CN102356130B - Process of preparing copper phthalocyanine particles exhibiting alpha crystallographic form - Google Patents

Process of preparing copper phthalocyanine particles exhibiting alpha crystallographic form Download PDF

Info

Publication number
CN102356130B
CN102356130B CN201080012409.5A CN201080012409A CN102356130B CN 102356130 B CN102356130 B CN 102356130B CN 201080012409 A CN201080012409 A CN 201080012409A CN 102356130 B CN102356130 B CN 102356130B
Authority
CN
China
Prior art keywords
cupc
particle
crystalline form
acid
functional group
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired - Fee Related
Application number
CN201080012409.5A
Other languages
Chinese (zh)
Other versions
CN102356130A (en
Inventor
李贤秀
朴在元
郑起硕
韩尚旻
金东润
郑铉锡
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Solvay SA
Original Assignee
Solvay SA
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Solvay SA filed Critical Solvay SA
Publication of CN102356130A publication Critical patent/CN102356130A/en
Application granted granted Critical
Publication of CN102356130B publication Critical patent/CN102356130B/en
Expired - Fee Related legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Images

Classifications

    • 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
    • C09B67/0017—Influencing the physical properties by treatment with an acid, H2SO4
    • C09B67/0019—Influencing the physical properties by treatment with an acid, H2SO4 of phthalocyanines
    • 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
    • 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
    • C09B67/0033—Blends of pigments; Mixtured crystals; Solid solutions
    • 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
    • C09B67/0033—Blends of pigments; Mixtured crystals; Solid solutions
    • C09B67/0034—Mixtures of two or more pigments or dyes of the same type
    • C09B67/0035—Mixtures of phthalocyanines
    • 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
    • C09B68/00—Organic pigments surface-modified by grafting, e.g. by establishing covalent or complex bonds, in order to improve the pigment properties, e.g. dispersibility or rheology
    • C09B68/40—Organic pigments surface-modified by grafting, e.g. by establishing covalent or complex bonds, in order to improve the pigment properties, e.g. dispersibility or rheology characterised by the chemical nature of the attached groups
    • C09B68/42—Ionic groups, e.g. free acid
    • C09B68/425—Anionic groups
    • C09B68/4253—Sulfonic acid groups
    • 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
    • C09B68/00—Organic pigments surface-modified by grafting, e.g. by establishing covalent or complex bonds, in order to improve the pigment properties, e.g. dispersibility or rheology
    • C09B68/40—Organic pigments surface-modified by grafting, e.g. by establishing covalent or complex bonds, in order to improve the pigment properties, e.g. dispersibility or rheology characterised by the chemical nature of the attached groups
    • C09B68/44—Non-ionic groups, e.g. halogen, OH or SH
    • C09B68/441—Sulfonic acid derivatives, e.g. sulfonic acid amides or sulfonic acid esters
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D11/00—Inks
    • C09D11/30—Inkjet printing inks
    • C09D11/32—Inkjet printing inks characterised by colouring agents

Abstract

There is provided a process of preparing copper phthalocyanine (CuPc) particles exhibiting an alpha crystallographic form, which comprises the following steps: (a) mixing crude copper phthalocyanine particles containing at least 50 wt % of particles exhibiting a beta crystallographic form with an acid in the presence of CuPc particles substituted by at least one functional group, such that at least part of the crude CuPc is dissolved in the acid; and (b) precipitating at least part of the dissolved CuPc in a medium. By adding CuPc derivatives in the acid-pasting step for the phase conversion from beta to alpha crystallographic type CuPc, the entire process time of producing blue pigments based on epsilon-CuPc, as well as the performance of the color filter pigment containing them, can be improved.

