CN102356130A - Process of preparing copper phthalocyanine particles exhibiting alpha crystallographic form - Google Patents
Process of preparing copper phthalocyanine particles exhibiting alpha crystallographic form Download PDFInfo
- Publication number
- CN102356130A CN102356130A CN2010800124095A CN201080012409A CN102356130A CN 102356130 A CN102356130 A CN 102356130A CN 2010800124095 A CN2010800124095 A CN 2010800124095A CN 201080012409 A CN201080012409 A CN 201080012409A CN 102356130 A CN102356130 A CN 102356130A
- Authority
- CN
- China
- Prior art keywords
- cupc
- crystalline form
- particle
- acid
- particulate
- 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.)
- Granted
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
The rights and interests of the European application that the application requires to submit on March 18th, 2009 number 09155545.8 are combined in this by reference with it.
Technical field
The method that present invention relates in general to CuPc (CuPc) and prepare it.More particularly, the present invention relates to prepare be used for CuPc pigment colour filter, that have better dispersibility, a kind of new effective and economic method and the CuPc pigment of preparation thus, this type of pigment is used 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 that is used 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 have a practical application those comprise α, β and the ε crystalline form of CuPc.A common convention is to use beta-crystalline form to produce the blueness of band pale green, and uses alpha crystalline form to produce with light red blueness.In addition, when need be than red more partially blue of the color of using alpha crystalline form to produce, use ε crystalline form.
Proposed diverse ways and be used to produce a kind of phthalocyanine pigment with each crystalline form.A kind of typical method that is used to produce ε crystalline form CuPc is a 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 preparing 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 handled) and a kind of sour slurry method (acid slurry process) (using the concentration have in a large number is that the rough CuPc of vitriolization that is not enough to dissolve pigment is to form a kind of vitriol).
Have poor crystal mass on the overall product that is obtained by sour paste method or slurry method and be that form with coacervate produces, these coacervates do not demonstrate desirable performance.In order to reach best application characteristic subsequently, 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 to produce pigment product by the substituted phthalocyanine derivates of polar group (for example sulfuric acid, carboxylic acid or sulfuryl amine group) through using.
For example, U.S. Patent number US 3024247 has described a kind of method in common: after the chlorating phthalocyanine, phthalocyanine is carried out the water slurry of sour pasteization and a kind of single sulfonic acid phthalocyanine and a kind of sour pasteization and admix to produce amorphous phthalocyanine coloring material.
In addition, U.S. Patent number US 5534055 has disclosed a kind of method that is used for from rough metal phthalocyanine pigment prepared α phase metal phthalocyanine pigment.A kind of method like this may further comprise the steps: (a) a kind of rough metal phthalocyanine pigment is carried out sour pasteization or acid plumping; (b) will carry out dry grinding through the metal phthalocyanine pigment of peracid pasteization or acid plumping; (c) come the final metal phthalocyanine pigment of handling this grinding through metal phthalocyanine pigment and a kind of final processing solvent mixture thorough mixing that will grind; And (d) α phase metal phthalocyanine pigment is separated.β CuPc is being carried out sour pasteization with after producing sedimentary CuPc, at the sulfone amide derivative of CuPc as in the presence of a kind of stablizer sedimentary CuPc and stablizer being carried out dry grinding to produce α CuPc.
U.S. Patent number US 6031030 has also disclosed a kind of method for preparing the coating enriched material; This method may further comprise the steps: (a) a kind of rough metal phthalocyanine is ground or sour pasteization to reduce its granularity, formed a kind of rough metal phthalocyanine of modification thus; And (b) the rough metal phthalocyanine of modification and the vectorial a kind of mixture of coating that comprises one or more paint solvents are mediated so that a kind of coating enriched material to be provided, this coating enriched material comprises and is in the metal phthalocyanine that is scattered in a kind of pigment form in the coating vehicle.Described in the presence of a kind of liquid agent (for example a kind of sulfonated CuPc) rough CuPc has been ground, to produce α CuPc.
