CN102264844A - Efficient process for preparation of copper phthalocyanine particles exhibiting epsilon crystallographic form - Google Patents
Efficient process for preparation of copper phthalocyanine particles exhibiting epsilon crystallographic form Download PDFInfo
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- CN102264844A CN102264844A CN2009801524406A CN200980152440A CN102264844A CN 102264844 A CN102264844 A CN 102264844A CN 2009801524406 A CN2009801524406 A CN 2009801524406A CN 200980152440 A CN200980152440 A CN 200980152440A CN 102264844 A CN102264844 A CN 102264844A
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
- C09B67/00—Influencing the physical, e.g. the dyeing or printing properties of dyestuffs without chemical reactions, e.g. by treating with solvents grinding or grinding assistants, coating of pigments or dyes; Process features in the making of dyestuff preparations; Dyestuff preparations of a special physical nature, e.g. tablets, films
- C09B67/0025—Crystal modifications; Special X-ray patterns
- C09B67/0026—Crystal modifications; Special X-ray patterns of phthalocyanine pigments
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
- C09B67/00—Influencing the physical, e.g. the dyeing or printing properties of dyestuffs without chemical reactions, e.g. by treating with solvents grinding or grinding assistants, coating of pigments or dyes; Process features in the making of dyestuff preparations; Dyestuff preparations of a special physical nature, e.g. tablets, films
- C09B67/0001—Post-treatment of organic pigments or dyes
- C09B67/0014—Influencing the physical properties by treatment with a liquid, e.g. solvents
- C09B67/0016—Influencing the physical properties by treatment with a liquid, e.g. solvents of phthalocyanines
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Abstract
The present disclosure teaches a new efficient and economical process for preparing epsilon-crystallographic type CuPc particles having a small particle size and narrow particle size distribution. The present disclosure is also directed to the epsilon-crystallographic type CuPc particles prepared by said process and to a liquid crystal display device in which the foregoing CuPc particles are incorporated as color filters. The process significantly reduces the entire processing time and provides copper phthalocyanine particles having good quality, by utilizing wet-cakes as a starting material.
Description
Technical field
This disclosure is at being used to prepare ε crystal formation CuPc with little granularity and narrow size-grade distribution (a kind of new effective and economic method of particulate of ε-CuPc).
Background technology
Liquid crystal colour disply comprises a plurality of color filter substrates with a glass substrate, and wherein red (R), green (G) and blue (B) pixel are arranged on this substrate regularly.Generally speaking, this colour filter further comprise a kind of be called as black matrix cover pattern (shade pattern), it is arranged to fills up the space that forms between a plurality of pixels.This has improved the contrast ratio from the image of the demonstration of background.
A kind of phthalocyanine based on pigment dyestuff is excellent on fastness and performance.It also is used as a kind of blue dyes that is used for coating or plastics.In all pigment, CuPc is especially stable and all is excellent having aspect the multiple fastness.In addition, CuPc has multiple crystalline form.In these crystalline forms, those of the known practical use that has been found that them comprise α, β and the ε crystalline form of CuPc.Common convention is to use beta-crystalline form to give green partially blue color and uses alpha crystalline form to give red partially blue color.Yet, when using ε crystalline form (BASF Corporation, Kirck Othmer Encylopedia when using red more partially blue of the obtainable color of alpha crystalline form; Journal of Solid State Chemistry 177, p1987-1993 (2004)).
Compare with alpha crystalline form, ε crystalline form CuPc has red partially tone, high sharpness and high tinting strength.In addition, they are higher than beta-crystalline form for the solvent resistance of the crystal growth of host crystal.In addition, their antagonism are higher than other polymorphism CuPcs to the solvent resistance of the crystal conversion of beta-crystalline form.Therefore, ε crystalline form CuPc is a kind of molecule aggregates with a kind of crystalline form, and it has very excellent characteristic, has less misgivings for the variation and the reduction on tinting strength and sharpness of tone.Also have, the thermodynamic stability of ε crystalline form approaches beta-crystalline form, and beta-crystalline form is the most stable crystalline form in these polymorphism crystal.
Be known in the art that, CuPc (on the crystallography primary or be purified α crystallization phases) changes into its ε crystalline form easily, for example by grind with a kind of lyonium salt, be in or be not in down depositing of a kind of salt that dry grinding then is a solvent treatment, under a kind of inert atmosphere with a kind of solid binder dry grinding do or water to grind then be to regulate.In conversion process, will in a kind of organic solvent, grind for a long time in the presence of the bead except that the crystal the ε crystalline form by a strong mechanical pressure.
