TWI418597B - Ε-type copper phthalocyanine pigment, its manufacturing method and coloring composition - Google Patents

Description

ε type copper phthalocyanine pigment, its production method and coloring composition

The present invention relates to a coloring composition containing an ε-type copper phthalocyanine pigment having a very small residual ratio of α -form crystal and a method for producing the same.

Ε-type copper phthalocyanine pigment, in the Cu K α X-ray diffraction diagram, has a very large diffraction intensity when the Bragg angle is 2θ=9.1°±0.2°, compared to the α -type copper phthalocyanine pigment with red A vivid hue, a blue pigment that has substantially superior properties without crystal transfer.

The method for producing the ε-type copper phthalocyanine pigment includes the following solvent treatment method, solvent dissolution polishing method, dry pulverization method, and the like.

In the production method of the solvent treatment method, the α -type, γ-type, and/or δ-type copper phthalocyanine pigments are dry-broken for a long time by a ball mill, and then treated by a solvent (refer to Japanese national speciality) JP-A-48-101419) and a method in which a crude ε-type copper phthalocyanine containing α -type copper phthalocyanine is dry-pulverized and then heat-treated in an organic solvent (Japanese Patent Laid-Open No. Hei-4-252273).

On the other hand, in the production method of the solvent dissolution polishing method, a mixture of α -type copper phthalocyanine and ε-type copper phthalocyanine is mixed and stirred in the same manner in a kneader or the like in the presence of a pigment inducer. In addition, a method of producing a fine ε-type copper phthalocyanine by a solvent-dissolving polishing method using a crude ε-type copper phthalocyanine containing α -type copper phthalocyanine is disclosed (JP-A-2002-121420).

In addition, in the production method of the dry pulverization method, a dry pulverization and a contact with an organic solvent are used to produce a method in which the crystallization is balanced and grown (Japanese Laid-Open Patent Publication No. 2004-244563).

Among them, the solvent dissolution grinding method using the batch type kneading machine is the most advantageous and widely used in the industry.

However, the ε-type copper phthalocyanine pigment produced by the above-described conventional method is not used for clarification, lithographic ink, gravure ink, paint, plastic colorant, coloring composition for color filter, and the like, and cannot completely satisfy the sharpness. The quality requirements of transparency and fluidity, especially when used in a gravure printing ink and a coloring composition for a color filter, are disadvantageous in that opacity tends to become high viscosity.

That is, the object of the present invention is used in inks, paints, plastic colorants, the color filter with the coloring composition and the like, can fully meet the vividness, transparency, flowability quality requirements, to provide the α-type copper phthalocyanine An ε-type copper phthalocyanine pigment having a substantially reduced cyanine to zero and a method for producing the same. Further, another object of the present invention is to provide a coloring composition of an ε-type copper phthalocyanine pigment.

As a result of intensive review, the present inventors have found that the ε-type copper phthalocyanine pigment produced by the conventional method contains a small amount of α -type copper phthalocyanine, and the above problems can be solved by reducing the content thereof, and the object of the present invention is attained.

That is, by the first aspect of the present invention, an ε-type copper phthalocyanine pigment can be provided, which is characterized by satisfying a variation curve of the diffraction amount of Cu K α X light, and when the Bragg angle is 2θ=5°, on the above-mentioned quantitative curve Point, and when the Bragg angle 2θ=12°, when the line connecting the points on the above-mentioned quantity change curve is used as the baseline, the diffraction intensity value of the Bragg angle 2θ=6.8° is set to A, and the Bragg angle 2θ= In the range of 9.1 ° ± 0.2 °, the maximum diffraction intensity value is set to B, the Bragg angle is 2θ = 8.6 ° ± 0.2 °, and the relationship between the minimum diffraction intensity value and C is set to C: -0.05 ≦(A-C)/(A-C+B)≦0.03

Further, a method for producing an ε-type copper phthalocyanine pigment can be provided by the second aspect of the present invention, which is characterized in that α-type copper phthalocyanine, crude ε-type copper phthalocyanine, a water-soluble inorganic salt, a water-soluble organic solvent, and the like are provided. The mixture is mixed with substantially uniform agitation.

The mixing and agitating of the foregoing mixture may be carried out in a continuous mixing mixer having an annular fixed disc and a rotating disc concentric with the fixed disc and rotating integrally around the driving shaft, the fixed disc and the rotating disc There is a crushing space between them.

Further, a colored composition comprising the ε-type copper phthalocyanine pigment of the present invention and a liquid medium component can be provided by the third aspect of the present invention.

The ε-type copper phthalocyanine pigment of the present invention is an ε-type copper phthalocyanine pigment which substantially reduces the content of α-type copper phthalocyanine to zero, and is compared with a conventional ε-type copper phthalocyanine pigment containing a small amount of α-type copper phthalocyanine. When used for a coloring composition for gravure inks and color filters, a transparent and low viscosity dispersion can be obtained.

Further, by the method for producing an ε-type copper phthalocyanine pigment of the present invention, an ε-type copper phthalocyanine pigment having a content ratio of α-type copper phthalocyanine reduced to zero can be easily obtained.

The ε-type copper phthalocyanine pigment of the present invention is a point of the ε-type copper phthalocyanine pigment having a very high purity, which is in the curve of the Cu K α X light diffraction intensity, and the Bragg angle 2θ=5°, on the above-mentioned quantitative curve. And when the Bragg angle 2θ=12°, when the straight line connecting the points on the above-mentioned quantitative curve is used as the baseline, the diffraction intensity value of the Bragg angle 2θ=6.8° is set to A, and the Bragg angle 2θ=9.1°± In the range of 0.2°, the maximum diffraction intensity value is set to B, the Bragg angle is 2θ=8.6°±0.2°, and the relationship between the minimum diffraction intensity value and C is set to C: -0.05≦(A) -C)/(A-C+B)≦0.03

The value represented by (A-C)/(A-C+B) is an index value of the residual ratio of α-type copper phthalocyanine. When the value of the index is large, the content of the α-type copper phthalocyanine pigment is large, and the small value indicates the α-type copper. The content of the phthalocyanine pigment is small.

Fig. 4 is a view showing an X-ray diffraction pattern of a mixture of α -type copper phthalocyanine and ε-type copper phthalocyanine in the middle of the ε-type copper phthalocyanine pigment (in the middle of crystallization transition), specifically illustrating the foregoing A value, B value and C value.