Yet a plurality of problems that the aforesaid method of preparation alpha crystalline form CuPc has because they have produced very large particle, need great amount of time to carry out particle size reduction and to the inversion of phases of ε shape in kneading step subsequently thus.In addition, because the dispersibility of the difference of the pigment that generates, has some shortcoming from the performance (for example contrast ratio) of the colour filter pigment of the sour paste method preparation of prior art.Therefore, a kind of effective method for preparing the alpha crystalline form CuPc of strong in the art hope development, this method is suitable for mediating with a kind of more effective mode, and is suitable for improving the performance of a kind of final pigment that is used for colour filter.
In order to solve problem (for example longer process period, low relatively dispersibility, the contrast ratio of coming the colour filter pigment of self-generating in conventional preparation method; Or the like); Ladies and gentlemen contriver of the present invention finds; When the sour paste step that is used for the inversion of phases from β to the alpha-crystal form adds some additives (for example CuPc derivative), the whole machining process time that can improve the performance of final colour filter pigment and be used to produce blue pigments.
Below the present invention is described in detail.
Therefore; The objective of the invention is to prepare CuPc particle (as being used to produce a kind of intermediate of CuPc particulate) with ε shape with alpha crystalline form; These particulate granularities are very little and its dispersibility is better, and the performance of the better colour filter of being produced with CuPc pigment is provided thus.In addition, another object of the present invention provides the method that a kind of preparation has the α shape CuPc of the granularity that reduces, the ε crystalline form CuPc that this method need obtain to have high crystallization purity the shorter time.In this regard, The present invention be directed to exploitation a kind of new and the more effective method for preparing CuPc, this method satisfies above-mentioned characteristic.
The acid pasteization is meant the rough CuPc of part at least is dissolved in the suitable acid (dissolving step) and the dissolved CuPc of institute is precipitated (settling step) in suitable medium.
In dissolving step, preferably use mineral acid, for example sulfuric acid, chlorsulfonic acid and Tripyrophosphoric acid, the particularly vitriol oil or vitriolic monohydrate.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%.Preferred about by weight 96% the vitriol oil that uses.The amount that the aqueous solution to be used is arranged in dissolving step is unrestricted.Yet because economically, the concentration of the rough CuPc of grinding can remain in the such scope, wherein the mixture that generates can be stirred or grind and mix.Definitely, the amount of the employed aqueous solution is 2 to 20 times based on rough pigment weight, preferred 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, about 2 hours time length was suitable.
In settling step, employed precipitation medium 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 that generates 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 also is suitable.Mixture acid/the CuPc that generates from dissolving step normally joined the precipitation medium to the ratio of 100g mixture acid/CuPc with every kilogram of precipitation medium 1g in 1 minute to 1 hour; Preferably (ratio of mixture acid/CuPc)/kg (precipitation medium) adds, and for example (ratio of mixture acid/CuPc)/kg (precipitation medium) adds with about 10g in about 10 minutes to 100g with 1g in 5 minutes to 30 minutes.Precipitating action can take place under turbulent-flow conditions.
Then the mixture that will generate from dissolving step filter, with water washing and carry out drying.Preferably, washing is carried out with distilled water, more preferably uses to have pH and carry out at least 6 distilled water.For filtering and drying step, can use any filtration that is known in the art or desiccating method.For example, can use a gravity system to accomplish filtration, and can for example be in 120 ℃ the baking oven of temperature at one and carry out drying.
The sour paste processing of this kind is described in for example Ullmann ' s Encyclopedia of Industrial Chemistry, the 5th complete revised edition, and 1992, the A20 volume is in the 225-226 page or leaf.
In one first embodiment of the present invention, CuPc (CuPc) particle that presents alpha crystalline form is through with the preparation of getting off:
(a) by at least one functional group will comprise the rough CuPc particle that the particle of 50wt% at least presents beta-crystalline form in the presence of the substituted CuPc particulate and mix with a kind of acid, make that like this this rough CuPc of part is dissolved in this acid at least; And
(b) making at least, this dissolved CuPc of part precipitates in a kind of medium.In concrete 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 the acid fully.In said dissolving step (a), by at least one functional group the ratio of substituted CuPc and the weight of rough CuPc be to be greater than or equal to 0.01 generally, preferably be greater than or equal to 0.03, and more preferably be greater than or equal to 0.05.A ratio so generally is to be less than or equal to 0.3, preferably is less than or equal to 0.2, and most preferably is less than or equal to 0.15.