English Patent publication No. GB1411880 has illustrated the production of the phthalocyanine pigment of ε crystalline form.Say that definitely the CuPc that will present α shape by ball milling changes into a kind of 1: 1 mixture of CuPc particulate with α and ε crystalline form.Then with this 1: change into ε shape thereby 1 mixture heats 50% the α CuPc particle that will be left in 8 hours in ethanol.With the particle of the ε shape that generates wash with water, dry and grind then.The disclosed publication No. of Japanese Patent (Hei) 4-252273 and China Patent No. CN1827703 have disclosed the method with above document similarity.
The disclosed publication No. 2000-258620 of Japanese Patent has disclosed a kind of method that is used to produce ε-CuPc fine pigments, and this method comprises grinds rough ε-CuPc, half rough ε-CuPc in the presence of a kind of organic solvent and a kind of mineral salt.It has also disclosed, and to have the BET specific surface area be 95-150m
2The production method of/g or littler ε type CuPc fine pigments, this method is by grinding ε type CuPc raw product and half rough ε type CuPc (comprising α type CuPc pigment or ε type CuPc pigment) in a kind of nitrogen absorption process.Use the mineral salt of raw product, half rough product or the pigment 8-20 weight part of solvent and every weight part then.After this, organic solvent and mineral salt are removed.
U.S. Patent Publication US 2005215780 has illustrated a kind of method that is used to form the crystalline form CuPc.This kind method is included in a kind of solvent in scope and CuPc is heat-treated in the presence of lewis acidic a kind of under 80 ℃ to 250 ℃ the temperature.
Yet, the time that is used for crystalline phase conversion and particle size reduction that the method needs of the above-mentioned ε of preparation crystalline form CuPc are too many.Wish a kind of method of exploitation thus, this method carries out with less time that crystalline phase transforms and reducing of granularity and effectively prepare ε crystalline form CuPc.
Summary of the invention
Therefore an object of the present invention is to provide a kind of method of the ε of preparation crystal formation CuPc, this method needs less time to obtain to have the high crystallization purity and the ε crystalline form CuPc of small grain size more.
Another purpose of this disclosure provides according to the available ε crystalline form CuPc primary granule with little granularity and narrow size-grade distribution of described method.It is to use described ε crystalline form CuPc particle in preparation colour filter pigment and manufacturing liquid-crystal display (LCD) device that this disclosure also has an order.
Ladies and gentlemen contriver of the present invention finds that the granules of pigments that is generated has littler granularity and can be shortened whole process period when (being called wet cake now) under the state between the drying when handling pigment in the conversion process (β is to α, or α is to ε).Though for example some reference documents of French Patent numbers 2417531, disclosed publication No. of Japanese Patent (Hei) 8 176457 etc. have disclosed this wet cake and are used to increase crystalline purposes, they are not taught or advise that this wet cake is used to the purposes that reduces process period in preparation has the CuPc of ε crystalline form.
Brief Description Of Drawings
Fig. 1 is the image from transmission electron microscope (TEM) of the CuPc particulate that presents the ε crystalline phase for preparing for by the method according to example 2.
Fig. 2 is the image from transmission electron microscope (TEM) of the CuPc particulate that presents the ε crystalline phase for preparing for by the method according to comparison example 1.
Describe in detail
Below the present invention is described in detail.
As used in this, term " wet cake " is defined as a kind of solid-liquid mixtures that is in form of suspension, comprises that value is a kind of liquid of about at least by weight percent 30.In another embodiment, wet cake can comprise preferred about at least percent 50, more preferably a kind of liquid of about at least percent 70 and more preferably about at least percent 80.
In one embodiment, CuPc (CuPc) is developed a kind of blue pigment that is used for effectively being used as the colour filter of LCD.This type of colour filter (for example phthalocyanine) must be highly transparent, uniform and be produced in the uniform layer of a thickness.These characteristics determined are in chemical purity, crystallization purity, primary particle size and the size-grade distribution of CuPc.In this regard, a kind of new and more effective method for preparing CuPc has been taught in this disclosure.
The CuPc particulate that presents a kind of alpha crystalline form from the particle of 50wt% at least presents a kind of CuPc (CuPc) particle of ε crystalline form as a kind of parent material.The water-content that this parent material has for by weight 30 at least percent, preferably by weight 50 at least percent, more preferably by weight 70 at least percent and most preferably by weight 80 at least percent.