The A value, the B value, and the C value are each in the range of the diffraction intensity value of the ε -type copper phthalocyanine pigment at a Bragg angle 2θ=6.8°, the Bragg angle 2θ=9.1°±0.2°, the maximum diffraction intensity value, and the Prague value. The angle of 2θ = 8.6 ° ± 0.2 °, its extremely small diffraction intensity value. It is not itself but the Cu K α X light diffraction intensity variation curve PF of the ε-type copper phthalocyanine pigment, the point P1 on the above-mentioned quantitative curve PF when the Bragg angle is 2θ=5°, and when the Bragg angle is 2θ When =12°, the calculated value is obtained when the straight line connected to the point P2 on the above-mentioned amount-variable curve is used as the baseline BS.

In more detail, the A value is the diffraction intensity value (the original diffraction intensity value of the α-type copper phthalocyanine pigment) A1 from the Bragg angle 2θ=6.8°, and deducted when the Bragg angle 2θ=6.8°, corresponding to the baseline BL The value calculated from the diffraction intensity value A2 of the point BP1. The B value is in the range of the Bragg angle 2θ=9.1°±0.2°, and its maximum diffraction intensity value (the original diffraction intensity value of the ε-type copper phthalocyanine pigment) B1, deducted from the Prague as the maximum diffraction intensity value B1. The angle 2θ value corresponds to the value calculated from the diffraction intensity value B2 of the point BP2 on the baseline BL. The C value is in the range of 2θ=8.6°±0.2°, and its extremely small diffraction intensity value C1 is deducted from the point BP3 on the baseline BL when the Bragg angle 2θ value of the minimum diffraction intensity value C1 is subtracted. The value calculated from the intensity value C2.

The (crude) ε-type copper phthalocyanine pigment obtained by the conventional production method has a value of (A-C)/(A-C+B) (hereinafter referred to as an index value) of more than 0.03, and a crude ε having an index value exceeding 0.03. The copper phthalocyanine pigment is dispersed in the liquid medium component, and then the ink and the coating material are prepared, and the sharpness, transparency, and fluidity are insufficient. On the other hand, the index value of the ε-type copper phthalocyanine pigment of the present invention is at least -0.05, and a more desirable index value than the ε-type copper phthalocyanine pigment of the present invention is -0.04 ≦(A-C)/(A- C+B)≦0.01

The ε-type copper phthalocyanine pigment of the present invention can be produced by substantially uniformly stirring and mixing a mixture containing α-type copper phthalocyanine, crude ε-type copper phthalocyanine, a water-soluble inorganic salt, a water-soluble organic solvent or the like.

The method for producing the ε-type copper phthalocyanine pigment of the present invention is characterized in that the mixture is substantially uniformly stirred and mixed. In the case of a method in which the above mixture is substantially uniformly stirred and mixed, it is a suitable method to use a continuous mixing mixer. In the conventional mixing and agitating method, a batch type mixing agitator is used, and when the mixed agitation material enters a dead angle, it is taken out without crystal transfer, so that it is difficult to obtain a high-purity ε-type copper phthalocyanine pigment. However, in the case of using a batch type mixing mixer, if the contents are completely taken out without increasing the production cost, and the mixture is stirred again, the mixture can be substantially uniformly mixed and stirred.

The following detailed description relates to a method of producing an ε-type copper phthalocyanine pigment using a continuous mixing mixer.

In the case of a continuous mixing mixer, the continuous mixing mixer has an annular fixed disc and a rotating disc concentric with the fixed disc and rotating integrally around the driving shaft, and the smash is defined between the fixed disc and the rotating disc space. Figure 1 is a cross-sectional view of a side view of one such continuous mixer. In the above-mentioned continuous mixing mixer which is suitable for use, for example, it is described in Japanese Patent Publication No. 2-92, and a continuous mixing mixer "Miracle K.C.K." manufactured by Asada Iron Works Co., Ltd. can be exemplified.

As shown in FIG. 1, the continuous mixing mixer 10 has a basic configuration of a feeder unit 1, a mixing and agitating unit 2, a discharge unit 3, and a dose feeder unit 4. The feeder portion 1 has a cylindrical casing 11 extending in the horizontal direction, and a spiral bar 12 concentric with the casing 11 and inserted in a sliding state. On the upper side of the outer casing 11, there is a raw material inlet port 111 which receives the raw material from the dosing unit 4. The base end portion (right side in FIG. 1) of the spiral wand 12 is concentrically fixed to the motor drive shaft 121, and is driven to rotate around the shaft center through the drive shaft 121 by driving by a drive motor (not shown). The outer peripheral surface of the spiral wand 12 is provided with a spiral wing 122 that is screwed in a predetermined direction, and the raw material supplied from the quantitative feeder unit 4 is rotated around the axis by the spiral blade 122, and is pumped to the mixing and stirring unit 2 .

The dose feeder portion 4 is for supplying a raw material (in the present invention, a mixture of α-type copper phthalocyanine, ε-type copper phthalocyanine, a water-soluble inorganic salt, and a water-soluble organic solvent) to the object of the continuous mixing and stirring treatment. The device of the feeder unit 1. The raw material hopper 41 accommodating the raw material, the dosing machine 42 that feeds the raw material that has been cut from the bottom of the raw material hopper 41 to the feeder unit 1, and the peripheral portion from the raw material inlet port 111 to the outer casing 11 are erected. The cylinder 43 covers the downstream end of the dosing unit 42.

The dosing machine 42 interposes between the opening of the bottom of the raw material hopper 41 and the opening of the upper portion of the connecting cylinder 43 with a cylindrical body 44 in which a spiral wing in a sliding state is mounted, and the concentric connection is measured at the base end (Fig. 1 right) The drive shaft of the feed motor (not shown). In other words, the shaft of the dosing machine 42 is rotated by the driving of the feed motor, and the raw material in the raw material hopper 41 is sent to the dosing device 42, and the pre-set is supplied through the interposing cylinder 44 and the interconnecting cylinder 43. The amount of conveyance is transferred to the outer casing 11.

The mixing and agitating unit 2 is configured by a plurality of fixed discs 21 and an annular mixing agitating cylinder 22 and a front surface (the surface of the upper and lower sides of FIG. 1) which are disposed between the fixed discs 21 and the fixed disc 21 in a clamped state. And the fixed disk 21 is opposed to the rotating disk 23 of the mixing agitating cylinder 22 in a state of being opposed and concentric. The plurality of fixed discs 21 and the mixing agitation cylinder 22 are inserted through a connecting rod (not shown), and the base end portion of the connecting rod is fixed to the outer casing 11 of the feeder portion 1, so that the fixed disc 21 and the mixing are fixed. The agitating cylinder 22 is integrated with the feeder unit 1.