Description

Preparation presents the method for the CuPc particle of alpha crystalline form
The application requires the rights and interests of the European application submitted on March 18th, 2009 number 09155545.8, and it is combined in to this by reference.
Technical field
The method that present invention relates in general to CuPc (CuPc) and prepare it.More particularly, the present invention relates to for the preparation of new effective and economic method colour filter, CuPc pigment that have better dispersibility, a kind of and the CuPc pigment prepared thus, this type of pigment is for color display.
Background technology
A kind of pigment dyestuff based on phthalocyanine is excellent with regard to not fading property and performance.Therefore, it typically uses as a kind of blue dyes for coating or plastics.In pigment, CuPc is very stable and is further desirable, because it has multiple not fading property.In addition, CuPc has multiple crystalline form.In these crystalline forms, known there is practical application those comprise α, β and the ε crystalline form of CuPc.A common convention is to produce the blueness with pale green with beta-crystalline form, and produces with light red blueness with alpha crystalline form.In addition, when blue, use the ε crystalline form when need to be than the color of using alpha crystalline form to produce more partially red.
Diverse ways has been proposed for the production of a kind of phthalocyanine pigment with each crystalline form.A kind of typical method for the production of ε crystalline form CuPc is solvent salt milling, and the CuPc particle that wherein will present alpha crystalline form grinds in a kind of organic solvent with the CuPc particle that presents the ε crystalline form.About prepare a kind of method of α shape CuPc from β shape CuPc, use the staining method of sulfuric acid (mineral acid a kind of) to be well known in the art.That is exactly, utilize a kind of sour paste method (acid pasting process) (when rough CuPc is dissolved in a large amount of vitriol oils, it being processed) and a kind of sour slurry method (acid slurry process) (being to be not enough to dissolve the rough CuPc of vitriolization of pigment to form a kind of vitriol by the concentration had in a large number).
Have poor crystal mass on the overall product obtained by sour paste method or slurry method and be to produce with the form of coacervate, these coacervates do not demonstrate desirable performance.In order to reach subsequently best application characteristic, so-called final processing (when adding tensio-active agent) under solvent is for example carried out.In addition, in order to improve performance, proposed in the art by using the phthalocyanine derivates for example, replaced by polar group (sulfuric acid, carboxylic acid or sulfuryl amine group) to produce pigment product.
For example, U.S. Patent number US 3024247 has described a kind of general method: after the phthalocyanine of chlorination, phthalocyanine is carried out to the water slurry of sour paste and a kind of single sulfonic acid phthalocyanine and a kind of sour paste and admix to produce amorphous phthalocyanine coloring material.
In addition, U.S. Patent number US 5534055 has disclosed a kind of method for preparing α phase metal phthalocyanine pigment for the metal phthalocyanine pigment from rough.A kind of method like this comprises the following steps: (a) a kind of rough metal phthalocyanine pigment is carried out to sour paste or acid plumping; (b) will carry out dry grinding through the metal phthalocyanine pigment of peracid paste or acid plumping; (c) fully mix with a kind of final processing solvent mixture the metal phthalocyanine pigment of finally processing this grinding by the metal phthalocyanine pigment by grinding; And (d) α phase metal phthalocyanine pigment is separated.β CuPc is being carried out sour paste with the CuPc that produces precipitation after, the CuPc of precipitation and stablizer carried out to dry grinding with generation α CuPc at the sulfone amide derivative of CuPc under as a kind of existence of stablizer.
U.S. Patent number US 6031030 has also disclosed a kind of method for preparing the coating enriched material, the method comprises the following steps: (a) a kind of rough metal phthalocyanine is ground or sour paste to reduce its granularity, formed thus a kind of rough metal phthalocyanine of modification; And (b) by the rough metal phthalocyanine of modification with comprise that the vectorial a kind of mixture of coating of one or more paint solvents mediated to provide a kind of coating enriched material, the metal phthalocyanine that this coating enriched material comprises a kind of pigment form in being scattered in coating vehicle.For example described, under the existence of a kind of liquid agent (a kind of CuPc of sulfonation) rough CuPc has been ground, to produce α CuPc.
Yet, prepare a plurality of problems that the aforesaid method of alpha crystalline form CuPc has, because they have produced very large particle, in kneading step subsequently, need thus a large amount of time to carry out particle size reduction and to the inversion of phases of ε shape.In addition, due to the dispersibility of the difference of the pigment generated, from the sour paste legal system of prior art, the performance of standby colour filter pigment (for example contrast ratio) has some shortcoming.Therefore, strong hope develops a kind of method that effectively prepares the alpha crystalline form CuPc in the art, and the method is suitable for being mediated in a kind of more effective mode, and is suitable for improving the performance for a kind of final pigment of colour filter.