The CuPc particle that presents a kind of alpha crystalline form of Shi Yonging can prepare by any method in the method for the invention.Preferably they are by using a kind of sour paste method by the CuPc granules preparation that presents a kind of beta-crystalline form.The beta-crystalline form CuPc can be purchased from different companies, for example Toyo Ink (Japan), Dainippon Ink; Chemicals Co. (Japan) etc.Make the beta-crystalline form CuPc stand to transform by sour paste processing to the crystalline phase of alpha crystalline form.The acid paste is handled and to be meant dissolving and the precipitation of pigment in a kind of suitable acid.The preferred acids that uses, for example sulfuric acid, chlorsulfonic acid are with, and Tripyrophosphoric acid.Precipitation medium generally includes water, organic solvent or their mixture.Precipitating action preferably takes place under turbulent-flow conditions.This kind processing spec is in for example Ullmann ' s Encyclopedia of Industrial Chemistry, the 5th complete revised edition, 1992, A20 volume, 225-226 page or leaf.
In first embodiment, the CuPc particle that presents a kind of ε crystalline form is by with the preparation of getting off: by parent material is heated being greater than or equal in the presence of a kind of first organic liquid under 50 ℃ the temperature, and randomly grind in the presence of bead.As defined above, the meaning of grinding is a solid through frayed, grinding etc. to reach a kind of method of particle size reduction.As defining at this, the meaning of dry grinding is that solid does not stand abrasion, grinding etc. to reach a kind of method of particle size reduction when having liquid substantially.Yet, can add a kind of low-level solvent.
In this embodiment, with the alpha crystalline form CuPc be greater than or equal to 50 ℃, preferably be greater than or equal to 60 ℃, more preferably be greater than or equal to 70 ℃ and most preferably be greater than or equal under 80 ℃ the temperature and handle.The temperature of heating steps is to be less than or equal to 210 ℃ generally, preferably is less than or equal to 150 ℃, more preferably less than or equal 120 ℃, and most preferably be less than or equal to 100 ℃.
In the process of this embodiment, the time length of heating steps is to be greater than or equal to 0.5 hour generally, more preferably is greater than or equal to 1 hour, still more preferably is greater than or equal to 2 hours, and most preferably is greater than or equal to 3 hours.This time length is to be less than or equal to 12 hours generally, preferably be less than or equal to 10 hours, more preferably less than or equal 8 hours, still more preferably less than or equal 6 hours, and most preferably be less than or equal to 4 hours.
In this embodiment, this heating steps is to carry out in the presence of a kind of first organic liquid.Be suitable for first organic liquid of the present invention and can include, but are not limited to N-N-methyl-2-2-pyrrolidone N-, tetramethylene sulfone, N, dinethylformamide; The derivative of glycols and glycols is as propylene glycol methyl ether acetate, Diethylene Glycol; Alcohols is if any diacetone alcohol; Acetonitrile; Mono chloro benzene; Ethylene glycol butyl ether; Ketone; And quinoline, preferred N-N-methyl-2-2-pyrrolidone N-and at least two kinds any mixture in them.This first organic liquid may further include water.
This first organic liquid and alpha crystalline form CuPc ratio by weight are to be greater than or equal to 0.033 and preferably be greater than or equal to 0.05 generally.This ratio normally be less than or equal to 0.2 and more preferably less than or equal 0.1.
Being suitable as a kind of bead that grinds the media use can include but not limited to: metal bead, plastic beads, inorganic oxide bead such as zirconium white, and glass beads, preferred zirconium white bead.Employed bead and alpha crystalline form CuPc ratio by weight are to be greater than or equal to 0.01 and preferably be greater than or equal to 0.166 generally.This ratio normally is less than or equal to 0.5, and more preferably less than or equal 0.333.
By the heat treated of above explanation, the alpha crystalline form CuPc can change into the ε crystalline form with narrow size-grade distribution effectively, and size-grade distribution is from the D by a particle size analyzer
10And D
90Percentile is determined.
In another embodiment, this method can may further comprise the steps: the CuPc particle that a) will present a kind of ε crystalline form is from first organic liquid and randomly isolate from bead; And the CuPc particle that b) will separate from step a) and at least a inorganic salt and a kind of second organic liquid are mediated the particle that has the mean particle size that is less than 30nm to obtain.
This separating step can be undertaken by the filtration means that are known in the art, and comprises the use of any suitable strainer, decant, centrifugation etc.Preferably, can use filtration to isolate the CuPc particle that presents a kind of ε crystalline form.In a preferred embodiment, after filtration, further water washs the CuPc particle that presents a kind of ε crystalline form.After further filtering, the phthalocyanine granulates that presents a kind of ε crystalline form that is generated can be used in subsequently the kneading step (as a wet cake) immediately, or can at first be dried.The phthalocyanine granulates that presents a kind of ε crystalline form that is generated preferably is used in subsequently the kneading step with a kind of form of wet cake.
Primary particle size for the ε crystalline form CuPc that reduces above conversion carries out the step that they are mediated with salt in the presence of at least a second organic liquid.For preferred salt kneading method, might use a kind of typical unit of knowing in the art of mediating continuously, comprise a kind of single kneading screw type and a kind of pair of kneading screw type.In addition, use a salt to mediate system.