Each of the rotating disks 23 is concentrically fitted from the leading end surface of the spiral bar 12 to the protruding rack shaft (not shown). Phosphorus is interposed between the rotating discs 23 with a cylindrical intermediate bolt 24, such that the rotating disc 23 and the bolt 24 are alternately mounted on the rack shaft. The outer diameter of the rotating disk 23 is set to be smaller than the inner diameter of the mixing drum 22, and the outer diameter of the intermediate bolt 24 is set to be smaller than the inner diameter of the fixed disk 21, so that each rotation The disk 23 and each of the intermediate bolts 24 are externally fitted to the rack shaft, and the outer peripheral surface thereof and the inner peripheral surface of the mixing agitating cylinder 22 and the fixed disc 21 are opposed to each other, and the raw material is retained. gap.

By the configuration of the continuous mixing mixer 10, the raw material loaded in the raw material hopper 41 is sent from the bottom of the raw material hopper 41 by the driving of the dosing machine 42, and is introduced into the feeder by interposing the cylindrical body 44 and the connecting cylinder 43. Inside the outer casing 11 of the portion 1. The material introduced into the casing 11 is rotated by the driving of the spiral rod 12, and the rotation of the spiral blades 122 is sequentially carried to the mixing and stirring unit 2 of the downflow measurement.

Therefore, the material to be conveyed to the kneading section 2 first passes through the outer peripheral surface of the intermediate bolt 24 on the most upstream side (right side in FIG. 1) about the axis, and the fixed disk 21 (drive shaft 121) on the uppermost flow side. Between the inner circumferential surfaces, then between the left side surface of FIG. 1 and the right side surface of the rotating disk 23 on the most upstream side of the rotation about the axis, through the fixed disk 21 on the most upstream side, when passing through the gaps, This raw material is subjected to a mixing and agitation treatment. The operation of mixing and stirring the raw materials is repeated a plurality of times between the fixed disk 21, the mixing agitating cylinder 22, the rotating disk 23, and the intermediate bolt 24. A plurality of components (in the present invention, α-type copper phthalocyanine, crude ε-type copper phthalocyanine, a water-soluble inorganic salt, and a water-soluble organic solvent) are mixed and stirred. The product obtained by the mixing and agitating treatment is discharged from the outer peripheral surface of the rotating disk 23 on the most downstream side and the inner peripheral surface of the fixed disk 21, that is, from the discharge portion 3.

Figure 2 is a front view of the embodiment of the fixed disc and the rotating disc of the continuous mixing mixer of Figure 1 (viewed from the right in Figure 1) and the rear view (viewed from the left in Figure 1) To the map). (a) is a fan-shaped hole fixing disk 21a, (b) is a fan-shaped hole rotating disk 23b, (c) is a daisy-shaped hole fixing disk 21c, and (d) is a daisy-shaped rotating disk 23d, (e) It is a 孔-shaped hole fixing disk 21e, and (f) is a 臼-shaped hole rotating disk 23f.

As shown in FIG. 2, the play hole 211 is designed in the fixed disc 21 so as to be in the middle of the concentric and pierced intermediate bolt 24 while being on the inside (front side and back side) of the fixed disc 21, from the tour The insertion hole 211 is provided with a plurality of recesses (holes (shredding spaces) 212) of equal magnitude in the radial direction in the circumferential direction of the recess. On the other hand, the rotating disk 23 is provided with an outer fitting hole 231 so as to be fitted with a concentric and threaded rack shaft (not shown) in a closed state, and a hole is provided in the front surface of the rotating disk 23 (Pulverization space) 232) corresponds to the hole 212 of the aforementioned fixed disk 21. The peripheral portion of the hole 232 of the rotating disk 23 is in an open state.

Therefore, the material introduced into the gap between the fixed disk 21 and the rotating disk 23 is pressed by the driving of the screw bar 12, and sequentially enters the holes 212, 213, in this state, by surrounding The rotating disk 23, which is rotated by the axis, places the interface between the holes 212 and 213, and applies shearing force to the raw materials in the holes 212 and 213. That is, the raw materials in the holes 212, 213 facing the fixed disk 21 and the rotating disk 23 are aligned by the ridgeline of the mountain portions of the respective holes 212, 213. The raw material is subjected to shearing force and displacement (the sheared raw material is sent out from the respective holes 212, 213, and new raw materials are introduced into the respective holes 212, 213), so that the raw materials are dispersed and dispersed.

The fixed disk 21 and the rotating disk 23 are divided into the following plural types according to the shapes of the holes 212 and 213, mainly for increasing the shearing force applied to the raw material in order to perform the mixing and stirring dispersion treatment.

2(a) and 2(b) are a fan-shaped hole fixing disk 21a and a fan-shaped hole rotating disk 23b, FIGS. 2(c) and 2(d) are a daisy-shaped hole fixing disk 21c, and a daisy type The hole rotating disk 23d, Fig. 2(e) and Fig. 2(f) are a 臼-shaped hole fixing disk 21e and a 臼-shaped hole rotating disk 23f.

That is, the void ratio of each of the holes 212, 213 (the area ratio (%) of each of the holes 212, 213 with respect to the surface area of the fixed disk 21 and the rotating disk 23) is a fan-shaped hole 212, 213, a daisy-shaped The order of the holes 212, 213 and the 臼-shaped holes 212, 213 is getting lower and lower, but as the void ratio is smaller, the shearing force applied to the raw material is greater.

Therefore, in the present embodiment, it is desirable to gradually increase the shearing force applied to the raw material when the raw material is subjected to the mixing and dispersing treatment. Therefore, the arrangement of the holes 212 and 213 from the upstream side to the downstream side is sequentially The fixed disk 21 and the rotating disk 23, the daisy-shaped fixed disk 21, the rotating disk 23, the 固定-shaped fixed disk 21, and the rotating disk 23.

In this way, because the raw material is not suddenly subjected to a large shearing force, but is accompanied by the mixing and dispersing treatment, the shearing force applied to the raw material is gradually increased, so that the raw material can be smoothly mixed. The treatment of stirring and dispersing is carried out, whereby a mixture containing α-type copper phthalocyanine, ε-type copper phthalocyanine, a water-soluble inorganic salt, a water-soluble organic solvent or the like is substantially uniformly mixed and stirred.

In the method using a continuous mixing mixer, the appropriate mixing temperature is 130 to 210 ° C depending on the transfer efficiency from the α-type copper phthalocyanine to the ε-type copper phthalocyanine pigment and the obtained particle size of the ε-type copper phthalocyanine pigment. The best is 140~180°C.

When the mixing temperature is too low, it is difficult to transfer from α-type copper phthalocyanine to ε-type copper phthalocyanine pigment. When the temperature is too high, since the ε-type copper phthalocyanine pigment particles are easily grown, it is difficult to obtain moderate particles as pigments. size.

