EP1720948A1 - Composition de phtalocyanine de cuivre du type beta et procede de conditionnement de cette composition - Google Patents

Composition de phtalocyanine de cuivre du type beta et procede de conditionnement de cette composition

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Publication number
EP1720948A1
EP1720948A1 EP05707798A EP05707798A EP1720948A1 EP 1720948 A1 EP1720948 A1 EP 1720948A1 EP 05707798 A EP05707798 A EP 05707798A EP 05707798 A EP05707798 A EP 05707798A EP 1720948 A1 EP1720948 A1 EP 1720948A1
Authority
EP
European Patent Office
Prior art keywords
weight
phthalocyanine
preferred
aromatic
unsubstituted
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.)
Withdrawn
Application number
EP05707798A
Other languages
German (de)
English (en)
Inventor
Thomas Healy
Ian Andrew Lambie
Laura Knight
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.)
BASF Schweiz AG
Original Assignee
Ciba Spezialitaetenchemie Holding AG
Ciba SC Holding AG
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 Ciba Spezialitaetenchemie Holding AG, Ciba SC Holding AG filed Critical Ciba Spezialitaetenchemie Holding AG
Priority to EP05707798A priority Critical patent/EP1720948A1/fr
Publication of EP1720948A1 publication Critical patent/EP1720948A1/fr
Withdrawn legal-status Critical Current

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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
    • C09B67/0014—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

Definitions

  • Beta copper phthalocyanine composition and conditioning process leading thereto Beta copper phthalocyanine composition and conditioning process leading thereto
  • the invention relates to a process for conditioning copper phthalocyanine so as to obtain pure ⁇ crystals in a columnar shape.
  • the instant process consists in heating finely ground crude copper phthalocyanine in a basic, aqueous alcohol, ketone or ester further comprising a small quantity of low polar, low volatile, low aromatic ink solvents.
  • the resulting highly concentrated pigment compositions are also an object of the invention, as well as their use for preparing coatings and inks.
  • US 2,857,400 discloses a process for the comminution of pigments by dry-milling under attrition and shear, followed by violent agitation slurried in an organic liquid. The pigment is then always isolated in dry powder form.
  • JP-A-11/60982 discloses a process for preparing printing inks by wet-milling crude copper phthalocyanine in a low-boiling aqueous solvent using beads of size from 0.2 to 0.5 mm.
  • the maximal concentration of copper phthalocyanine reaches only 40% by weight.
  • US 2,982,666 discloses the kneading of crude pigments in the presence of organic conditioning agents and large quantities of salt. Under controlled conditions, it is possible to obtain nearly isometric crystals with high tinctorial strength, gloss and flowability.
  • organic conditioning agents which are selected from glycols or derivatives thereof, have no solvent action whatsoever and do not act to convert ⁇ to ⁇ crystals of copper phthalocyanine.
  • EP0638615A2 further discloses that excellent fluidity, gloss and tinting strength are obtained by kneading in the presence of copper phthalocyanine ammonium sulfonates, which prevent crystal growth and re-aggregation during kneading.
  • EP0638615A2 does not enable the preparation of inks with a pigment concentration of more than 40% by weight.
  • EP 0699720 A1 discloses a process for preparing ⁇ -phase metal phthalocyanine pigments, wherein an acid treated crude metal phthalocyanine is dry-milled in the presence of a stabilizer, preferably aminoalkyl-sulfonamide substituted phthalocyanines, followed by finishing preferably in water-immiscible organic solvents such as esters of carboxylic acids, and final isolation of the ⁇ -phase metal pigment.
  • a stabilizer preferably aminoalkyl-sulfonamide substituted phthalocyanines
  • Ketones, lower alcohols, glycols and esters thereof are disclosed not to form the ⁇ -phase under such conditions.
  • JP-A-10/001 619 discloses a copper phthalocyanine composition for rotogravure inks comprising a mixture of ⁇ and ⁇ copper phthalocyanines obtained by dry-grinding, and a dialkylamino or aminoalkyl-sulfonamide substituted phthalocyanine which is added after grinding.