The time length that kneading step carries out is to be greater than or equal to 2 hours generally, preferably is greater than or equal to 3 hours, more preferably is greater than or equal to 5 hours, and most preferably is greater than or equal to 6 hours.This time length is to be less than or equal to 36 hours generally, preferably be less than or equal to 18 hours, more preferably less than or equal 12 hours, and most preferably be less than or equal to 8 hours.
The temperature of carrying out this kneading step is to be greater than or equal to 0 ℃ generally, and preferably is greater than or equal to 10 ℃ and most preferably be greater than or equal to 50 ℃.This temperature is to be less than or equal to 130 ℃ generally, preferably is less than or equal to 80 ℃, and more preferably less than or equal 60 ℃.
Second organic liquid that is used for kneading step can include but not limited to: the N-N-methyl-2-2-pyrrolidone N-, tetramethylene sulfone, N, dinethylformamide, Diethylene Glycol, the N-methylformamide, diacetone alcohol, glycerine, ethylene glycol, propylene glycol, polypropylene glycol, butoxy ethanol, triethylene glycol, diethylene glycol monomethyl ether, triethylene glycol monomethyl ether, dipropylene glycol monomethyl ether, 1-methoxyl group-2-propyl alcohol, 1-oxyethyl group-2-propyl alcohol, ketone, quinoline, and both any mixtures at least in them, and this second organic liquid N-N-methyl-2-2-pyrrolidone N-preferably.This second organic liquid may further include water.
In this kneading step, this second organic liquid and ε crystalline form CuPc ratio by weight are to be greater than or equal to 0.033 and more preferably be greater than or equal to 0.050 generally.This ratio be generally be less than or equal to 1.0 and more preferably less than or equal 0.666.
In addition, be applicable to that the inorganic salt of salt kneading step can include but not limited to: Tai-Ace S 150, sodium sulfate, calcium chloride, Repone K or sodium-chlor, and preferred sodium-chlor, but it if desired and the time spent can contain crystal water.These inorganic salt and ε crystalline form CuPc ratio by weight are to be greater than or equal to 0.067 and more preferably be greater than or equal to 0.1 generally.This ratio be generally be less than or equal to 1.0 and more preferably less than or equal 0.2.
These inorganic salt have the mean particle size that is greater than or equal to 0.3 μ m generally.Record through particle-size analyzer, this mean particle size is to be less than or equal to 200 μ m generally, preferably is less than or equal to 50 μ m.These inorganic salt are dissolvable in water water generally, and preferred degree is the water of 10g/100ml at least.
In this kneading step, solid phase prod (that is: inorganic salt and ε crystalline form CuPc) and liquid product (that is: second organic liquid and optional water) ratio by weight normally at least 3.5, preferably at least 4, more preferably at least 4.5, especially at least 5, especially at least 5.5, for example about 6.Optional water can be from the use of the wet cake of phthalocyanine granulates, may reside in second organic liquid or can be used as a kind of extra liquid to be added in the mixture.
Employed in the present invention salt is mediated the rotating speed of system should adjust (in case of necessity cooling being taken into account), and its mode is that (under uniform share) makes the equal phase shift of the composition of being mediated under uniform shearing force.Preferably in the salt kneading process, rotating speed remained on from 30 to 150rpm, more preferably from 50 to 120rpm scope.
In another embodiment again, crystalline phase transforms and size reduces to take place simultaneously.In other words, mediate, together with so that reduce the primary particle size of CuPc so that the α crystalline phase is changed into the ε crystalline phase.
In another embodiment, kneading is to carry out in the presence of at least a liquid and at least a inorganic salt.Preferably, kneading is to carry out under such temperature condition, and making temperature profile curve display as the function of time go out at least two is the derivative that equals 0 temperature about the time (dT/dt).These two temperature with differ at least 10 ℃ to equal 0 derivative relevant.In another embodiment, kneading is to carry out constantly changing under the temperature profile curve of (or at least once, sectional).Preferably, mediate in first temperature and carry out under second temperature then, wherein this first temperature is that 80 ℃-150 ℃ (preferred 100 ℃-120 ℃) and this second temperature are 30 ℃-70 ℃ (preferred 50 ℃-60 ℃).This embodiment provides the change of temperature in the process of kneading step, and the CuPc particle that presents alpha crystalline form thus changes into the ε crystalline form and their granularity reduces significantly.In addition, this method has reduced the time that is used for crystalline phase conversion and particle size reduction.