In the method of using a continuous mixing agitator, in order to control the amount of treatment and the quality of the pigment, the mixing ratio of the mixing and agitating composition, the supply speed of the mixing and agitating composition, the mixing and stirring temperature, and the mechanical energy input amount (the number of spindle rotations, the main axis) are adjusted. Power load, etc.).

Next, a mixture (mixing and stirring composition) containing α-type copper phthalocyanine, crude ε-type copper phthalocyanine, a water-soluble inorganic salt, and a water-soluble organic solvent to be mixed and stirred will be described.

For the raw material of the present invention, the weight ratio of the α-type copper phthalocyanine to the crude ε-type copper phthalocyanine used is suitably 0.05 to 0.6 ratio of ε-type copper phthalocyanine/α-type copper phthalocyanine, ε When the weight ratio of the copper phthalocyanine/α-type copper phthalocyanine exceeds 0.6, the production efficiency is lowered and it is not economical. When it is less than 0.05, the time from the transfer of the α-type copper phthalocyanine to the ε-type copper phthalocyanine tends to become longer. The weight ratio of the better ε-type copper phthalocyanine/α-type copper phthalocyanine is 0.05 to 0.55, and preferably 0.1 to 0.4. The crude ε-type copper phthalocyanine used as described above has an index value exceeding 0.03, so commercially available ε-type copper phthalocyanine should meet this demand.

The water-soluble inorganic salt to be used in the present invention is not particularly limited, and examples thereof include a salt (sodium salt), potassium salt, sodium sulfate, lead salt, calcium salt or a mixture thereof.

When the amount of the water-soluble inorganic salt is too small, the transfer from the α-type copper phthalocyanine to the ε-type copper phthalocyanine pigment and the refinement of the obtained ε-type copper phthalocyanine pigment are difficult to proceed, and when the amount is too large, the amount of the pigment is reduced. , low productivity is not conducive to industry. Therefore, the water-soluble inorganic salt to be used is suitably in the range of 2 to 20 times the weight based on the total weight of the α-type copper phthalocyanine and the crude ε-type copper phthalocyanine. Even better is the weight in the range of 5 to 14 times. The amount of the water-soluble inorganic salt can also be selected in accordance with the target pigment particle size.

The water-soluble organic solvent is added in order to uniformly form the α-type copper phthalocyanine, the crude ε-type copper phthalocyanine, and the water-soluble inorganic salt into a block shape, and is freely mixed with water or cannot be freely mixed, and can be removed by industrial washing with water. Solubility. The water-soluble organic solvent is not particularly limited as long as it can promote the crystal transfer of the α-type copper phthalocyanine and the particle growth of the obtained ε-type copper phthalocyanine pigment, but the temperature rises during the mixing and the solvent is easily evaporated. More suitable for safety considerations are high boiling solvents. As the solvent, for example, 2-(methoxymethoxy)-p-aminobenzoic acid di- or 2-butoxy-p-aminobenzoic acid di- or 2-(isopentyloxy)p-aminobenzoic acid , 2-(hexyloxy)p-aminobenzoic acid di-, diethylene glycol, diethylene glycol monomethyl ether, diethylene glycol monoethyl, diethylene glycol monobutyl ether, triethylene glycol, three Glycol monomethyl ether, liquid polyethylene glycol, 1-methoxy-2-propanol, 1-ethoxy-l-propanol, propylene glycol, propylene glycol monomethyl ether, propylene glycol Ethyl ether, low molecular weight polypropylene glycol, aniline, pyridine, oxolane, dioxane, methanol, p-aminobenzoic acid, isopropanol, n-propanol, isobutanol, n-butyl Alcohol, ethylene glycol, propylene glycol, diol monomethyl ether acetate, ethyl acetate, isopropanol acetate, acetone, methyl ethyl ketone, dimethylformamide, dimethyl Sulfone, N-methylpyrrolidone, and the like. Further, two or more solvents may be used in combination as needed.

When the amount of the water-soluble organic solvent in the kneading composition is too small, the kneading composition is too hard to make the mixing mixer difficult to operate stably, and when the mixture is too much, the kneading composition is too soft to cause crystallization of α-type copper phthalocyanine. The obtained ε-type copper phthalocyanine pigment has a low level of miniaturization. Therefore, the water-soluble organic solvent to be used is suitably a weight in the range of 0.5 to 5 times with respect to the total weight of the α-type copper phthalocyanine and the crude ε-type copper phthalocyanine. Within this range, it is selected in accordance with the amount of the water-soluble inorganic salt and the hardness of the kneading composition.

The mixed agitation composition may contain a phthalocyanine inducer, and the phthalocyanine inducer may have at least one substituent represented by the following general formula (1), and a metal or metal phthalocyanine inducer.

General formula (1): -X-Y

In the general formula (1), X is a direct combination or a 2 to 50 atom selected from a hydrogen atom, a carbon atom, a nitrogen atom, an oxygen atom and a sulfur atom to form a chemically rational combination into a divalent bonding group. Y is a nitro group or a halogen atom substituted with a phenylphosphorylimidomethyl group, -NR1R2, -SO3M or -COOM. R1 and R2 are each independently a hydrogen atom, may be substituted with an alkyl group, may be substituted with an alkenyl group, may be substituted with a phenyl group, or R1 and R2 may be those bonded nitrogen atoms, and may be substituted for inclusion. A complex ring of nitrogen, oxygen or a sulfur atom. M is 1/i hydrogen ion, 1 to 3 valent metal ion or at least one hydrogen is replaced by an alkyl group to form an ammonium salt ion, and i represents a valence of M (for example, in -COOM, M is 1 hydrogen atom) 1/2 calcium atom (in this case 2 COO- and 1 atom of calcium combined) and so on.)

The specific substituent of the substituent represented by the general formula (1) may, for example, be phenylphosphodiimidemethyl, 4-nitrophenylphosphazimidomethyl or 4-chlorophenylphosphonate. Diimide methyl, tetrachlorophenylphosphazinylmethyl, Carbamoyl, carbamoyl, aminomethyl, dimethylaminomethyl, diethylaminomethyl, dibutylamino Methyl, diethyl piperidinylmethyl, dimethylaminopropylaminosulfonyl, diethylaminopropylaminosulfonyl, dibutylaminopropylaminosulfonyl, morpholinoethylaminosulfonyl, Diethylaminopropylaminosulfonyl, 4-(diethylaminopropylaminocarbonyl)phenylaminocarbonyl, dimethylaminomethylcarbonylaminomethyl, diethylaminopropylaminomethylcarbonylamino Base, dibutylaminopropylaminomethylcarbonylaminomethyl, sulfamic acid group, sodium sulfonate ( Base), calcium sulfonate ( Base), aluminum sulfonate ( Base), calcium dodecyl sulfonate ( Base), ammonium stearyl sulfonate ( Base), ammonium trimethyl octadecyl sulfonate ( Base), ammonium dimethyl diacetophenone sulfonate ( Base), carvone group, 2-aluminum aluminate (aluminum) )-5-nitrobenzamide ) methyl and so on.