In some concrete embodiments, this functional group is selected from-SO
3M ,-SO
2NR
1R
2, and-R
3-NR
4R
5At least a, R wherein
1And R
2Separate 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 a metallic cation; R
3Can be singly-bound, alkylidene group or an arylidene, wherein said alkylidene group and arylidene can be replaced by at least one substituting group; And R
4And R
5Separate and can be hydrogen, alkyl, alkenyl, aryl, cycloalkyl, or form a condensation structure jointly, this condensation structure comprises-CO-,-SO
2-or-at least a among the N=N-.
More properly, the CuPc particle can be selected from-SO
3H ,-SO
2NHR
1And
At least one functional group replace R wherein
1Be hydrogen, alkyl, alkenyl, aryl or cycloalkyl.More properly, this functional group is-SO
3H,
Their a kind of mixture.In another embodiment, by a functional group substituted CuPc particle be at least two kinds of different a kind of mixtures of substituted CuPc particulate, for example by-SO
3The substituted CuPc particle of H with by
A kind of mixture of substituted CuPc particulate.
In another embodiment; Remain as a kind of blue pigments CuPc particle that use, that present the ε crystalline form through with the preparation of getting off: will heat being greater than or equal in the presence of a kind of organic liquid under 50 ℃ the temperature according to first embodiment CuPc particle preparation, that present a kind of alpha crystalline form, and randomly grinding in the presence of bead.Such as this definition, the meaning of grinding is to make solid stand to wear away, mill etc. to reach a kind of method of particle size reduction.Such as this definition, the dry gound meaning is when not having liquid basically, 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 take place simultaneously.In this embodiment, kneading is in the presence of at least a liquid and at least a inorganic salt, to carry out.Preferably, kneading is under certain temperature condition, to carry out, and makes temperature profile curve display as the function of time go out temperature like this and equals 0 with respect at least two derivatives of time (dT/dt).These two temperature are relevant with the derivative that equals 0, differ at least 10 ℃.In another embodiment, kneading is to carry out constantly changing under the temperature profile curve of (or at least once, sectional).
The specified conditions of in PCT application number PCT/EP2008/065448 and PCT/EP2008/062266, having described kneading or heating steps (for example; Time length, organic liquid, liquid, bead, inorganic salt; Deng), they are combined in this in full by reference with it.
Through in sour paste process, adding the CuPc derivative, method of the present invention can produce the alpha crystalline form CuPc with littler average primary particle size, and this granularity preferably is not more than 100nm for being not more than 140nm.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 that generates from the granules of pigments preparation.
In addition, in another embodiment, add by at least one substituted CuPc particle of functional group at kneading or heating steps and in sour paste step.For example, by being selected from-SO
3H ,-SO
2NHR
1And
At least one substituted CuPc particle of functional group (R wherein
1Be hydrogen, alkyl, alkenyl, aryl or cycloalkyl, preferred
) may reside in the dissolving step (a), and by-SO
3H substituted CuPc particle can mediate or the process of heating steps in (especially in kneading step) further add.
The invention still further relates to the available alpha crystalline form CuPc of the method according to this invention particle.This embodiment is used to prepare the CuPc particulate purposes that presents the ε crystalline form to the CuPc particle that the method according to this invention can arrive.It also relates to the colour filter of CuPc particulate that comprises the available ε of the appearing crystalline form of the method according to this invention.
Instance
Instance 1 (sour paste β-CuPc and phthalimide methyl-CuPc (phthaloimidomethyl-CuPc))
Rough CuPc of 20g and 1g are joined in the sulfuric acid of the 200g 95wt% in the glass beaker of a 1L by the substituted CuPc of phthalimide methyl (PIM).In addition, the miscellany that generates is stirred 2 hours down with suspension-s or the solution of preparation vitriol in sulfuric acid by an impeller agitator (stirring impeller) (special teflon whizzer, rotating speed are 300rpm) at 30 ℃.This suspension-s or solution are poured in the 2L water to obtain a kind of alpha crystalline form CuPc, then it is carried out drying with twice of distilled water wash and under warm air.After the solid abrasive dust that generates, research confirms through XRD, has obtained almost quantitative alpha crystalline form CuPc with regard to crystallization yields.