  • the fluidity and storage stability are disclosed to be improved, as compared with the products of the prior art treated with crystallisation solvents such as water, xylene, or aqueous alcohols.
  • EP 0422907 A2 discloses copper phthalocyanine pigment compositions comprising a mixture of ⁇ and ⁇ copper phthalocyanines obtained by dry-grinding crude copper phthalocyanine in the absence of a milling aid but in the presence of a very broad choice of phthalocyanine derivatives, amongst them bis-diethylaminomethyl copper phthalocyanine.
  • EP 0629668 A1 slightly modifies this method by milling with only one part of the additive and adding the remaining part after milling. The products are disclosed to have excellent fluidity, tinting strength and dispersion stability in coating and ink compositions.
  • copper phthalocyanine in the pure ⁇ phase is much preferable and most desirable for coloristic and stability reasons.
  • JP-A-60/133065 discloses the preparation of ⁇ copper phthalocyanine by wet-milling crude copper phthalocyanine together with a phthalocyanine derivative, an inorganic salt, a conditioning liquid and a phase-directing solvent, thus increasing the specific surface area.
  • the conditioning liquid is a polyalkylene glycol and the phase-directing solvent is acetone or xylene.
  • JP-A-07/310024 discloses a process for producing pure ⁇ copper phthalocyanine by dry grinding crude copper phthalocyanine so as to obtain a mixture of ⁇ and ⁇ phases, followed by treating with an organic solvent to obtain the ⁇ phase.
  • Suitable solvents include lower alcohols, ketones and esters as well as mineral spirits, amides and mixtures therof.
  • the preferred embodiment uses a ternary mixture of isopropyl alcohol, xylene and water in a ratio of about 10: 1 : 7.
  • Essential are the addition of copper phthalocyanine derivatives, amongst them dialkylamino copper phthalocyanines, in order to suppress crystal growth, as well as a final mechanical dispersion step.
  • EP0317876A2 discloses a process for producing an aqueous dispersion of pigmentary, isometric ⁇ copper phthalocyanine, by dry-milling crude copper phthalocyanine together with a small amount of a phase-directing solvent, adding the milled product to an emulsion comprising a second phase directing solvent, wet milling the emulsion and isolating the pigment as an aqueous presscake.
  • Suitable solvents are amongst many others aliphatic or aromatic hydrocarbons, aliphatic Ci-Cealcohols, C 3 -Ceketones and C 2 -C 4 diols or ethers thereof. Mineral spirits and ethylene glycol monobutyl ether are preferred. Only solvents immiscible or only partially miscible with water are suitable as the second phase-directing solvents.
  • EP 0407831 A1 discloses a similar process, but granulates the product in a two- phase water/ butoxyethanol system instead of the second wet-milling step.
  • EP 0803545 A2 discloses a process for producing ⁇ copper phthalocyanine by dry- milling at high temperature followed by treating in a liquid mixture of water and an organic solvent. Suitable are many solvents and mixtures thereof (without any specific example of a mixture), amongst them mineral spirit and alcohols. The colour strength, clearness, fluidity and hue are disclosed to be improved as compared with conventional wet-milling with salt, and the aspect ratio is lower than when milled at lower temperatures. However, high temperature milling requires an inert gas and is also problematic in many other aspects.
  • WO 99/54410 discloses a process for preparing ⁇ copper phthalocyanine by milling crude copper phthalocyanine together with a resin, isolating the milled mass and conditioning under various conditions, especially in azeotropic aqueous alcohols under basic conditions. Copper phthalocyanine derivatives may be added at any stage to improve the performance of the resulting pigments, for example dimethyl- aminomethyl copper phthalocyanine during the final processing stage.
  • this method gives excellent dispersibility, colour strength and gloss in inks, the acicular products are still not entirely satisfactory with respect to their rheology, as compared with isometric products obtained by salt kneading.