The phthalocyanine-inducing body having such a substituent can be produced by a method described in, for example, Japanese Patent Publication No. Sho 39-28884, Japanese Patent Publication No. Sho 57-15620, No. Sho 58-28303, and Japanese Patent Publication No. Sho 64-5070. .

When the ε -type copper phthalocyanine pigment of the present invention and the resin described later are mixed to prepare a pigment dispersion, the phthalocyanine inducer can improve the fluidity and stability of the pigment dispersion. The weight of the appropriate phthalocyanine inducing body is 0.3 to 50 parts, more preferably 3 to 30 parts by weight, based on 100 parts by weight of the raw material α-type copper phthalocyanine pigment and ε-type copper phthalocyanine pigment.

The mixing and stirring composition after mixing and stirring can be treated according to the usual method, that is, the mixing and stirring composition is treated with water or a mineral acid aqueous solution, filtered, washed with water to remove the water-soluble inorganic salt and the water-soluble organic solvent, and the ε type is separated. Copper phthalocyanine pigment. The ε -type copper phthalocyanine pigment can be used in this wet state by drying. It can also be used in a powder state after pulverization. If necessary, it can be added after mixing the resin, surfactant and other additives.

Further, the obtained ε -type copper phthalocyanine pigment can be further mixed with a water-soluble inorganic salt and a water-soluble organic solvent to be further refined. The water-soluble inorganic salt and the water-soluble organic solvent may be the same amount as used in the method for producing the ε -type copper phthalocyanine pigment of the present invention, and the mixing temperature at the time of miniaturization is suitably 40 to 130 ° C, which is most appropriate. It is 60~110 °C. When the mixing temperature exceeds 130 ° C, the ε -type copper phthalocyanine pigment particles are easily grown, so that it is difficult to refine.

The ε -type copper phthalocyanine pigment and the liquid medium component of the present invention are mixed and colored, and can be used for printing inks, paints, coloring resists for color filters, inkjet inks, toners, and molded plastics. The weight of the ε -type copper phthalocyanine pigment may be 0.1 to 80% based on the weight of the coloring composition (100%), and the weight of the liquid medium component may be 20 to 99.9%.

The liquid medium component used in the coloring composition of the present invention includes a liquid medium for lithographic printing ink, a liquid medium for gravure printing ink, a liquid medium for coating, a liquid medium for coloring the dyeing agent, and a liquid medium for inkjet ink. , resin for toner, resin for molding plastic, and the like.

The liquid medium for lithographic inks is, for example, rosin to phenyl resin, petroleum resin, alkyd resin, or resin such as a resin such as sesame oil, tung oil, soybean oil, etc., n-paraffin, and the like. Paraffin, aromatic a composition of a solvent such as a cycloalkane or an α -olefin. Based on the total weight of the liquid medium component (100%), the appropriate mixing ratio is resin: vegetable oil: solvent = 10 to 50%: 0 to 30%: 20 to 60%. A well-known additive such as an ink solvent, a desiccant, an adjustment modifier, and a tackifier can be suitably blended in the lithographic ink as needed.

Further, the liquid medium for gravure ink is a composition of a resin and a solvent. Based on the total weight of the liquid medium component (100%), the appropriate mixing ratio is in the range of resin: solvent = 5 to 40%: 60 to 95%.

As the resin, for example, gum rosin, wood rosin, toluene gum rosin, liming rosin, lime rosin, rosin ester, horse sputum acid resin, hard asphalt, Dama, shellac, and polysaccharides can be mentioned. Amine resin, vinyl resin, nitrocellulose, cyclized rubber, salinized rubber, ethyl cellulose, cellulose acetate, ethylene vinyl acetate copolymer resin, urethane resin, polyester resin, alkyd resin, etc. Wait. As the solvent, for example, n-hexane, toluene, methanol, p-aminobenzoic acid, acetone, ethyl acetate, ethyl lactate, ethylene glycol monoethyl ether, 1, 2 may be mentioned. - ethylene glycol monomethyl ether, ethylene glycol monobutane, isopropyl alcohol, chlorobenzene, ethyl ether, methyl ethyl ketone, ethyl acetoacetate and many more.

If necessary, it is possible to suitably mix body pigments such as barium sulfate, barium carbonate, calcium carbonate, gypsum, alumina white, clay, alumina, alumina white, talc, calcium silicate, and precipitated magnesium carbonate in the gravure ink, and subsidies. A well-known additive such as a agent, a plasticizer, an ultraviolet preventive agent, an oxidation preventive agent, and a charge preventive agent.

The liquid medium for coating is a composition of a resin and a solvent. Based on the total weight of the liquid medium component (100%), the appropriate mixing ratio is in the range of resin: solvent = 5 to 45%: 55 to 95%.

Examples of the resin include nitrocellulose, amino alkyd resin, acrylic resin, amino acrylic resin, urethane resin, polyvinyl acetal resin, epoxy resin, polyester resin, and salted vinyl. Resin, fluorinated vinylidene resin, fluorinated vinyl resin, polyethyl sulfone resin, and the like. The solvent may, for example, be an aliphatic carbonized water system, an aromatic carbonized water system, a halogenated carbonized water acid system, an alcohol system, a ketone system, an ester system, an ether system or an ether. Alcohol, ether. Ester-based organic solvents, water, and the like.

The liquid medium for coloring the anti-staining agent for producing a color filter is a thermoplastic resin, a thermosetting resin, or a composition of an active energy ray-curable resin and a monomer and/or an oligomer and a solvent. Based on the total weight of the liquid medium component (100%), the appropriate mixing ratio is resin: monomer and/or oligomer: solvent = 4 to 15%: 2 to 8%: 77 to 94%. The thermoplastic resin may, for example, be a butyral resin, a styrene-horazolyl acid copolymer, a salted polyethylene, a salted polypropylene, a polybasic vinyl group, or a salted vinyl group. Vinyl acetate copolymer, polyvinyl acetate, polyurethane resin, polyester resin, propylene resin, alkyd resin, polystyrene resin, polyamide resin, gel resin, cyclized rubber resin, Cellulose, polyethylene, polybutadiene, polyamide resin, and the like. Further, examples of the thermosetting resin include epoxy resin, phenylguanine amine resin, rosin-denatured horse sinensis acid resin, rosin-denatured fumaric acid resin, synthetic resin, urea resin, phenol resin, and the like. .