In this embodiment, this liquid normally is selected from down at least a liquid of group, and this group is made up of and the following: N-N-methyl-2-2-pyrrolidone N-, Diethylene Glycol, diacetone alcohol, glycerine, ethylene glycol, propylene glycol, polypropylene glycol, butoxy ethanol, triethylene glycol, diethylene glycol monomethyl ether, triethylene glycol monomethyl ether, dipropylene glycol monomethyl ether, 1-methoxyl group-2-propyl alcohol, 1-oxyethyl group-2-propyl alcohol, quinoline and water.
In this embodiment, the ratio (by weight) of solid phase prod (that is: inorganic salt and CuPc) and liquid product (that is: be included in the water in the wet cake and the liquid of optional other addings) normally at least 3.5, preferably at least 4, more preferably at least 4.5, especially at least 5, especially at least 5.5, for example about 6.
Other conditions in kneading process with before those of kneading step be identical, wherein heating steps (for crystalline phase transforms) and kneading step (particle size reduction) carry out respectively.
For all embodiments of above disclosure, this method may further include following steps: reclaim recycling step of CuPc particulate by removing organic liquid and inorganic salt.
After last step, the CuPc particle is reclaimed by removing inorganic salt and liquid.Removal can be finished by any means, for example uses filtration, decant, centrifugation of any appropriate filter etc.Preferably, can use filtration to isolate the CuPc particle that presents a kind of ε crystalline form.Preferably finish, especially use the water of demineralize by water flush away inorganic salt and liquid.
The method according to this invention can comprise an other drying step after recycling step.This drying step preferably is being greater than or equal to-20 ℃ and be less than or equal under 250 ℃ the temperature and be greater than or equal to 10
-1Pa and be less than or equal to 10
5Carry out under the pressure of Pa, very particularly preferably the temperature about 80 ℃ and 10
4Pressure about Pa.
The CuPc particulate dispersibility that presents a kind of ε crystalline form that generates in order to increase, in the sour paste treatment step of the method according to this invention and/or heating steps (can randomly in the presence of the bead) process and/or at kneading step b) in the process, can further add the CuPc particle that replaces by a kind of functional group (dispersing auxiliary).In addition, this method may further include dry mixed step, wherein further sneaks into the CuPc particle that is replaced by a kind of functional group after this recycling step.
The CuPc particle that uses as a kind of dispersing auxiliary can be selected from by at least one-SO
3M ,-SO
2NR
1R
2And-R
3-NR
4R
5Functional group replace R
1And R
2Independently of one another and can be selected from down group, this group is made up of and the following: hydrogen, alkyl, alkenyl, aryl or cycloalkyl; M can be proton, ammonium cation or metallic cation; R
3Can be singly-bound, alkylidene group, arylidene, and wherein said alkylidene group and arylidene can be replaced by at least one substituting group; And R
4And R
5Independently of one another and can be hydrogen, alkyl, alkenyl, aryl, cycloalkyl, or form a kind of condensation structure jointly, this condensation structure contains-CO-,-SO
2-or-at least a among the N=N-.
More preferably, the CuPc particle can be by-SO
3H ,-SO
2NHR
1Functional group replaces, wherein R
1Be hydrogen, alkyl, alkenyl, aryl, cycloalkyl or
Although compare with the existing method in this area and to have reduced the kneading time, method of the present invention can obtain to have littler average primary particle size, the narrower size-grade distribution and the better ε crystalline form CuPc of primary particle shape.
Average primary particle size by the final CuPc that obtains of illustrated method is less than or equal to 30nm generally, preferably is less than or equal to 20nm, and this is less than the average primary particle size of those commercially available products.Owing to have the better contrast that the ε crystalline form CuPc of small grain size has more caused colour filter, they can be effectively as the blue colour filter of LCD device.Can determine this average primary particle size by the mean value of in transmission electron microscope (TEM) image, selecting at least 50 primary particles (these particles form aggregation) and obtaining vertical diameter then.
An embodiment is at the available ε crystalline form of the method according to this invention CuPc particle.Another embodiment is at its purposes in preparation colour filter pigment.
In addition, another embodiment is at comprising the ε crystalline form CuPc particulate colour filter pigment for preparing according in this disclosed method.And, the present invention is directed to its purposes in the manufacturing of liquid crystal indicator.
Example
The present invention is described in detail below with reference to example and comparison example.Yet the scope that these examples should not be construed as limiting the invention in all senses.In addition, except as otherwise noted, unit is to express by weight.
Example 1. CuPcs transform from the crystalline phase of beta-crystalline form to alpha crystalline form
80 parts rough CuPc by weight added by weight in 800 parts the sulfuric acid of 95wt%.In addition, the gained miscellany is stirred 3 hours with suspension or the solution of preparation vitriol in sulfuric acid.This suspension or solution are poured into for twice in the 8L water to obtain a kind of alpha crystalline form CuPc.By after filter removing solvent, make the wet cake of the alpha crystalline form CuPc that comprises by weight percent 80 water directly stand subsequently conversion process to the ε crystalline form.