For solve problem in conventional preparation method (for example longer process period, relatively low dispersibility, carry out the contrast ratio of the colour filter pigment of self-generating, etc.), ladies and gentlemen contriver of the present invention finds, for example, when the sour paste step of the inversion of phases for from β to the alpha-crystal form adds some additives (CuPc derivative), can improve the performance of final colour filter pigment and for the production of whole process period of blue pigments.
Below the present invention is described in detail.
Therefore, the objective of the invention is the CuPc particle (as a kind of intermediate of the CuPc particle for the production of thering is ε shape) that preparation has alpha crystalline form, the granularity of these particles is very little and its dispersibility is better, and the performance of the better colour filter of producing with CuPc pigment is provided thus.In addition, another object of the present invention is to provide a kind of method for preparing the α shape CuPc with the granularity reduced, and the method needs the shorter time to obtain the ε crystalline form CuPc with high crystallization purity.In this regard, the present invention be directed to exploitation a kind of new and the more effective method for preparing CuPc, the method meets above-mentioned feature.
The acid paste refers at least part of rough CuPc is dissolved in suitable acid to (dissolving step) and dissolved CuPc is precipitated in suitable medium to (settling step).
In dissolving step, preferably use mineral acid, for example the monohydrate of sulfuric acid, chlorsulfonic acid and Tripyrophosphoric acid, the particularly vitriol oil or sulfuric acid.These acid are used with a kind of form of the aqueous solution usually.If use sulfuric acid, its concentration should be to be equal to or greater than by weight 90% so, preferably is equal to or greater than by weight 95%.Preferably use about 96% the vitriol oil by weight.The amount that the aqueous solution to be used is arranged in dissolving step is unrestricted.Yet due to economically, the concentration of the rough CuPc of grinding can remain in such a scope, wherein the mixture of generation can be stirred or grinds and mix.Definitely, the amount of the aqueous solution used is for based on 2 to 20 times of rough pigment weight, preferably 5 to 15 times.The temperature of dissolving step is normally from 0 ℃ to 100 ℃, preferably from 5 ℃ to 60 ℃, and more preferably from 10 ℃ to 40 ℃, room temperature for example.The time length of dissolving step is from 30 minutes to 5 hours generally, and particularly, from 1 hour to 3 hours, the time length of about 2 hours is suitable.
In settling step, the precipitation medium used can comprise: water, organic solvent or their mixture, preferably water, particularly distilled water.Precipitation medium is from 1 to 50 with the ratio of the mixture acid/CuPc generated from dissolving step generally, preferably from 5 to 20, for example about 10.The temperature of settling step can be from 0 ℃ to 100 ℃, and particularly from 5 ℃ to 60 ℃, more particularly from 10 ℃ to 50 ℃, operation at room temperature is also suitable.Mixture acid/the CuPc generated from dissolving step normally joining precipitation medium with every kilogram of precipitation medium 1g to the ratio of 100g mixture acid/CuPc in 1 minute to 1 hour, preferably in 5 minutes to 30 minutes, with 1g, to the ratio of 100g (mixture acid/CuPc)/kg (precipitation medium), add, for example in about 10 minutes, the ratio with about 10g (mixture acid/CuPc)/kg (precipitation medium) adds.Precipitating action can occur under turbulent-flow conditions.
The mixture that then will generate from dissolving step filters, washes with water and carries out drying.Preferably, washing is carried out with distilled water, more preferably with having the distilled water of pH at least 6, carries out.For filtering and drying step, can use any filtration be known in the art or desiccating method.For example, can complete filtration by a gravity system, and can be at one in for example in the baking oven of temperature of 120 ℃, carrying out drying.
This kind of sour paste processing is described in for example Ullmann ' s Encyclopedia of Industrial Chemistry, the 5th complete revised edition, and 1992, A20 volume, in the 225-226 page.
In first embodiment of the present invention, CuPc (CuPc) particle that presents alpha crystalline form is by with the preparation of getting off:
(a) will comprise the rough CuPc particle that the particle of 50wt% at least presents beta-crystalline form under the existence of the CuPc particle replaced by least one functional group and be mixed with a kind of acid, and make like this this at least part of rough CuPc be dissolved in this acid; And
(b) CuPc of this at least part of dissolving is precipitated in a kind of medium.In specific embodiment, the mean number of the functional group of every CuPc molecule is 0.5 to 2, preferably approximately 1.
In dissolving step (a), rough CuPc preferably is dissolved in acid fully.In described dissolving step (a), the CuPc replaced by least one functional group is greater than or equal to 0.01 with the ratio of the weight of rough CuPc generally, preferably greater than or equal to 0.03, and more preferably greater than or equal to 0.05.Such a ratio is generally less than or equal to 0.3, preferably less than or equal to 0.2, and most preferably less than or equal to 0.15.