  • EP0819740A1 discloses a process for producing a printing ink comprising low aspect ratio ⁇ copper phthalocyanine by dry-milling crude copper phthalocyanine with 20-80% by weight of a resin and heating the mixture in a printing ink solvent.
  • the invention relates to a process for preparing a phthalocyanine pigment, comprising heating to a temperature of from 50 to 200°C a slurry comprising:
  • a phthalocyanine consisting of primary particles having an average particle size of maximally 0.5 ⁇ m, preferably an average particle size of from 0.01 to 0.3 ⁇ m;
  • the average particle size (length) is meant by weight distribution.
  • Methods for determining the particle size distribution of particles are well-known in the art, for example from the light transmission of a highly dilute sample, by static light scattering (300-1500 nm) or by quasielastic light scattering (10-3000 nm).
  • the relationship between the turbidity and particle radius of spheres is described by Mie's theory [M. Kerker The Scattering of Light and other Electromagnetic Radiation," in E. M. Loebl (ed.): Physical Chemistry, Academic Press, New York 1969)].
  • the preferred method is to use transmission electron microscopy.
  • the vast majority of the primary particles, such as > 95% by weight of the primary particles has preferably a particle size of from 0.01 to 0.05 ⁇ m. Standard pressure is 1.01325 - 10 5 Pa.
  • the phthalocyanine can be either unsubstituted or substituted by from 1 to 16 halogen atoms, especially chlorine and /or bromine, either metal-free or metallized, for example with copper, nickel or zinc.
  • halogen atoms especially chlorine and /or bromine
  • copper phthalocyanine especially unsubstituted copper phthalocyanine.
  • crude copper phthalocyanine may be prepared by reaction of phthalic anhydride with urea and a copper salt in the presence of a catalytic amount of a transition metal compound such as ammonium molybdate, the reaction being carried out at elevated temperature in a high boiling aromatic solvent such as nitrobenzene or in the absence of a solvent in a "dry-bake" melt process.
  • a transition metal compound such as ammonium molybdate
  • Crude copper phthalocyanine generally has particles of size above 1 ⁇ m, typically ranging from 5 to 100 ⁇ m. Hence, such coarse crude phthalocyanines need to be milled before they can be used in the instant conditioning process.
  • the milling technique is not particularly relevant, as long as it leads to a primary particle size within the instantly required range.
  • Conventional grinding, attrition, kneading and other wet- or dry-milling methods with or without grinding auxiliaries are generally suitable.
  • the preferred method is dry-milling, whereby it is understood that the phthalocyanine essentially retains the properties of a powder during milling. This is still the case when small quantities of liquids or low-melting materials are added, such as up to about 10% of liquids, based on the solid to be milled. It is most preferable to mill in the absence of any liquid.
  • the phthalocyanine consisting of primary particles having an average particle size of maximally 0.5 ⁇ m to have any particular crystal phase as starting material; on the contrary, any crystal phase can be used, such as mixtures of ⁇ and ⁇ crystal phases as usually obtained by dry-milling. It is preferable to use a phthalocyanine comprising at least 20% by weight of the ⁇ phase and at least 5% by weight of the ⁇ phase, most preferred from 45 to 65% by weight of the ⁇ phase.
  • the phthalocyanine pigment obtained by the instant process is preferably essentially (at least about 90% by weight thereof, most preferred at least about 95% by weight thereof) in the ⁇ crystal phase.
  • auxiliaries in the dry-milling step resins and /or water-soluble salts are most suitable. It is preferable to use at least one kind of milling auxiliary, most preferable to use both resins and water-soluble salts, especially when the dry-milling method is used.
  • Suitable equipment for dry-milling such as for example rotating or vibrating ball mills, may work batchwise or continuously.
  • Grinding auxiliaries are materials used to aid the reduction in size of crude phthalocyanine using kneading, attrition, wet- or dry-milling technology. Grinding auxiliaries suitable for use in this invention include, for example, calcium chloride, sodium chloride, sodium sulfate, sodium formate, sodium acetate or other organic or any inorganic salt with or without crystal water, in particular alkali and earth alkali salts.
