shape rotating disk

23d. . . Cavity-rose-shape rotating disk

23f. . . Cavity - mortar - shape rotating disk

twenty four. . . Intermediate screw

41. . . Raw material hopper

42. . . Screw feeder

43. . . Connecting cylinder

44. . . Intermediate cylinder

111. . . Raw material inlet

121. . . Drive shaft

122. . . Fin

211. . . Assembly hole

212. . . Cavity

231. . . Assembly hole

232. . . Cavity

Fig. 1 is a side sectional view showing a specific example of a continuous kneader used in the present invention.

Fig. 2 shows a front view and a rear view of a fixed disk and a rotary disk used in a specific example of the continuous kneading machine shown in Fig. 1. In Fig. 2, (a) is a cavity-magnetic region-shaped fixed disk, (b) is a cavity-magnetic region-shaped rotating disk, (c) is a cavity-rose-shaped fixed disk, and (d) is The cavity-rose-shaped rotating disk, (e) is a cavity-mortar-shaped fixed disk, and (f) is a cavity-mortar-shaped rotating disk.

1. . . Feed section

2. . . Kneading section

3. . . Draw section

4. . . Metering feeder section

10. . . Continuous kneading machine

11. . . casing

12. . . Spiral rod

twenty one. . . Fixed disk

twenty two. . . Kneading cylinder

twenty three. . . Rotating disk

twenty four. . . Intermediate screw

41. . . Raw material hopper

42. . . Screw feeder

43. . . Continuous cylinder

44. . . Intermediate cylinder

111. . . Raw material inlet

121. . . Drive shaft

122. . . Fin

Claims (4)

A method for producing an ε-type phthalocyanine pigment, which comprises kneading a kneaded mixture containing α-form phthalocyanine, ε-form phthalocyanine, a water-soluble inorganic salt and a water-soluble organic solvent by a continuous kneading machine, the kneading The machine includes a cylindrical sleeve, an annular fixed disk concentrically mounted in the sleeve, a drive shaft, a rotary disk rotated by the drive shaft, and a crushing space formed in a gap between the fixed disk and the rotary disk. The manufacturing method of claim 1, wherein the kneaded mixture further comprises a phthalocyanine derivative. The manufacturing method of claim 1, wherein the ε-type phthalocyanine pigment is an ε-form metal phthalocyanine pigment or a metal-free ε-type containing a central metal selected from the group consisting of copper, zinc, nickel, and cobalt. Benzene blue pigment. The manufacturing method of claim 2, wherein the ε-type phthalocyanine pigment is an ε-form metal phthalocyanine pigment or a metal-free ε-type containing a central metal selected from the group consisting of copper, zinc, nickel, and cobalt. Benzene blue pigment.