In some specific embodiments, this functional group is be selected from-SO 3m ,-SO 2nR 1r 2, and-R 3-NR 4r 5at least one, R wherein 1and R 2separate and can be selected from lower group, this group is comprised of the following: hydrogen, alkyl, alkenyl, aryl or cycloalkyl; M can be proton, ammonium cation or a metallic cation; R 3can be singly-bound, alkylidene group or an arylidene, wherein said alkylidene group and arylidene can be replaced by least one substituting group; And R 4and R 5separate and can be hydrogen, alkyl, alkenyl, aryl, cycloalkyl, or jointly form a condensation structure, comprise-CO-of this condensation structure ,-SO 2-or-at least one in N=N-.
More properly, can be selected from-SO of CuPc particle 3h ,-SO 2nHR 1and
Figure BPA00001437697500041
at least one functional group replace, R wherein 1hydrogen, alkyl, alkenyl, aryl or cycloalkyl.More properly, this functional group is-SO 3h, their a kind of mixture.In another embodiment, the CuPc particle replaced by a functional group is a kind of mixture of the CuPc particle of at least two kinds of different replacements, for example, by-SO 3the CuPc particle that H replaces with by
Figure BPA00001437697500052
a kind of mixture of the CuPc particle replaced.
In another embodiment, remaining, CuPc particle that present ε crystalline form that use as a kind of blue pigments by with the preparation of getting off: CuPc particle that prepare according to the first embodiment, that present a kind of alpha crystalline form is heated under a kind of existence of organic liquid at the temperature greater than or equal to 50 ℃, and optionally grind under the existence of bead.As defined at this, the meaning of grinding is to make solid stand to wear away, mill etc. to reach a kind of method of particle size reduction.As defined at this, the dry gound meaning is when substantially there is no liquid, to make solid stand to wear away, mill etc. to reach a kind of method of particle size reduction.Yet, can add a kind of low-level solvent.
In another embodiment again, crystalline phase transforms and particle size reduction can occur simultaneously.In this embodiment, kneading is to carry out under the existence of at least one liquid and at least one inorganic salt.Preferably, kneading is to carry out under certain temperature condition, makes like this temperature profile curve display as the function of time go out temperature and equals 0 with respect at least two derivatives of time (dT/dt).These two temperature are relevant to the derivative that equals 0, differ at least 10 ℃.In another embodiment, kneading is to carry out under the temperature profile curve of constantly changing (or at least one times, segmentation).
The specified conditions of kneading or heating steps have been described in PCT application number PCT/EP2008/065448 and PCT/EP2008/062266 (for example, time length, organic liquid, liquid, bead, inorganic salt, Deng), they are combined in to this in full by reference with it.
By in sour paste process, adding the CuPc derivative, method of the present invention can produce the alpha crystalline form CuPc with less average primary particle size, and this granularity, for being not more than 140nm, preferably is not more than 100nm.In addition, when in sour paste process, adding this type of CuPc derivative, can obtain the better dispersibility of granules of pigments, this has produced the improved contrast ratio of the colour filter generated from the granules of pigments preparation.
In addition, in another embodiment, at kneading or heating steps and add the CuPc particle replaced by least one functional group in sour paste step.For example,, by be selected from-SO 3h ,-SO 2nHR 1and
Figure BPA00001437697500061
the CuPc particle that replaces of at least one functional group (R wherein 1hydrogen, alkyl, alkenyl, aryl or cycloalkyl, preferably ) may reside in dissolving step (a), and by-SO 3the CuPc particle that H replaces can (especially in kneading step) further add in the process of kneading or heating steps.
The invention still further relates to the available alpha crystalline form CuPc of the method according to this invention particle.The CuPc particle that this embodiment can arrive for the method according to this invention is for the preparation of the purposes of the CuPc particle that presents the ε crystalline form.It also relates to a colour filter of the CuPc particle that comprises the available ε of the presenting crystalline form of the method according to this invention.
Example
Example 1 (sour paste β-CuPc and phthalimide methyl-CuPc (phthaloimidomethyl-CuPc))
The CuPc that the rough CuPc of 20g and 1g are replaced by phthalimide methyl (PIM) joins in the sulfuric acid of the 200g 95wt% in the glass beaker of a 1L.In addition, the miscellany generated is stirred to 2 hours to prepare suspension or the solution of vitriol in sulfuric acid under 30 ℃ by an impeller agitator (stirring impeller) (special teflon whizzer, rotating speed is 300rpm).This suspension or solution are poured in 2L water to obtain a kind of alpha crystalline form CuPc, then it is carried out to drying with twice of distilled water wash and under warm air.After the solid abrasive dust generated, through XRD, studies confirm that, obtained with regard to crystallization yields almost quantitative alpha crystalline form CuPc.
Example 2 (sour paste β-CuPc and single sulfonation-CuPc)
Except adding the mono-sulfonation of 1g-CuPc particle to replace phthalimide methyl-CuPc particle, in a kind of mode identical with example 1, obtained the CuPc particle that presents alpha crystalline form.
Example 3 (sour paste β-CuPc and single sulfonation-and phthalimide methyl-CuPc particle)
Except adding the mono-sulfonation of 0.5g-CuPc particle and 0.5g phthalimide methyl-CuPc particle to replace 1g phthalimide methyl-CuPc particle, in a kind of mode identical with example 1, obtained the CuPc particle that presents alpha crystalline form.
Comparison example 1 (only sour paste β-CuPc)
