JP2004099793A - METHOD FOR MANUFACTURING beta-COPPER PHTHALOCYANINE PIGMENT - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a method for manufacturing a β-copper phthalocyanine pigment with excellent tinting power and clearness for a colored product such as printing ink, a paint and a colored molding. <P>SOLUTION: This method for manufacturing the β-phthalocyanine pigment is characterized in that an average diameter of a primary particle is 0.01-1.00μm and crude copper phthalocyanine with β-crystal of ≥85% by mass is subjected to pigmentation treatment. The crude copper phthalocyanine is obtained via a solid-phase method. <P>COPYRIGHT: (C)2004,JPO

Description

【００４３】
上記表１の結果から、微細な粗製銅フタロシアニンを顔料化処理して得た顔料を用いた最終平版印刷インキは、従来使用されている平均一次粒子径が数十〜数百μｍのβ型結晶粗大粒子から成る粗製銅フタロシアニンを同様に顔料化処理して得た顔料を用いた最終平版印刷インキと比較した結果、着色力と鮮明性により優れていることが明らかである。さらに、同一着色力対比での単位時間当たりの顔料の生産性にも優れていることが明らかである。
従来は着色力が飽和した後でも、顔料化時間の経過に伴って、着色力が少しずつ上昇する傾向があるのに対して、本発明の製造方法においては、その傾向が見られず、実製造時での顔料化処理の時間制御がより容易となる。
【００４４】
【発明の効果】
本発明の製造方法によれば、平均一次粒子径が０．０１〜１．００μｍ、且つβ型結晶が質量換算で８５％以上の粗製銅フタロシアニンを用いて顔料化処理することにより、従来法の粗製銅フタロシアニンでは得られなかった平版印刷インキ用途において着色力と鮮明性により優れたβ型銅フタロシアニン顔料を製造できるという格別顕著な効果を奏する。
【図面の簡単な説明】
【図１】実施例１〜２及び比較例１における、顔料化時間と平版印刷インキの着色力の関係を示した図である。[0001]
TECHNICAL FIELD OF THE INVENTION
The present invention relates to a method for producing a β-type copper phthalocyanine pigment.
[0002]
[Prior art]
As a conventional method for producing a β-type copper phthalocyanine pigment, a crude copper phthalocyanine composed of β-type crystal coarse particles having an average primary particle diameter of several tens to several hundreds μm is synthesized, and the coarse copper phthalocyanine is subjected to grinding assistance such as salt. A solvent salt milling method in which mechanical grinding is performed using a kneading device such as a kneader in the presence of an organic solvent together with an agent is known (for example, see Non-Patent Document 1).
As another method, a solvent in which the crude copper phthalocyanine is dry-ground using an attritor or the like and the resulting fine crude copper phthalocyanine (a mixed crystal ground material of α-type crystals and β-type crystals) is heated in an organic solvent. A method is known (for example, refer to Patent Document 1).
However, the pigment obtained by the above-mentioned production method has a disadvantage that a colored material having higher coloring power and sharpness cannot be obtained.
[0003]
[Non-patent document 1]
Co-authored by The Coloring Material Association, the Pigment Technology Research Group, and the Japan Pigment Technology Association, “The 41st Introduction to Pigment Textbook (1999)” (pages 207 to 208).
[Patent Document 1]
JP-A No. 10-101955 (pages 2 to 5).
[0004]
[Problems to be solved by the invention]
The problem to be solved by the present invention is to provide a method for producing a β-type copper phthalocyanine pigment capable of improving the coloring power and clarity of coloring matters such as printing inks, paints, and colored molded products.
[0005]
[Means for Solving the Problems]
The inventors of the present invention have conducted intensive studies to solve the above-mentioned problems, and as a result, as a raw material used in the pigmentation treatment, crude copper phthalocyanine composed of β-type crystal coarse particles having an average primary particle diameter of several tens to several hundreds μm. Instead of using crude copper phthalocyanine having an average primary particle diameter of 0.01 to 1.00 μm and a β-type crystal having a mass conversion of 85% or more, printing inks, paints, colored molded products, etc. The present inventors have found that a β-type copper phthalocyanine pigment excellent in coloring power and sharpness can be produced, and have completed the present invention.
[0006]
That is, the present invention provides a process for producing a β-type copper phthalocyanine pigment characterized in that crude copper phthalocyanine having an average primary particle size of 0.01 to 1.00 μm and β-type crystals having a mass conversion of 85% or more is pigmented. About the method.
[0007]
BEST MODE FOR CARRYING OUT THE INVENTION
Hereinafter, the present invention will be described in detail.