The active energy ray-curable resin may, for example, be a guanidinium isocyanate group (for example) Base) And an epoxy group or the like, and a photopolymerizable group such as an acrylate compound or cinnamic acid is introduced into a linear polymer resin having a reactive substituent such as a hydroxide ion, a carboxyl group or an amino group.

As the monomer and the oligomer, for example, methyl (order) acrylate, ethyl (order) acrylate, 2-hydroxyethyl ethyl (step) acrylate, 2-hydroxyethyl propyl ( Order) acrylate, cyclohexyl (step) acrylate, β-carboxyethyl (order) acrylate, polyethylene glycol di(order) acrylate, 1,6-hexane diol (step) acrylate, three Glycol di(order) acrylate, tripropenol di(order) acrylate, trimethylolpropane tris (order) acrylate, pentaerythritol tris (order) acrylate, 1,6-hexanediol shrinkage liver oil base Ether (s) acrylate, diphenol A dihydrated liver oil based ether (secondary) acrylate, neopentyl glycol dihydrated liver oil based ether (secondary) acrylate, dipentaerythritol hexa(meth) acrylate, three Cyclohexyl (order) acrylate ( ( ) ), ester acrylate, methylolated synthetic melamine (order) acrylate, epoxy (meth) acrylate, urethane acrylate and other acrylates and methacrylate, (order) acrylic Ester acid, styrene, vinyl acetate, hydroxyethyl ethyl vinyl ether, ethylene glycol divinyl ether, pentaerythritol vinyl ether, (order) acrylate decylamine, N-hydroxyl Methyl (order) acrylate decylamine, N-vinyl formyl amide, acrylonitrile, and the like. These can be used alone or in combination of two or more.

The solvent may, for example, be cyclohexanone, ethyl glycol monoethyl ether acetate, diethylene glycol dimethyl ether, ethylbenzene or ethylene glycol. Ethyl ether, xylene, methyl ethyl ketone, ethyl acetate, etc., aliphatic carbonized water system, aromatic carbonized water system, halogenated carbonized water, alcohol, ketone, ester, etheric, ether. Alcohol, ether. Ester-based organic solvent.

A photopolymerization initiator and a sensitizer can be blended in the coloring inhibitor.

The liquid medium for inkjet ink is a composition of a resin and a solvent. Based on the total weight of the liquid medium component (100%), the appropriate mixing ratio is in the range of resin: solvent = 1 to 10%: 90 to 99%. The resin may, for example, be an acrylate, a styrene-acrylate, a polyester, a polyamine, a polycarbamate, a fluorocarbon resin or the like dissolved in water, and a colloidal dispersion of an emulsion which is not dispersible in water. Function resin. Neutralizing agents such as ammonia, amino groups, and inorganic bases may be added to these resins as necessary. Further, as the solvent, for example, water, ethylene glycol, polyethylene glycol, ethylene glycol monomethyl ether, substituted pyrrolidone or the like can be mentioned. Further, in order to accelerate the drying property of the inkjet ink, alcohols such as methanol, p-aminobenzoic acid, isopropyl alcohol or the like may be used. Further, in order to improve the dispersion stability of the preservative, the penetrating agent, the chelating agent and the pigment in the inkjet ink, an anionic, nonionic, cationic or zwitterionic active agent may be blended.

Inkjet inks can also be used in the manufacture of color filters.

As the resin for the toner, there are polystyrene, styrene-acrylate copolymer, salted resin, styrene-vinyl acetate copolymer, rosin-denatured horse sinensis resin, phenol resin, ring Oxygen resin, polyester resin, low molecular weight polyethylene, low molecular weight polypropylene, ionic polymer resin, polyurethane resin, enamel resin, rosin ester, rosin, and the like.

For the resin used for molding plastics, there are polypropylene, polyethylene, and ethylene. Propylene copolymer, alpha olefin and acrylate acid or copolymer of horse sinensis, ethylene. a vinyl resin such as a vinyl acetate copolymer, a copolymer of ethylene and acrylate acid or anhydrous horse sinensis, a vinyl resin such as a polysaturated vinyl or a polyvinyl acetate, or a furr ( Resin and butyral resin, such as acetal resin, polyacrylonitrile and methacrylic resin, acrylic resin, polystyrene and acrylonitrile. Butadiene. a styrene resin such as a styrene copolymer, a polyester resin such as polyethylene terephthalate or polycarbonate, a nylon such as 6-nylon, an unsaturated polyester resin, an epoxy resin, a urea resin, Synthetic resin, cellulose resin, and the like.

[Examples]

The invention will be described in more detail below with reference to examples and comparative examples, but the invention is not to be construed as limited. In addition, in the embodiment, "part" means "weight part" and "%" means "weight%".

Before explaining the embodiment, a method of measuring the contrast and a method of preparing the acrylic resin solution used in the examples and the comparative examples will be described. The molecular weight of the resin is a weight average molecular weight in terms of polystyrene measured by GPC (gel permeation process chromatography).

Further, the contrast of the coating film was measured by the following method using the measuring device shown in Fig. 3. The light emitted from the liquid crystal display backlight unit 7 is polarized by the polarizing plate 6, and the dried coating film 4 on which the colored composition is applied onto the glass substrate 5 reaches the polarizing plate 3. If the polarizing surfaces of the polarizing plate 6 and the polarizing plate 3 are parallel, light will penetrate the polarizing plate 3, but if the polarizing surfaces of the polarizing plate 6 and the polarizing plate 3 are perpendicularly intersected, the light is blocked by the polarizing plate 3. . However, when the light polarized via the polarizing plate 6 passes through the dried coating film 4 of the coloring composition, it is scattered due to the pigment particles and the like. When the position of the partial polarizing surface is deviated, in the case where the polarizing surfaces of the two polarizing plates 6 and 3 are parallel, the amount of light transmitted through the polarizing plate 3 is reduced, and the polarizing surfaces of the two polarizing plates 6 and 3 are perpendicularly intersected. In some cases, part of the light passes through the polarizing plate 3. The transmitted light is taken as the luminance on the polarizing plate, measured by the luminance meter 1, and the luminance (parallel luminance) of the polarizing surfaces of the polarizing plates 3 and 6 in parallel is calculated, and the polarizing surfaces of the polarizing plates 3 and 6 are perpendicular. The ratio of the luminance (vertical intersecting luminance) at the time of intersection (contrast). That is, the contrast is calculated by the following calculation formula.