Except not adding the CuPc derivative, in a kind of mode identical with example 1, obtained the CuPc particle that presents alpha crystalline form.When with transmission electron microscope (TEM), some dry samples of the generated CuPc particle that presents alpha crystalline form being analyzed, demonstrate them and there is the mean particle size (Fig. 3) that is greater than 140 μ m.
As shown in the TEM image in Fig. 1-3, the mean particle size of the α that uses method of the present invention (example 1 and example 2) to generate-CuPc particle (, about 97nm) be markedly inferior to the mean particle size (that is, being greater than 140 μ m) of the α for preparing by conventional sour paste method (comparison example 1)-CuPc particle.The size of the α by reducing to remain to mediate-CuPc particle, kneading time can reduce significantly, and the dispersibility of the particle generated can be improved.
Example 4 (crystalline phase of CuPc from alpha crystalline form to the ε crystalline form transforms)
To the CuPc particle that presents a kind of alpha crystalline form and 12g ε type CuPc and 80g Diethylene Glycol and the 400g sodium-chlor that add 50g to obtain from example 1 or 2 in the kneader of a laboratory-scale.By this mixture 130 ℃, mediate 2 hours (first stage) and then with same speed of rotation, under 80 ℃, mediate 8 hours (subordinate phase) with the speed of rotation of 50rpm.After kneading, the gained particle carries out purifying by filtration and the temperature and 10 of 80 ℃ 4carry out drying under the pressure of Pa.
Example 5 (crystalline phase of CuPc from alpha crystalline form to the ε crystalline form transforms under the existence of single sulfonation-CuPc)
Obtained presenting the CuPc particle of ε crystalline form from α-CuPc (obtaining from example 3) in a kind of mode identical with example 4.Yet, before kneading step, alpha crystalline form CuPc and ε type CuPc are processed to 2 hours (replacing the first stage) and add 6.2g MS-CuPc in the processes of kneading step under 130 ℃ in Diethylene Glycol.
Example 6 (crystalline phase of CuPc from alpha crystalline form to the ε crystalline form transforms under the existence of single sulfonation-CuPc)
Obtained presenting the CuPc particle of ε crystalline form from α-CuPc (obtaining from example 1) in a kind of mode identical with example 4.Yet, before kneading step, alpha crystalline form CuPc and ε type CuPc are processed to 2 hours (replacing the first stage) and add 6.2g MS-CuPc in kneading steps under 130 ℃ in Diethylene Glycol.
Example 7 (crystalline phase of CuPc from alpha crystalline form to the ε crystalline form transforms under the existence of single sulfonation-CuPc)
Except add 6.2g MS-CuPc in kneading step, in a kind of mode identical with example 4, obtained presenting the CuPc particle of ε crystalline form from α-CuPc (obtaining from example 1).
Example 8 (crystalline phase of CuPc from alpha crystalline form to the ε crystalline form transforms under the existence of cetyltrimethyl ammonium list sulfo group CuPc (cetyltrimethyl ammonium monosulfo CuPc))
Except add 6.2g cetyltrimethyl ammonium list sulfo group CuPc in kneading step, in a kind of mode identical with example 4, obtained presenting the CuPc particle of ε crystalline form from α-CuPc (obtaining from example 1).
Comparison example 2 (crystalline phase of CuPc from alpha crystalline form to the ε crystalline form transforms when adding PIM-CuPc and MS-CuPc)
Except sequentially adding PIM-CuPc and MS-CuPc, in a kind of mode identical with example 4, obtained presenting the CuPc particle of ε crystalline form from α-CuPc (obtaining from comparison example 1) in kneading step.
The test of the particle in example 9. colour filters
Be used as the ε shape CuPc granules of pigments from according to example 4 to 8 and comparison example 2 preparations of pigment to manufacture colour filter.Contrast ratio and the brightness of the colour filter produced are summarised in following table 1.These results demonstrate, and with the contrast ratio of comparison example 2, compare, and example 4 to 8 has produced about improvement of 4% to 21% on contrast ratio, as shown in Table 1.In addition, when from example 5, (wherein sour paste step, adding PIM-CuPc and MS-CuPc, and further add MS-CuPc in kneading step) while preparing colour filter, (wherein in sour paste step, only add PIM-CuPc with example 6, and further add MS-CuPc in kneading step) to compare, they have produced better effect in contrast ratio and brightness.With example 8 (utilizing cetyltrimethyl ammonium list sulfo group CuPc), compare, the colour filter of manufacturing from example 7 (utilizing MS-CuPc) has also produced improved effect.
Table 1
Contrast ratio (a.u. *) Brightness (a.u.)
Comparison example 2 5630 Do not measure
Example 4 5850 Do not measure
Example 5 6815 18.44
Example 6 6625 18.27
Example 7 6815 18.20
Example 8 6673 18.19
*arbitrary unit
Brief Description Of Drawings
Fig. 1 is an image from transmission electron microscope (TEM) of the CuPc particle that presents the α crystalline phase for preparing for the method by according to example 1.
Fig. 2 is an image from TEM of the CuPc particle that presents the α crystalline phase for preparing for the method by according to example 2.
Fig. 3 is an image from TEM of the CuPc particle that presents the α crystalline phase for preparing for the method by according to comparison example 1.
Industrial application
Will be clear that without deviating from the spirit and scope of the present invention and can make different changes and change to the present invention those of ordinary skills.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.
Conflict with this disclosure if be combined in by reference this any patent, patent application and the disclosure of announcing, just make a unclear aspect of term, this disclosure should be preferential.