Example 2. CuPcs transform from the crystalline phase of alpha crystalline form to the ε crystalline form
With 300 parts resulting wet cake by weight (water that comprises 80wt% is like this corresponding to 60 parts alpha crystalline form CuPc by weight) and by weight 12 parts a kind of dried ε crystalline form CuPc handling 2 hours down at 130 ℃ in 750 parts the N-N-methyl-2-2-pyrrolidone N-(NMP) by weight.With the CuPc particle filtration of inversion of phases to remove NMP and washing with water after 2 to 3 times subsequently, make the wet cake (comprising about 70% water) of the CuPc particulate that is generated stand the following kneading process of slightly saying, and do not have drying.When dry sample of CuPc particulate that some generated being analyzed with transmission electron microscope (TEM), the CuPc particle that has obtained to present a kind of pure ε crystalline form (determine by XRD institute, demonstrate the existence that does not have beta-crystalline form) and had the mean particle size of about 100 μ m.
Comparison example 1
Will be except at first as a kind of CuPc of parent material with α shape dry and pulverize, obtained to present the CuPc particle of ε crystalline form in a kind of and example 2 identical modes.When some dry samples of CuPc particulate that present the ε crystalline form that generated being analyzed, demonstrate the mean particle size (Fig. 2) that they have 300 to 500 μ m with transmission electron microscope (TEM).
The primary particle size of example 3. ε crystalline form CuPcs reduces
The wet cake (water that comprises 70wt% is like this corresponding to about 50 parts by weight resulting CuPc) and 80 parts Diethylene Glycol and 800 parts sodium-chlor by weight by weight that in the kneader of a laboratory-scale, add by weight 170 parts the resulting ε of presenting crystalline form.This mixture was mediated 12 hours at 80 ℃ under the rotating speed of 45rpm.After kneading, with the particle that generated by filtering purifying and 10
4Dry under 80 ℃ temperature under the pressure of Pa.When particle being analyzed, compare resulting CuPc particle with those commercially available CuPc particles and have littler primary particle size and better particle shape with TEM.
Comparison example 2
Except use the CuPc particle that presents the ε crystalline form in comparison example 1, obtain and regulate the kneading time so as to obtain to have can with the particle of those primary particle sizes compared of example 3 and particle shape, mediate in a kind of and example 3 identical modes.Must be adjusted to 24 to 36 hours the kneading time.Be used to obtain to have the time long 12 to 24 hour of particulate whole process period of desirable granularity like this than embodiment according to the present invention.
Will be clear that for those of ordinary skills need not to deviate from the spirit and scope of the present invention can make different changes and change to the present invention.Therefore, the present invention is intended to contain these changes of the present invention and variant, and prerequisite is that they are within the scope of claims and equivalent thereof.
Claims (15)
1. one kind is used to prepare CuPc (CuPc) the particulate method that presents the ε crystalline form, described method from as parent material, have the CuPc particle that particle greater than 50wt% presents alpha crystalline form and prepare, the water-content that wherein said parent material has is by weight 30 at least percent.
2. the method for claim 1, the water-content that wherein said parent material has for by weight 50 at least percent, preferably by weight 70 at least percent, more preferably by weight 80 at least percent.
3. method as claimed in claim 1 or 2, described method comprise by described parent material is being greater than or equal to the heating steps that heats under 50 ℃ the temperature in the presence of first liquid, and randomly grind in the presence of bead.
4. method as claimed in claim 3, described method also comprises:
A) the CuPc particle that will present the ε crystalline form is isolated in the described bead to described first liquid of small part and if you are using;
B) the described CuPc particle that will separate from step a) is mediated in the presence of at least a inorganic salt and at least a second liquid to obtain having mean particle size and is the CuPc particle less than 30nm; And
C) reclaim described CuPc particle by removing to described second liquid and the described inorganic salt of small part.
5. as claim 3 or 4 described methods, wherein said heating steps is to carry out being less than or equal under 210 ℃ the temperature.
6. method as claimed in claim 1 or 2, be included under the existence of at least a fluid cpds and at least a inorganic salt described parent material is mediated under following temperature condition, make temperature profile curve display as the function of time go out at least two temperature and equal 0, equal relevant described at least two temperature of 0 derivative and differ at least 10 ℃ with at least two for the derivative (dT/dt) of time.
7. method as claimed in claim 6 also comprises by at least a portion of removing described liquid and described inorganic salt and reclaims described CuPc particulate recycling step.