Instance 2 (sour paste β-CuPc and single sulfonation-CuPc)
Replace phthalimide methyl-CuPc particle except adding the single sulfonation of 1g-CuPc particle, obtained to appear the CuPc particle of alpha crystalline form with a kind of and instance 1 identical mode.
Instance 3 (sour paste β-CuPc and single sulfonation-and phthalimide methyl-CuPc particle)
Replace 1g phthalimide methyl-CuPc particle except adding the single sulfonation of 0.5g-CuPc particle and 0.5g phthalimide methyl-CuPc particle, obtained to appear the CuPc particle of alpha crystalline form with a kind of and instance 1 identical mode.
Comparison example 1 (only sour paste β-CuPc)
Except not adding the CuPc derivative, obtained to appear the CuPc particle of alpha crystalline form with a kind of and instance 1 identical mode.When some dry samples of CuPc particulate that present alpha crystalline form that generated being analyzed, demonstrate them and have mean particle size (Fig. 3) greater than 140 μ m with transmission electron microscope (TEM).
As shown in the TEM of Fig. 1-3 image; Use that method of the present invention (instance 1 with instance 2) generates α-CuPc particulate mean particle size (promptly; About 97nm) is markedly inferior to α-CuPc particulate mean particle size (that is, greater than 140 μ m) through sour paste method (comparison example 1) preparation of routine.Through the α-CuPc particulate size that reduces to remain to be mediated, the kneading time can reduce significantly, and the particulate dispersibility that generates can be improved.
Instance 4 (CuPc transforms from the crystalline phase of alpha crystalline form to the ε crystalline form)
In the kneader of a laboratory-scale, add 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 50g obtains from instance 1 or 2.With this mixture 130 ℃, mediate 2 hours (fs) and mediate 8 hours (subordinate phase) with same speed of rotation down at 80 ℃ then with the speed of rotation of 50rpm.After the kneading, the gained particle carries out purifying through filtration and 80 ℃ temperature and 10
4Carry out drying under the pressure of Pa.
Instance 5 (CuPc transforms from the crystalline phase of alpha crystalline form to the ε crystalline form in the presence of single sulfonation-CuPc)
Obtained appearing the CuPc particle of ε crystalline form from α-CuPc (obtaining) from instance 3 with a kind of and instance 4 identical modes.Yet, before kneading step, alpha crystalline form CuPc and ε type CuPc are being handled adding 6.2g MS-CuPc in 2 hours (replacing the fs) and the process at kneading step under 130 ℃ in Diethylene Glycol.
Instance 6 (CuPc transforms from the crystalline phase of alpha crystalline form to the ε crystalline form in the presence of single sulfonation-CuPc)
Obtained appearing the CuPc particle of ε crystalline form from α-CuPc (obtaining) from instance 1 with a kind of and instance 4 identical modes.Yet, before kneading step, alpha crystalline form CuPc and ε type CuPc are handled 2 hours (replacing the fs) and in kneading step, are added 6.2g MS-CuPc under 130 ℃ in Diethylene Glycol.
Instance 7 (CuPc transforms from the crystalline phase of alpha crystalline form to the ε crystalline form in the presence of single sulfonation-CuPc)
Except in kneading step, adding 6.2g MS-CuPc, obtained appearing the CuPc particle of ε crystalline form from α-CuPc (obtaining) with a kind of and instance 4 identical modes from instance 1.
Instance 8 (CuPc transforms from the crystalline phase of alpha crystalline form to the ε crystalline form in the presence of cetyltrimethyl ammonium list sulfo group CuPc (cetyltrimethyl ammonium monosulfo CuPc))
Except in kneading step, adding 6.2g cetyltrimethyl ammonium list sulfo group CuPc, obtained appearing the CuPc particle of ε crystalline form from α-CuPc (obtaining) with a kind of and instance 4 identical modes from instance 1.
Comparison example 2 (CuPc transforms from the crystalline phase of alpha crystalline form to the ε crystalline form when adding PIM-CuPc and MS-CuPc)
Except in kneading step, sequentially adding PIM-CuPc and the MS-CuPc, obtained appearing the CuPc particle of ε crystalline form from α-CuPc (obtaining) with a kind of and instance 4 identical modes from comparison example 1.