Claims (6)

1. a method for preparing the CuPc particle (CuPc) that presents the ε crystalline form, being included in the CuPc particle that will present alpha crystalline form under certain temperature condition is mediated, make temperature profile curve display as the function of time go out temperature and equal 0 at least two derivatives (dT/dt) of time, wherein at least described, equal at least two temperature that 0 derivative is relevant and differ at least 10 ℃, wherein:
The described particle that is more than or equal to 50wt% under the existence of liquid and at least one inorganic salt presents alpha crystalline form;
By the method comprised the steps, prepared by the described CuPc particle that presents alpha crystalline form:
(a) will comprise the rough CuPc particle that 50wt% at least presents the particle of beta-crystalline form under the existence of the CuPc particle replaced by least one functional group and be mixed with acid, and make at least part of rough CuPc be dissolved in this acid; With
(b) CuPc of at least part of described dissolving is precipitated in medium; And
The described CuPc particle replaced by least one functional group in step (a) comprise by
Figure FSB0000113281760000011
the CuPc particle replaced, and in described kneading step, further add by-SO 3the CuPc particle that H replaces.
2. the method for claim 1, wherein said acid be selected from following at least one: sulfuric acid, chlorsulfonic acid and Tripyrophosphoric acid.
3. method as claimed in claim 1 or 2, wherein said medium is at least one being selected from water, organic solvent or their mixture.
4. method as claimed in claim 1 or 2, wherein the mean number of the functional group of every CuPc molecule is 0.5 to 2.
5. method as claimed in claim 1 or 2, wherein at the serve as reasons-SO of CuPc particle replaced by functional group described in step (a) 3the CuPc particle that H replaces with by the mixture of the CuPc particle replaced.
6. a colour filter, comprise CuPc particle obtainable by the described method of any one in claim 1 to 5, that present the ε crystalline form.
CN201080012409.5A 2009-03-18 2010-03-12 Process of preparing copper phthalocyanine particles exhibiting alpha crystallographic form Expired - Fee Related CN102356130B (en)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
EP09155545 2009-03-18
EP09155545.8 2009-03-18
PCT/EP2010/053184 WO2010105982A2 (en) 2009-03-18 2010-03-12 Process of preparing copper phthalocyanine particles exhibiting alpha crystallographic form