The crude copper phthalocyanine used in the present invention has an average primary particle diameter of 0.01 to 1.00 μm and a β-type crystal having a mass conversion of 85% or more by mass (hereinafter, referred to as a fine crude copper phthalocyanine). It is. Here, the fine crude copper phthalocyanine preferably has an average primary particle diameter as small as possible within the above-mentioned range, and has a β-crystal content as high as possible within the above-mentioned range.
[0008]
The average primary particle diameter in the present invention refers to the longer diameter (50 pieces of coarse copper phthalocyanine primary particles constituting the aggregate) on a two-dimensional image obtained by photographing particles in a visual field with a transmission electron microscope. (Major axis) were obtained, and the average value was obtained. At this time, the crude copper phthalocyanine as a sample is ultrasonically dispersed in a solvent and photographed with a microscope.
[0009]
The content ratio of the β-type crystal can be determined by a known and commonly used method such as measurement using an X-ray diffraction measuring device. The content ratio (%) of the β-type crystal is, for example, the peak height of the powder X-ray diffraction diagram at a CuKα ray and a wavelength of 0.1541 nm, which represents the crude copper phthalocyanine as a raw material and the α-type and β-type crystal forms of the copper phthalocyanine pigment. When Lα and Lβ are defined as Lα and Lβ, it can be obtained from a calibration curve of Lα / Lβ and the content. 100% crystals of α-form crystals or β-form crystals can be prepared by known and commonly used production methods, respectively. In the powder X-ray diffraction pattern, Lα was the peak height at which the specific Bragg angle 2θ was 6.8 ° ± 0.2 °, and Lβ was the peak height at 9.2 ° ± 0.2 °.
[0010]
The fine crude copper phthalocyanine may be produced by any method.
[0011]
The fine crude copper phthalocyanine used in the present invention is, for example, phthalic anhydride and / or a derivative thereof, copper and / or a compound thereof, urea and / or a derivative thereof, in the presence of a catalyst in a grinding aid or It can be obtained by performing a heat reaction at 150 to 300 ° C. under normal pressure or under pressure in the absence, in an organic solvent or in the absence thereof. In order to remove inorganic and organic impurities, the obtained reaction product is preferably dispersed in an aqueous alkaline solution and / or an aqueous acidic solution, and is preferably filtered and washed. In the above reaction, the pressure conditions are not limited, but the reaction under pressure is preferable from the viewpoint of saving urea and / or its derivative by suppressing thermal decomposition and improving quality by suppressing side reactions.
[0012]
Examples of the phthalic anhydride and / or derivatives thereof include phthalic acid, phthalic anhydride, phthalimide, salts such as sodium phthalate, phthalamide acid and salts or esters thereof, and phthalonitrile. It may be a mixture. Further, the phthalic anhydride and / or its derivative may have a substituent such as a chloro group, an alkyl group, a benzyl group or a phenyl group.
[0013]
Examples of the copper and / or its compound include metal copper, halides of copper (I) or copper (II), copper oxide, copper sulfate, copper sulfide, and copper hydroxide. The amount of copper and / or its compound used is 0.2 to 0.4 mol, preferably 0.25 to 0.35 mol, per 1 mol of phthalic anhydride and / or its derivative.
[0014]
Examples of the urea and / or derivatives thereof include urea, burette, and ammonia. The amount of urea and / or a derivative thereof to be used is 2.5 to 4.5 mol, preferably 3 to 4 mol, per 1 mol of phthalic anhydride and / or a derivative thereof.
[0015]
Examples of the catalyst include ammonium molybdate, molybdenum oxide, molybdenum compounds such as phosphomolybdic acid, titanium compounds such as titanium tetrachloride and titanate, zirconium compounds such as zirconium chloride and zirconium carbonate, boric acid, antimony oxide and the like. Is mentioned.
[0016]
Examples of the grinding aid include alkali metal salts such as sodium chloride, sodium sulfate, potassium chloride, and potassium sulfate; and alkaline earth metal salts such as magnesium chloride, calcium chloride, and barium chloride. More than one species may be present in admixture.
[0017]
The organic solvent is not particularly limited as long as it is inert to a raw material such as phthalic anhydride during the synthesis, and various compounds known in various documents can be used without any particular limitation. For example, aromatic hydrocarbons such as alkylbenzene, alkylnaphthalene and tetralin; alicyclic hydrocarbons such as alkylcyclohexane, decalin and alkyldecalin; aliphatic hydrocarbons such as decane and dodecane; aromatic nitro such as nitrobenzene and O-nitrotoluene Compounds; aromatic halogenated hydrocarbons such as trichlorobenzene and chloronaphthalene; ethers such as diphenyl ether; sulfur compounds such as sulfolane, dimethyl sulfoxide, methyl sulfolane, dimethyl sulfolane, and N-methyl sulfolane; N-methylpyrrolidone and dimethyl imidazolidy And heterocyclic compounds such as nonone. These may be a mixture of two or more.