Particulate test in instance 9. colour filters
Use as pigment from having made colour filter according to the instance 4 to 8 and the ε shape CuPc granules of pigments of comparison example 2 preparations.The contrast ratio and the brightness of the colour filter that produces are summarised in the following table 1.These results demonstrate, and compare with the contrast ratio of comparison example 2, and instance 4 to 8 has produced about improvement of 4% to 21% on contrast ratio, as shown in the table 1.In addition; When (wherein sour paste step, adding PIM-CuPc and MS-CuPc from instance 5; And in kneading step, further add MS-CuPc) during the preparation colour filter; (wherein in sour paste step, only add PIM-CuPc with instance 6; And in kneading step, further add MS-CuPc) compare, they have produced better effect in contrast ratio and brightness.Compare with instance 8 (utilizing cetyltrimethyl ammonium list sulfo group CuPc), the colour filter of making from instance 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 |
| Instance 4 | 5850 | Do not measure |
| Instance 5 | 6815 | 18.44 |
| Instance 6 | 6625 | 18.27 |
| Instance 7 | 6815 | 18.20 |
| Instance 8 | 6673 | 18.19 |
*Arbitrary unit
Brief Description Of Drawings
Fig. 1 is the image from transmission electron microscope (TEM) of the CuPc particulate that presents the α crystalline phase for preparing for through the method according to instance 1.
Fig. 2 is the image from TEM of the CuPc particulate that presents the α crystalline phase for preparing for through the method according to instance 2.
Fig. 3 is the image from TEM of the CuPc particulate that presents the α crystalline phase for preparing for through the method according to comparison example 1.
Industrial application
Will be clear that as far as 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 accompanying claims and equivalent thereof.
Conflict with this disclosure if be combined in this any patent, patent application and the disclosure of announcing by reference, just make a unclear aspect of term, this disclosure should be preferential.
Claims (15)
1. one kind prepares CuPc (CuPc) the particulate method that presents alpha crystalline form, comprising:
(a) by at least a functional group will comprise the rough CuPc particle of particulate that 50wt% at least presents beta-crystalline form in the presence of the substituted CuPc particulate and mix with acid, make that the rough CuPc of part is dissolved in this acid at least; With
(b) making at least, the said dissolved CuPc of part precipitates in medium.
2. the method for claim 1, wherein said acid be selected from following at least a: sulfuric acid, chlorsulfonic acid and Tripyrophosphoric acid, preferred concentration are by weight greater than 90% sulfuric acid.
3. method as claimed in claim 1 or 2, wherein said medium are to be selected from least a in water, organic solvent or their mixture.
4. like each the described method in the claim 1 to 3, the mean number of the functional group of wherein every CuPc molecule is 0.5 to 2, and preferably approximately 1.
5. one kind prepares the CuPc particulate method that presents the ε crystalline form; Be included under the certain temperature condition and will mediate according to the CuPc particle that presents alpha crystalline form of each said method preparation in the claim 1 to 4; 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 differ at least 10 ℃ with said at least 0 at least two the relevant temperature of derivative of equaling, wherein the said particle more than or equal to 50wt% presents alpha crystalline form in the presence of liquid and at least a inorganic salt.
6. one kind prepares CuPc (CuPc) the particulate method that presents the ε crystalline form, comprises being greater than or equal to the heating steps that heats under 50 ℃ the temperature according to the alpha crystalline form of the said method preparation of in the claim 1 to 4 each.
7. like claim 5 or 6 described methods, wherein in said kneading or heating steps, further add said by the substituted CuPc particle of at least a functional group.
8. like each the described method in the claim 1 to 7, wherein said functional group be selected from following at least a :-SO
3M ,-SO
2NR
1R
2, and-R
3-NR
4R
5,
R wherein
1And R
2Separate and be hydrogen, alkyl, alkenyl, aryl or cycloalkyl; M is proton, ammonium cation or metallic cation; R
3Be singly-bound, alkylidene group or arylidene, wherein said alkylidene group and arylidene can be replaced by at least one substituting group; R
4And R
5Separate and be hydrogen, alkyl, alkenyl, aryl, cycloalkyl, or form the condensation structure jointly, this condensation structure comprises-CO-,-SO
2-and-at least a among the N=N-.
9. method as claimed in claim 8, wherein said functional group is-SO
3H ,-SO
2NHR
1Or
R wherein
1Be hydrogen, alkyl, alkenyl, aryl or cycloalkyl.