Publications (2)

Publication Number Publication Date
CN102356130A CN102356130A (en) 2012-02-15
CN102356130B true CN102356130B (en) 2014-01-08

Family

ID=41034249

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201080012409.5A Expired - Fee Related CN102356130B (en) 2009-03-18 2010-03-12 Process of preparing copper phthalocyanine particles exhibiting alpha crystallographic form

Country Status (5)

Country Link
JP (2) JP2012520914A (en)
KR (1) KR20110134478A (en)
CN (1) CN102356130B (en)
TW (1) TWI466956B (en)
WO (1) WO2010105982A2 (en)

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR102243520B1 (en) * 2019-11-20 2021-04-21 포항공과대학교 산학협력단 Novel phthalocyanine nanowire and use thereof

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR1116429A (en) * 1953-08-29 1956-05-08 Basf Ag Process for the production of the alpha modification of copper phthalocyanine which modification is stable to solvents
US4039346A (en) * 1975-02-18 1977-08-02 Basf Aktiengesellschaft Conversion of crude copper phthalocyanines into pigments
CN1323857A (en) * 2000-02-04 2001-11-28 大日精化工业株式会社 Dyestuff compositions, its mfg. method, colouring pigment and colouring material
EP1580239A1 (en) * 2004-03-26 2005-09-28 Toyo Ink Mfg. Co., Ltd. Process for the production of E crystal form copper phthalocyanine
CN1837219A (en) * 2004-03-26 2006-09-27 东洋油墨制造株式会社 Copper phthalocyanine-iodine intermolecular compound and preparation method therefor
WO2008095801A2 (en) * 2007-02-07 2008-08-14 Ciba Holding Inc. Blue phthalocyanine pigment composition and its preparation

Family Cites Families (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3024247A (en) 1958-05-26 1962-03-06 Standard Ultramarine & Color C Non-crystallizing phthalocyanine coloring matters
JPH06136280A (en) * 1992-10-21 1994-05-17 Mitsubishi Paper Mills Ltd Production of alpha-type nonmetallic phthalocyanine
US5534055A (en) * 1994-08-24 1996-07-09 Bayer Corporation Process for alpha-phase metal phthalocyanine pigments
GB9709762D0 (en) 1997-05-15 1997-07-09 Ciba Geigy Ag Production process
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
JP4398101B2 (en) * 2000-02-04 2010-01-13 大日精化工業株式会社 Blue ink composition for color filter, method for producing color filter using the same, and color filter
JP2002121420A (en) * 2000-08-07 2002-04-23 Dainippon Ink & Chem Inc Copper phthalocyanine pigment and method for producing the same
JP2005272760A (en) * 2004-03-26 2005-10-06 Toyo Ink Mfg Co Ltd epsilon-TYPE CRYSTAL FORM COPPER PHTHALOCYANINE AND METHOD FOR PRODUCING THE SAME
JP2005306841A (en) * 2004-03-26 2005-11-04 Toyo Ink Mfg Co Ltd METHOD FOR PRODUCING COPPER PHTHALOCYANINE HAVING epsilon-CRYSTAL FORM
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
JP2008019367A (en) * 2006-07-14 2008-01-31 Toyo Ink Mfg Co Ltd Method for producing fine organic 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