[0018]
Examples of the reactor include a kneader, a Banbury mixer, a ball mill, a vibration mill, an extruder, a kiln, a rotary dryer, and a glass-lined reactor.
[0019]
As the fine crude copper phthalocyanine used in the present invention, those obtained by a solid phase method in which the reaction is carried out in the absence of an organic solvent are preferable.
[0020]
The pigmentation treatment in the production method of the present invention is the same as the conventionally known pigmentation method for crude copper phthalocyanine. Here, “pigmenting” refers to reducing the crude copper phthalocyanine to a particle size that can be used as a colorant. Specific examples of the pigmentation treatment include the following methods.
(1) Solvent salt milling method A method in which a grinding aid such as salt and an organic solvent that promotes crystal transition to β-form are added to crude copper phthalocyanine and mechanically ground with a grinding device such as a kneader. As the grinding aid, for example, a water-soluble inorganic salt such as salt or sodium sulfate is used. As the organic solvent, for example, a water-soluble and highly viscous liquid such as ethylene glycol and diethylene glycol is used. This method can be carried out at a temperature of 80 to 200 ° C. for 1 to 10 hours using 100 to 1000 parts of a grinding aid and 50 to 500 parts of an organic solvent per 100 parts of crude copper phthalocyanine in terms of mass. Examples of the grinding device include a device forming a closed system of a kneader, a Banbury mixer, a Nauta mixer, and an extruder. According to this method, a β-type copper phthalocyanine pigment having the most excellent coloring power and sharpness can be obtained as compared with the following pigmentation methods (2) and (3).
(2) Solvent method A method in which crude copper phthalocyanine is dry-ground with an attritor or the like, and then heat-treated with an organic solvent or the like. As the organic solvent, for example, an alcohol-based, ketone-based, ester-based, or ether-based organic solvent is used. These organic solvents can be used as a mixture of two or more kinds, or a mixed system of these organic solvents or a mixture thereof and water can be used. This method can be carried out at a temperature of 30 to 200 ° C. for 0.5 to 20 hours using 1 to 100 parts of an organic solvent per 100 parts of crude copper phthalocyanine in terms of mass. This method has a simplified process as compared with the solvent salt milling method, and is a very effective means for producing a β-type copper phthalocyanine pigment with higher productivity.
(3) Bead mill method A method in which an aqueous dispersion containing crude copper phthalocyanine is mechanically ground using a dispersing device such as a bead mill in the presence or absence of a grinding aid and an organic solvent. Examples of the dispersing device include a ball mill, an attritor, a dyno mill, a nanomill, and a dry mill. The method uses 200 to 2000 parts of an aqueous medium and 0 to 200 parts of a grinding aid per 100 parts of crude copper phthalocyanine in terms of mass, and is used at a temperature of 20 to 150 ° C. for 0.5 to 24 hours, or a pass number of 1 to 10 Can be done with a pass.
[0021]
In the production method of the present invention, when a solvent salt milling method is employed as a pigmentation treatment, a case where crude copper phthalocyanine composed of β-type crystal coarse particles having a conventionally used average primary particle diameter of several tens to several hundreds μm is used. In comparison with the conventional method, the amount of the grinding aid can be greatly reduced to about 1/2 to 1/4, and the grinding time can be significantly reduced to about 1/2 to 1/4 compared to the conventional method. A higher-quality β-type copper phthalocyanine pigment than before can be obtained with high productivity. Further, when a pigmentation treatment is performed under conventionally known conditions, a β-type copper phthalocyanine pigment excellent in coloring power and sharpness, which could not be expected in the past, can be obtained.
[0022]
Similarly, in the solvent method, the dry milling time is about one time smaller than the conventional method using crude copper phthalocyanine composed of β-type crystal coarse particles having an average primary particle diameter of several tens to several hundreds μm. With a ratio of ２〜 to １ ／, a β-type copper phthalocyanine pigment having a quality equal to or higher than that of the conventional art can be obtained.
[0023]
In the bead mill method, the average primary particle diameter conventionally used is equal to or higher than the solvent salt milling method which cannot be achieved when using crude copper phthalocyanine composed of β-type crystal coarse particles of several tens to several hundreds μm. A β-type copper phthalocyanine pigment having the following quality is obtained.