8. as claim 6 or 7 described methods, wherein mediate and under second temperature, carrying out under first temperature and then, and wherein said first temperature is 80 ℃-150 ℃, preferred 100 ℃-120 ℃, and described second temperature is 30 ℃-70 ℃, preferred 50 ℃-60 ℃.
9. as each the described method in the claim 1 to 8, the wherein said CuPc particle that presents alpha crystalline form is prepared by the CuPc particle that presents beta-crystalline form by using sour paste method.
10. as each the described method in claim 3 to 5 and 9, wherein said first liquid is to be selected from least a in following: the N-N-methyl-2-2-pyrrolidone N-; Tetramethylene sulfone; N, dinethylformamide; Glycol is as propylene glycol methyl ether acetate, Diethylene Glycol; Alcohol is as diacetone alcohol; Acetonitrile; Mono chloro benzene; Ethylene glycol butyl ether; Ketone; Quinoline; And water.
11. as each the described method in the claim 4,5,9 and 10, wherein said second liquid is to be selected from least a in following: N-N-methyl-2-2-pyrrolidone N-, Diethylene Glycol, diacetone alcohol, glycerine, ethylene glycol, propylene glycol, polypropylene glycol, butoxy ethanol, triethylene glycol, diethylene glycol monomethyl ether, triethylene glycol monomethyl ether, dipropylene glycol monomethyl ether, 1-methoxyl group-2-propyl alcohol, 1-oxyethyl group-2-propyl alcohol, quinoline and water.
12. as each the described method in the claim 6 to 9, wherein said liquid is to be selected from least a in following: N-N-methyl-2-2-pyrrolidone N-, Diethylene Glycol, diacetone alcohol, glycerine, ethylene glycol, propylene glycol, polypropylene glycol, butoxy ethanol, triethylene glycol, diethylene glycol monomethyl ether, triethylene glycol monomethyl ether, dipropylene glycol monomethyl ether, 1-methoxyl group-2-propyl alcohol, 1-oxyethyl group-2-propyl alcohol, quinoline and water.
13. as each the described method in the claim 4 to 12, wherein said inorganic salt are to be selected from least a in following: Tai-Ace S 150, sodium sulfate, calcium chloride, Repone K and sodium-chlor.
14., wherein in described sour paste step or in described kneading step, further add by the CuPc particle that at least a functional group replaced that is selected from following :-SO as each the described method in the claim 4 to 13
3M ,-SO
2NR
1R
2, and-R
3-NR
4R
5,
R wherein
1And R
2Independently of one another and be hydrogen, alkyl, alkenyl, aryl or cycloalkyl; M is proton, ammonium cation or metallic cation; R
3Be singly-bound, alkylidene group, arylidene, wherein said alkylidene group and arylidene can be replaced by at least one substituting group; And R
4And R
5Independently of one another and be hydrogen, alkyl, alkenyl, aryl or cycloalkyl, or form the condensation structure jointly, described condensation structure comprises-CO-,-SO
2-and-at least a among the N=N-.
15. as each the described method in the claim 4,5 and 7 to 13, also comprise the dry blending step, wherein after recycling step, will further join in the described phthalocyanine granulates that is reclaimed :-SO by the CuPc particle that at least one functional group replaced that is selected from following
3M ,-SO
2NR
1R
2, and-R
3-NR
4R
5,
R wherein
1And R
2Independently of one another and be hydrogen, alkyl, alkenyl, aryl or cycloalkyl; M is proton, ammonium cation or metallic cation; R
3Be singly-bound, alkylidene group, arylidene, described alkylidene group and arylidene can be replaced by at least one substituting group; And R
4And R
5Independently of one another and be hydrogen, alkyl, alkenyl, aryl or cycloalkyl, or form the condensation structure jointly, described condensation structure comprises-CO-,-SO
2-and-at least a among the N=N-.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| EP08172708 | 2008-12-23 | ||
| EP08172708.3 | 2008-12-23 | ||
| PCT/EP2009/066574 WO2010072561A1 (en) | 2008-12-23 | 2009-12-08 | An efficient process for preparation of copper phthalocyanine particles exhibiting epsilon crystallographic form |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN102264844A true CN102264844A (en) | 2011-11-30 |