Contrast = parallel luminance / vertical intersection luminance

When the scattering due to the pigment of the dried coating film 4 of the coloring composition is caused, the parallel luminance is lowered, and since the vertical intersecting luminance is increased, the contrast is lowered.

In addition, the luminance meter 1 uses a color luminance meter ( The "BM-5A" manufactured by the company, and the polarizing plate is a polarizing plate ("NPF-G1220DUN" manufactured by Nitto Denko Corporation). In the measurement, in order to block the unnecessary light, the black portion 2 of the 1 cm hole is used to block the measured portion.

<Preparation of Acrylic Resin Solution> The detachable four ethyl sulfhydryl groups (with a thermometer, a cooling tube, a nitrogen gas introduction tube, a stirring device, and a dropping tube) In the reaction vessel, 800 parts of cycloacetone was placed, and nitrogen gas was injected into the container and heated to 100 °C. A mixture of 60.0 parts of styrene, 60.0 parts of methacrylic acid, 65.0 parts of methacrylate, 65.0 parts of nitrile acrylate, and 10.0 parts of azoisobutyronitrile was dropped from the dropping tube at about the same temperature for about 1 hour. The polymerization was carried out.

After the dropwise addition, the mixture was further reacted at 100 ° C for 3 hours, and then 2.0 parts of azoisobutyronitrile was added to dissolve 50 parts of cyclohexanone, and the reaction was further continued at 100 ° C for 1 hour to obtain a weight average molecular weight of about 40,000. A solution of acrylic resin.

After cooling to room temperature, about 2 g of the resin solution was sampled, and dried by heating at 180 ° C for 20 minutes, and the nonvolatile matter was measured. According to the measured value, cyclohexanone was added so that the non-fluorescent component in the previously synthesized resin solution was about 20 %, modulating the acrylic resin solution.

[Example 1]

65 parts of α-type copper phthalocyanine, 35 parts of crude ε-type copper phthalocyanine (indicator value: 0.062), 800 parts of sodium salt, and 150 parts of diethylene glycol were placed in a conversion stirrer (Asada Iron) It is prepared by the company to mix for 5 minutes to obtain a substantially uniform degree. This mixture was supplied to a continuous mixing mixer using a spiral type feeder (the miracle manufactured by Asada Iron Works Co., Ltd.) KCK-42 type"), the mixture is mixed and stirred. The condition of the continuous mixing mixer is that the feeder portion has a spiral diameter of 120 mm, the number of mixing and stirring portions of the fixed disc and the rotating disc is 8 groups, the amount of the stirring composition is 25 kg/hour, the residence time is 10 minutes, and the spindle rotates. The number was 50 rpm and was operated while the mixing temperature was 140 °C. Here, the obtained kneading composition was taken out from 3,500 parts of a 1% sulfuric acid aqueous solution at 70 ° C, and after stirring for 1 hour, it was filtered, washed with water, and dried. With respect to the obtained ε -type copper phthalocyanine pigment, a diffraction intensity amount curve was obtained in the range of 2θ=3.5 to 15° using an X-ray diffraction apparatus (RINT2000 manufactured by RIGAKU Co., Ltd.). When the Bragg angle 2θ=5°, the point on the diffraction intensity variation curve, and the diffraction intensity at 6.8° when the Bragg angle 2θ=12° is the line connecting the points on the diffraction intensity variation curve as the baseline A is 1300 cps, the maximum diffraction intensity B of 9.1 ° ± 0.2 ° is 4190 cps, and the minimum diffraction intensity C of 8.6 ° ± 0.2 ° is 1270 cps (Fig. 5). The index value for calculating the purity is (A-C) / (A - C + B) = 0.007.

[Example 2]

The mixing temperature was 160 ° C, and the same operation as in Example 1 was carried out to obtain an ε-type copper phthalocyanine pigment. With respect to the obtained ε-type copper phthalocyanine, the X-ray diffraction intensity (Fig. 6) was measured in the same manner, and the index value of the purity was calculated. The results are shown in Table 1.

[Comparative Example 1]

The mixing temperature was set to 90 ° C, and the same operation as in Example 1 was carried out to obtain an ε-type copper phthalocyanine pigment. With respect to the obtained ε-type copper phthalocyanine, the X-ray diffraction intensity (Fig. 7) was measured in the same manner, and the index value of the purity was calculated. The results are shown in Table 1.

[Comparative Example 2]

65 pieces of α-type copper phthalocyanine, 35 pieces of crude ε-type copper phthalocyanine (indicator value: 0.062), 800 parts of sodium salt, and 180 parts of diethylene glycol were placed in the 1500-volume part. The kneading machine was mixed and stirred at 140 ° C for 10 hours. The obtained mixed stirring composition was taken out from 3,500 parts of a 1% sulfuric acid aqueous solution at 70 ° C, and after stirring for 1 hour, the mixture was filtered, washed with water, and dried to obtain a pigment. The obtained kneading composition was subjected to the same post treatment as in Example 1, and the X-ray diffraction intensity (Fig. 8) was measured about the obtained ε-type copper phthalocyanine, and the index value of the purity was calculated. Table 1 shows.

Comparative Example 1 was the same as Example 1 except for the mixing and stirring temperature. However, in Examples 1 and 2 in which the mixing temperature was high, an ε-type copper phthalocyanine pigment having a high purity was obtained. Further, Examples 1 and 2 could not be obtained by one-time mixing and stirring (Comparative Example 2) by a conventional batch type mixer, and after mixing and stirring by a specific continuous mixing mixer, a high-purity ε-type copper phthalocyanine pigment can be obtained. .

[Example 3]

10 parts of ε-type copper phthalocyanine pigment obtained in Example 1, paint for gravure printing ink (nitrocellulose resin 17%, ethyl acetate 60%, methanol 15%, toluene 8%) 90 parts, and 3 mm glass beads 300 The mixture was mixed, and then dispersed with a paint conditioner for 60 minutes to prepare a gravure ink, and the viscosity was measured at 25 ° C using a B-type viscometer (6 rpm). In addition, the prepared ink is colored in a transparent plastic film by a bar code, and then the black paper is placed on the obtained color developing matter, and the L ^* value is measured. The results are shown in Table 2.

[Example 4, Comparative Examples 3, 4]

The pigment used in Example 3, as shown in Table 2, was changed to each of the different ε-type copper phthalocyanine pigments, and the gravure printing ink was prepared as in Example 3, and the transparency and viscosity were measured. The results are shown in Table 2. Show.

The gravure inks of Example 3 and Example 4 have lower viscosity than the gravure inks of Comparative Example 3 and Comparative Example 4, and the gravure inks of Examples 3 and 4 have smaller L ^* values. Transparent.