[0024]
The copper phthalocyanine pigment obtained by the methods (1) to (3) can be used for various purposes by filtering and washing, and drying with a wet cake or further drying with a powder. If necessary, grinding and classification may be performed.
[0025]
In the production method of the present invention, it is preferable to carry out a surface treatment as necessary in order to obtain more excellent dispersibility, dispersion stability, fluidity, etc. for each of various coloring applications.
[0026]
Examples of the surface treatment agent for performing the surface treatment include a surfactant, a rosin, a copper phthalocyanine derivative, a resin varnish, and a metal salt. For example, the copper phthalocyanine derivative has a substituent on at least one of the four benzene nuclei of copper phthalocyanine, and examples of the substituent include a sulfonic acid group or a metal salt thereof, and a quaternary ammonium salt.
[0027]
According to the production method of the present invention, it is possible to obtain a β-type copper phthalocyanine pigment suitable for preparing a printing ink, for example, a lithographic printing ink.
[0028]
【Example】
Next, the present invention will be specifically described with reference to Examples and Comparative Examples. Hereinafter, unless otherwise specified,% means% by mass and part means part by mass.
[0029]
<Synthesis Example 1> (Synthesis of fine crude copper phthalocyanine)
1000 parts of phthalic anhydride, 1800 parts of urea, 180 parts of cuprous chloride, 5 parts of ammonium molybdate, 1000 parts of magnesium chloride, and 1000 parts of sodium chloride were added to a 10 L glass-lined autoclave vessel, and the mixture was gradually heated to 170 ° C. Thereafter, the mixture was heated and stirred at 170 ° C. for 4 hours to terminate the reaction. After cooling, the reaction product was taken out, washed and filtered repeatedly in the order of a 10-fold amount of a 2% aqueous NaOH solution, a 1% aqueous HCl solution, and hot water, and then dried to obtain 780 parts of crude copper phthalocyanine. The crude copper phthalocyanine obtained above was a fine crude copper phthalocyanine having an average primary particle diameter of 0.05 to 0.3 μm and 100% β-type crystals, as determined by the measurement method described above. In addition, JEM-2010 manufactured by JEOL Ltd. was used as a transmission electron microscope, and LINT1100 manufactured by Rigaku Corporation was used as an X-ray diffractometer (the same applies hereinafter).
[0030]
<Example 1> (Solvent salt milling pigmentation-1)
To a 2 L double-arm kneader were added 225 parts of the fine crude copper phthalocyanine obtained in Synthesis Example 1, 675 parts of sodium chloride, and 140 parts of diethylene glycol, and the mixture was heated and ground at 90 to 95 ° C. for 7 hours. During that time, diethylene glycol was added as appropriate so that the contents maintained uniform viscosity. The obtained ground material was washed with 20-fold warm water, filtered, and dried to obtain a β-type copper phthalocyanine pigment.
[0031]
<Example 2> (Solvent salt milling pigmentation-2)
A β-type copper phthalocyanine pigment was obtained in exactly the same manner as in Example 1, except that 120 parts of the fine crude copper phthalocyanine obtained in Synthesis Example 1 above, 840 parts of salt, and 140 parts of diethylene glycol were used.
[0032]
<Example 3> (Solvent method pigmentation)
A 5 L attritor was filled with 13 kg of 3/8 inch steel beads, 500 parts of the fine crude copper phthalocyanine obtained in Synthesis Example 1 was added, and the mixture was dry-milled at 90 ° C. for 20 minutes to obtain α-type crystals 60% and β. Crude copper phthalocyanine composed of 40% of the type crystals and having an average primary particle diameter of 0.001 to 0.1 μm was obtained. Next, 30 parts of the above crude copper phthalocyanine, 100 parts of isobutanol and 200 parts of water were added to a 500 ml flask, and the mixture was heated at 89 ° C. for 4 hours. Then, isobutanol was distilled off, followed by filtration, washing and drying to obtain β-form. A copper phthalocyanine pigment was obtained.
[0033]
<Comparative Synthesis Example 1> (Synthesis of crude copper phthalocyanine)
In a 10 L glass-lined autoclave container, 1200 parts of phthalic anhydride, 1565 parts of urea, 200 parts of cuprous chloride, 5 parts of ammonium molybdate, tert-amylbenzene (trade name, Hisol P, Nippon Oil Co., Ltd., alkylbenzene mixture) ) Add 4L, gradually heat to 200 ° C, heat and stir for 2 hours to complete the reaction. After cooling, the reaction product was taken out, washed and filtered repeatedly in the order of a 10-fold amount of a 2% aqueous NaOH solution, a 1% aqueous HCl solution, and hot water, and then dried to obtain 1065 parts of crude copper phthalocyanine. The crude copper phthalocyanine obtained above was a coarse particle having an average primary particle diameter of 2 to 100 μm and composed of 100% β-type crystals.