| CN102264844B CN102264844B (en) | 2014-11-05 |
Family
ID=40902164
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN200980152440.6A Expired - Fee Related CN102264844B (en) | 2008-12-23 | 2009-12-08 | Efficient process for preparation of copper phthalocyanine particles exhibiting epsilon crystallographic form |
Country Status (5)
| Country | Link |
|---|---|
| JP (1) | JP5566399B2 (en) |
| KR (1) | KR20110119661A (en) |
| CN (1) | CN102264844B (en) |
| TW (1) | TWI478985B (en) |
| WO (1) | WO2010072561A1 (en) |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE2554252A1 (en) * | 1975-12-03 | 1977-06-16 | Basf Ag | PROCESS FOR CONVERTING RAW COPPER PHTHALOCYANINES INTO A PIGMENT FORM |
| DE2742066A1 (en) * | 1976-09-21 | 1978-03-23 | Ciba Geigy Ag | COPPER PHTHALOCYANINE PIGMENT COMPOSITIONS AND PROCESS FOR THEIR PRODUCTION |
| WO2008095801A2 (en) * | 2007-02-07 | 2008-08-14 | Ciba Holding Inc. | Blue phthalocyanine pigment composition and its preparation |
Family Cites Families (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR2417531A1 (en) * | 1978-02-21 | 1979-09-14 | Ugine Kuhlmann | NEW PROCESS FOR THE PREPARATION OF PHTALOCYANIN PIGMENTS |
| JP2517292B2 (en) * | 1987-06-23 | 1996-07-24 | 住友化学工業株式会社 | Method for producing copper phthalocyanine pigment |
| JP3560075B2 (en) * | 1994-12-22 | 2004-09-02 | 三菱化学株式会社 | Electrophotographic photoreceptor |
| JP4097053B2 (en) * | 1999-03-08 | 2008-06-04 | 東洋インキ製造株式会社 | Method for producing coloring composition for color filter and method for producing color filter |
| JP2002121420A (en) * | 2000-08-07 | 2002-04-23 | Dainippon Ink & Chem Inc | Copper phthalocyanine pigment and method for producing the same |
| JP2005234009A (en) * | 2004-02-17 | 2005-09-02 | Dainippon Ink & Chem Inc | Blue pigment composition for color filter, its manufacturing method, and color filter containing the same in blue pixel portion |
| JP2004231973A (en) * | 2004-04-08 | 2004-08-19 | Orient Chem Ind Ltd | Oxy-molybdenum phthalocyanine having new crystal transformation and its producing method |
| JP4815895B2 (en) * | 2005-06-29 | 2011-11-16 | Ｄｉｃ株式会社 | ε-type copper phthalocyanine pigment composition and method for producing the same |
| JP2007100008A (en) * | 2005-10-07 | 2007-04-19 | Toyo Ink Mfg Co Ltd | METHOD FOR PREPARING epsilon-PHTHALOCYANINE PIGMENT |
| DE102007001851A1 (en) * | 2007-01-12 | 2008-07-17 | Clariant International Ltd. | Finely divided epsilon-copper phthalocyanine composition (Pigment Blue 15: 6) for use as a pigment |
| EP2039727A1 (en) * | 2007-09-18 | 2009-03-25 | SOLVAY (Société Anonyme) | Preparation of epsilon copper phthalocyanine of small primary particle size and narrow particle size distribution |
| EP2060608A1 (en) * | 2007-11-15 | 2009-05-20 | SOLVAY (Société Anonyme) | Preparation of epsilon copper phthalocyanine of small primary particle size and narrow particle size distribution by kneading |
-
2009
- 2009-12-08 WO PCT/EP2009/066574 patent/WO2010072561A1/en active Application Filing
- 2009-12-08 CN CN200980152440.6A patent/CN102264844B/en not_active Expired - Fee Related
- 2009-12-08 JP JP2011542750A patent/JP5566399B2/en not_active Expired - Fee Related
- 2009-12-08 KR KR1020117017299A patent/KR20110119661A/en not_active Application Discontinuation
- 2009-12-14 TW TW098142698A patent/TWI478985B/en not_active IP Right Cessation
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE2554252A1 (en) * | 1975-12-03 | 1977-06-16 | Basf Ag | PROCESS FOR CONVERTING RAW COPPER PHTHALOCYANINES INTO A PIGMENT FORM |
| DE2742066A1 (en) * | 1976-09-21 | 1978-03-23 | Ciba Geigy Ag | COPPER PHTHALOCYANINE PIGMENT COMPOSITIONS AND PROCESS FOR THEIR PRODUCTION |
| WO2008095801A2 (en) * | 2007-02-07 | 2008-08-14 | Ciba Holding Inc. | Blue phthalocyanine pigment composition and its preparation |
Also Published As
| Publication number | Publication date |
|---|---|
| WO2010072561A1 (en) | 2010-07-01 |
| CN102264844B (en) | 2014-11-05 |
| TW201035248A (en) | 2010-10-01 |
| JP2012513510A (en) | 2012-06-14 |
| JP5566399B2 (en) | 2014-08-06 |
| TWI478985B (en) | 2015-04-01 |
| KR20110119661A (en) | 2011-11-02 |
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