[Embodiment 5]

The following composition mixture containing the ε-type copper phthalocyanine pigment obtained in Example 1 was uniformly stirred, and then 1 mm of zirconia beads were used in the machine ( ) After dispersing for 5 hours in the "mini model M-250 MKII" manufactured by the Japanese company, it was filtered through a 5 um filter to prepare a blue pigment dispersion.

The copper phthalocyanine 1.0-part phosphate-based pigment dispersant having 1.0 part of the ε-type copper phthalocyanine pigment obtained in Example 1 and having a dibutylaminomethyl group ( The company manufactures "BYK111") acrylic resin solution 40.0 parts of ethyl ketone 48.0

Then, the following composition mixture containing the obtained blue pigment dispersion was uniformly stirred and mixed, and then filtered using a 1 μm filter to prepare a coloring resist for a color filter.

Blue pigment dispersion 45.0 parts Acrylic resin solution 15.0 parts Trimethylolpropane triacrylate 9.0 (New Nakamura Chemical Co., Ltd. product "NK ATMPT") Photopolymerization starter 2.0 (Chiba. . Company manufacturing products" 907") Sensitizer ("EAB-F" manufactured by Hodogaya Chemical Co., Ltd.) 0.2 parts of 2 parts of cyclohexanone

[Example 6 and Comparative Examples 5 and 6]

The ε-type copper phthalocyanine pigment used in Example 5 was changed to a different ε-type copper phthalocyanine pigment as shown in Table 3, and a coloring resist for a color filter was prepared as in Example 5.

The coloring anti-staining agent for each of the color filters obtained in Examples 5 and 6 and Comparative Examples 5 and 6 was used as an implement ( The coating was applied to a glass substrate of 100 mm × 100 mm and 1.1 mm thick at a number of revolutions of 500 rpm, 1000 rpm, and 1500 rpm. In order to form a calibration curve, three types of coated substrates having different film thicknesses were obtained. Each coated substrate was dried at 70 ° C for 20 minutes, and then subjected to ultraviolet light exposure using an ultrahigh pressure mercury lamp at an integrated light amount of 150 mJ. After heating at 230 ° C for 1 hour, after cooling, the contrast was measured. Next, the chromaticity (Y, x, y) was measured using a microscopic spectrophotometer ("OSP-SP100" manufactured by Olympus Optics Co., Ltd.) on the C light source of the coating film. With respect to the results of measurement of contrast and chromaticity of the three substrates coated with the same anti-staining agent, the contrast at y = 0.14 was obtained by an approximation method, and the results are shown in Table 3.

The coloring resists for color filters of Example 5 and Example 6 were superior to the coloring resists for color filters of Comparative Example 5 and Comparative Example 6, and the contrast was high.

1. . . Feeder section

2. . . Mixing section

3. . . Polarizer, discharge

4. . . Dry coating

5. . . glass substrate

6. . . Polarizer

7. . . Backlight unit for liquid crystal display

10. . . Mixing mixer

11. . . Cylindrical shell

12. . . Spiral rod

twenty one. . . Fixed disc

twenty two. . . Mixing cylinder

twenty three. . . Rotating disc

twenty four. . . bolt

41. . . Raw material hopper

42. . . Feeder

43. . . Contact cylinder

44. . . Intermediate cylinder

111. . . Raw material inlet

121. . . Motor drive shaft

122. . . Spiral wing

211, 212. . . Swipe hole

231. . . Outer hole

232. . . hole

2θ. . . Prague angle

BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 is a cross-sectional view showing a side view of an example of a continuous mixing mixer used in the present invention.

Figure 2 is a front view and a rear view showing the form of a fixed disc and a rotating disc suitable for the continuous mixer of Figure 1. (a) is a fan-shaped hole fixing disc, (b) is a fan-shaped hole rotating disc, (c) is a daisy-shaped hole fixing disc, (d) is a daisy-shaped rotating disc, and (e) is a 臼 type The hole fixing disc and (f) are 臼-shaped hole rotating discs.

Figure 3 is a conceptual diagram of a measuring device for measuring contrast.

Fig. 4 is a view showing an X-ray diffraction pattern of a mixture of α -type copper phthalocyanine and ε-type copper phthalocyanine at the middle of the ε-type copper phthalocyanine pigment (in the middle of crystallization transition).

Fig. 5 is a view showing an X-ray diffraction pattern of the ε-type copper phthalocyanine pigment obtained in the first embodiment.

Fig. 6 is a view showing an X-ray diffraction pattern of the ε-type copper phthalocyanine pigment obtained in the second embodiment.

Fig. 7 is a view showing an X-ray diffraction pattern of the ε-type copper phthalocyanine pigment obtained in Comparative Example 1.

Fig. 8 is a view showing an X-ray diffraction pattern of the ε-type copper phthalocyanine pigment obtained in Comparative Example 2.

2θ. . . Prague angle

Claims (5)

An ε -type copper phthalocyanine pigment characterized by satisfying substantially uniform agitation of a mixture containing α-type copper phthalocyanine, crude ε-type copper phthalocyanine, a water-soluble inorganic salt and a water-soluble organic solvent by using a continuous mixing mixer Hybrid to manufacture, in the Cu K α X light diffraction intensity variation curve, the Bragg angle 2θ=5°, the point on the above-mentioned quantitative curve, and the point on the above-mentioned quantitative curve when the Bragg angle 2θ=12° When the straight line is used as the baseline, the diffraction intensity value of the Bragg angle 2θ=6.8° is set to A, the Bragg angle is 2θ=9.1°±0.2°, and the maximum diffraction intensity value is set to B, and Prague is set. In the range of angle 2θ=8.1°~8.2°, the relationship between the minimum diffraction intensity value and C is set to C: -0.05≦(AC)/(A-C+B)≦0.03. A method for producing an ε-type copper phthalocyanine pigment according to the first aspect of the invention, characterized in that it comprises a copper phthalocyanine, a crude ε-type copper phthalocyanine, a water-soluble inorganic salt and a water-soluble substance by a continuous mixing mixer. A mixture of organic solvents, which is substantially uniformly stirred and mixed. A method for producing an ε-type copper phthalocyanine pigment according to claim 2, characterized in that the mixture is stirred at 130 to 210 °C. A method for producing an ε-type copper phthalocyanine pigment according to claim 2, characterized in that: The mixing and agitating can be carried out in a continuous mixing mixer having an annular fixed disc and a rotating disc concentric with the fixed disc and rotating integrally around the driving shaft, between the fixed disc and the rotating disc Smash the space. A colored composition containing the ε-type copper phthalocyanine pigment and the liquid medium component as described in claim 1 of the patent application.