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR1116429A (en) * 1953-08-29 1956-05-08 Basf Ag Process for the production of the alpha modification of copper phthalocyanine which modification is stable to solvents
US4039346A (en) * 1975-02-18 1977-08-02 Basf Aktiengesellschaft Conversion of crude copper phthalocyanines into pigments
CN1323857A (en) * 2000-02-04 2001-11-28 大日精化工业株式会社 Dyestuff compositions, its mfg. method, colouring pigment and colouring material
EP1580239A1 (en) * 2004-03-26 2005-09-28 Toyo Ink Mfg. Co., Ltd. Process for the production of E crystal form copper phthalocyanine
CN1837219A (en) * 2004-03-26 2006-09-27 东洋油墨制造株式会社 Copper phthalocyanine-iodine intermolecular compound and preparation method therefor
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
WO2010105982A2 (en) 2010-09-23
JP2012520914A (en) 2012-09-10
CN102356130A (en) 2012-02-15
JP2015143368A (en) 2015-08-06
KR20110134478A (en) 2011-12-14
TW201100497A (en) 2011-01-01
WO2010105982A3 (en) 2010-12-09
TWI466956B (en) 2015-01-01

Similar Documents

Publication Publication Date Title
CN1329455C (en) Method for the production of phthalocyanine pigment preparations
US2861005A (en) Phthalocyanine pigments
CN106752059B (en) A kind of preparation method of red dye Lumogen Red F300
JPH0376877A (en) Use of perylene-3,4,9,10- tetracarboxylic acid diimide pigment
US3523030A (en) Pigment treatment
CN101918496B (en) Preparation of epsilon copper phthalocyanine of small primary particle size and narrow particle size distribution by kneading
CN107429077B (en) Process for producing quinacridone pigment composition
JPS596261A (en) Manufacture of high grade pigment from crude pigment
AU685666B2 (en) Pigmentary solid solutions of pyrrolo(3,4-C)pyrroles and quinacridones
CN102356130B (en) Process of preparing copper phthalocyanine particles exhibiting alpha crystallographic form
US3984433A (en) Process for preparing copper phthalocyanine pigments of the α-modification
CN101864198A (en) Production process of novel phthalocyanine blue pigment
CN101457027A (en) High-grade glow blue pigment and preparation method thereof
CN106084884A (en) Pigment red 3 BL pigmentation processes technique
CN103403101A (en) Process of preparing product based on copper phthalocyanine (CuPc) particles
JP2010535874A (en) Preparation method of organic pigment
US2930796A (en) Conditioning of crude polychloro copper phthalocyanines
CN111763433A (en) Copper chloride phthalocyanine pigment composition for non-bronze plastic coloring and preparation method thereof
JPH08231870A (en) Preparation of organic pigment
JPH04320458A (en) Production of copper phthalocyanine pigment
CN111363379B (en) Pigment violet 23 composition and preparation method and application thereof
US3880890A (en) Manufacture of 3,4,9,10-perylenetetracarboxylic acid dianhydride pigments having high tinctorial strength
CN102264844B (en) Efficient process for preparation of copper phthalocyanine particles exhibiting epsilon crystallographic form
CN103289435A (en) Pigment derivative used for liquid crystal display and its making method
JPS61118460A (en) Production of pigment composition

Legal Events

Date Code Title Description
C06 Publication
PB01 Publication
C10 Entry into substantive examination
SE01 Entry into force of request for substantive examination
C14 Grant of patent or utility model
GR01 Patent grant
CF01 Termination of patent right due to non-payment of annual fee

Granted publication date: 20140108

Termination date: 20170312

CF01 Termination of patent right due to non-payment of annual fee