10. like claim 8 or 9 described methods, wherein said is at least two kinds of substituted CuPc particulate of difference mixtures by the substituted CuPc particle of functional group, is preferably by-SO
3The substituted CuPc particle of H with by
Substituted CuPc particulate mixture.
11. method as claimed in claim 7, wherein by
Substituted CuPc particle exists in step (a), and wherein by-SO
3The substituted CuPc particle of H is in the process of said kneading or heating steps, further to add.
The CuPc particle that 12. each the said method through in claim 1 to 4 and 8 to 10 is obtainable, present alpha crystalline form.
13. CuPc particle according to claim 12, wherein these particles have the mean particle size that is not more than 100nm.
14. be used to prepare the CuPc particulate purposes that presents the ε crystalline form like claim 12 or 13 described CuPc particles.
15. a colour filter comprises obtainable by each described method in claim 5 to 7 and 11, as to present ε crystalline form CuPc particle.
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 true CN102356130A (en) | 2012-02-15 |
| CN102356130B 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)
| 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)
| 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)
| 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 |
-
2010
- 2010-03-12 KR KR1020117024358A patent/KR20110134478A/en not_active Application Discontinuation
- 2010-03-12 WO PCT/EP2010/053184 patent/WO2010105982A2/en active Application Filing
- 2010-03-12 JP JP2012500196A patent/JP2012520914A/en active Pending
- 2010-03-12 CN CN201080012409.5A patent/CN102356130B/en not_active Expired - Fee Related
- 2010-03-15 TW TW99107451A patent/TWI466956B/en not_active IP Right Cessation
-
2015
- 2015-03-12 JP JP2015049301A patent/JP2015143368A/en active Pending
Patent Citations (6)
| 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 |
|---|---|
| JP2012520914A (en) | 2012-09-10 |
| JP2015143368A (en) | 2015-08-06 |
| CN102356130B (en) | 2014-01-08 |
| WO2010105982A3 (en) | 2010-12-09 |
| WO2010105982A2 (en) | 2010-09-23 |
| TWI466956B (en) | 2015-01-01 |
| TW201100497A (en) | 2011-01-01 |
| KR20110134478A (en) | 2011-12-14 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| 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 | |
| JPH0429707B2 (en) | ||
| JPS596261A (en) | Manufacture of high grade pigment from crude pigment | |
| 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 | |
| CN102356130B (en) | Process of preparing copper phthalocyanine particles exhibiting alpha crystallographic form | |
| CA1037471A (en) | PROCESS FOR PREPARING COPPER PHTHALOCYANINE PIGMENTS OF THE .alpha.-MODIFICATION | |
| CN101864198A (en) | Production process of novel phthalocyanine blue pigment | |
| CN101457027A (en) | High-grade glow blue pigment and preparation method thereof | |
| KR20100016078A (en) | Method of finishing organic pigments | |
| CN106084884A (en) | Pigment red 3 BL pigmentation processes technique | |
| JP2010535874A (en) | Preparation method of organic pigment | |
| EP0696620B1 (en) | Solid solutions of pyrrolo- 3,4-c -pyrroles with quinacridonequinones | |
| US2213693A (en) | Pigment preparation | |
| DE2252461C3 (en) | Process for the production of strongly colored 3,4,9,10-perylenetetracarboxylic acid dianhydride pigments | |
| US2930796A (en) | Conditioning of crude polychloro copper phthalocyanines | |
| CN103403101A (en) | Process of preparing product based on copper phthalocyanine (CuPc) particles | |
| JPH08231870A (en) | Preparation of organic pigment | |
| JPH04320458A (en) | Production of copper phthalocyanine pigment | |
| US3880890A (en) | Manufacture of 3,4,9,10-perylenetetracarboxylic acid dianhydride pigments having high tinctorial strength | |
| JP2005029633A (en) | Treated pigment and method for producing the same | |
| CN102264844B (en) | Efficient process for preparation of copper phthalocyanine particles exhibiting epsilon crystallographic form | |
| JPS61118460A (en) | Production of pigment composition | |
| GB2214190A (en) | Pigmentary salts of triphenylmethane compounds |
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 | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20140108 Termination date: 20170312 |