[0034]
<Comparative Example 1> (solvent salt milling pigmentation)
Except that 120 parts of the crude copper phthalocyanine, 840 parts of salt and 140 parts of diethylene glycol obtained in Comparative Synthesis Example 1 were used, the same operation as in Example 1 was performed to obtain a β-type copper phthalocyanine pigment.
[0035]
<Comparative Example 2> (Solvent method pigmentation)
The same procedure as in Example 3 was carried out except that 500 parts of the crude copper phthalocyanine obtained in Comparative Synthesis Example 1 was added and dry-milled at 90 ° C. for 60 minutes to obtain a β-type copper phthalocyanine pigment.
[0036]
Using the β-type copper phthalocyanine pigments obtained in Examples 1 to 3 and Comparative Examples 1 and 2, lithographic printing inks were prepared by the following test methods, and clarity and coloring power were evaluated.
[0037]
[Test example]
<< Lithographic printing ink color test >>
This test method was performed in accordance with JIS K-5101-4 A method (1985).
[0038]
(Dark color ink)
0.32 parts of the β-type copper phthalocyanine pigment of Examples 1 to 3 and Comparative Examples 1 and 2 and 1.68 parts of a resin varnish for lithographic printing ink (manufactured by Dainippon Ink and Chemicals, Inc.) were used with Hoover Mahler (Toyo Seiki Co., Ltd.) The mixture was kneaded by repeating 100 rotations three times under a load of 150 lb with a load of 150 lb to prepare a lithographic printing ink (dark ink).
[0039]
(Light color ink)
Using 0.10 part of the dark ink and 2.00 parts of the white ink (30% white pigment manufactured by Dainippon Ink and Chemicals, Inc.) obtained above using a Hoover Mahler (manufactured by Toyo Seiki Co., Ltd.). The milling was performed by repeating 50 rotations three times under a load of 50 lb to prepare a lithographic printing ink (light-colored ink).
[0040]
Each of the obtained dark ink and light ink is used as a test ink, the dark ink is spread on an art paper with a proof bow printing machine, and the art paper is colored using a colorimetric spectrometer (GREPM MACBETH SPM50). The force was measured. The sharpness was determined on the above art paper in 9 stages of visual judgment [1 (small sharpness) >> 5 (standard) >> 9 (large sharpness)]. The tinting strength was represented by the ratio of cyan concentration using the pigment of each comparative example as a standard (100%).
[0041]
Table 1 shows the measurement results of the lithographic printing inks of Examples 1 to 3 and Comparative Examples 1 and 2 regarding clarity and coloring power.
[0042]
[Table 1]
Table 1

[0043]
From the results in Table 1 above, the final lithographic printing ink using a pigment obtained by subjecting fine crude copper phthalocyanine to a pigmentation treatment is a β-type crystal having a conventionally used average primary particle diameter of several tens to several hundreds μm. As compared with a final lithographic printing ink using a pigment obtained by similarly subjecting a crude copper phthalocyanine composed of coarse particles to a pigmentation treatment, it is clear that the coloring power and the sharpness are superior. Further, it is clear that the productivity of the pigment per unit time at the same coloring power is excellent.
Conventionally, even after the coloring power is saturated, the coloring power tends to gradually increase with the elapse of the pigmentation time, whereas in the production method of the present invention, such a tendency is not observed. The time control of the pigmentation treatment at the time of production becomes easier.
[0044]
【The invention's effect】
According to the production method of the present invention, a pigmentation treatment is performed using crude copper phthalocyanine having an average primary particle diameter of 0.01 to 1.00 μm and a β-type crystal having a mass conversion of 85% or more in terms of mass. This has a particularly remarkable effect that a β-type copper phthalocyanine pigment excellent in tinting strength and sharpness can be produced in lithographic printing ink applications which cannot be obtained with crude copper phthalocyanine.
[Brief description of the drawings]
FIG. 1 is a diagram showing the relationship between the pigmentation time and the coloring power of a lithographic printing ink in Examples 1 and 2 and Comparative Example 1.

Claims (2)

A method for producing a β-type copper phthalocyanine pigment, wherein a crude copper phthalocyanine having an average primary particle diameter of 0.01 to 1.00 μm and β-type crystals having a mass conversion of 85% or more is pigmented. The method according to claim 1, wherein the crude copper phthalocyanine is a crude copper phthalocyanine obtained by a solid phase method.

Images