  • the preferred grinding auxiliaries are sodium chloride, sodium formate and sodium acetate.
  • the grinding auxiliary is suitably used in an amount of up to 40% by weight, preferably from 1 to 30% by weight, most preferred from 5 to 20% by weight, based on the phthalocyanine weight.
  • the grinding auxiliaries dissolve in the conditioning mixture, so that it is not necessary to remove them before conditioning.
  • Higher amounts of grinding auxiliaries such as the 2- to 10-fold of the phthalocyanine weight usual in the salt-kneading method, can also be used if desired. Generally, however, they will be removed or their amount reduced to an acceptable lower level for the conditioning step by usual methods, for example by washing with water.
  • Neutral organic conditioning liquids are polar hydrophilic solvents capable of forming a binary azeotropic mixture with water, with a suitable melting point below 25°C.
  • Especially useful neutral organic conditioning liquids are at least partially miscible with water, with at least about 2 g of water soluble in 100 g of neutral organic conditioning liquid and preferably at least about 2 g of neutral organic conditioning liquid soluble in 100 g of water, each measured at 25°C.
  • neutral organic conditioning liquids which are water-miscible in any ratio.
  • the neutral organic conditioning liquid is generally used in an amount of from 4 to 500% by weight, based on the weight of the phthalocyanine, preferably from 10 to 200% by weight, in particular from 10 to 100% by weight, based on the weight of the phthalocyanine.
  • the neutral organic conditioning liquids are preferably selected from the group consisting of saturated and mono-unsaturated alcohols, ketones and esters having up to 8 C atoms, preferably from 2 to 6 C atoms, most preferred 3, 4, 5 or 6 C atoms.
  • the azeotrope contains preferably from 20 to 80% by weight of water in the gas phase.
  • Suitable examples of neutral conditioning liquids comprise saturated or mono- unsaturated alcohols, ketones and esters, such as ethanol, n-propanol, isopropanol, n-butanol, isobutanol, amyl alcohol, cyclohexanol or other isomers of linear, branched or cyclic d-C ⁇ alcohols, ethyl acetate, butyl acetate, or other d-C ⁇ alcanoic C ⁇ -C alkyl esters, acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone or other dialkyl or cycloalkyl ketone, 2-methoxy ethanol, 2-ethoxy ethanol or other C ⁇ -C 4 alkoxy C ⁇ -C 4 alkyl alcohols. • '->
  • Preferred neutral organic conditioning liquids are ethanol, n-propanol, isopropanol, n-butanol, isobutanol and n-pentanol.
  • Suitable weight ratios of neutral organic conditioning liquid to water in the conditioning aqueous slurry are from 50 : 50 to 1 : 99 by weight, preferably from 25 : 75 to 2 : 98 by weight, especially from 20 : 80 to 2 : 98% by weight, most preferred from 10 : 90 to 2 : 98% by weight.
  • the respective amounts of neutral organic conditioning liquid and water are preferably chosen so that no phase separation occurs even when the miscibility with water is only partial.
  • Suitable weight ratio of aqueous liquid (comprising water and organic conditioning liquid) to phthalocyanine is from 1 ⁇ : 1 to 20 : 1 by weight, preferably from 2 : 1 to 10 : 1 by weight, most preferred from 21 : 1 to 7 : 1 by weight.
  • hydrophilic, neutral organic conditioning liquids are instantly used in combination with high boiling point, non-aromatic hydrocarbons and an aqueous base.
  • Non-aromatic hydrocarbons can be single compounds or preferably mixtures lacking or with a low content of aromatics, especially ⁇ 5% by weight, preferably ⁇ 2% by weight, most preferred ⁇ 1 % by weight of aromatics.
  • Suitable non-aromatic hydrocarbons and oxygen-comprising derivatives thereof have at least 12 C atoms and a boiling point of from 150 to 350°C. Some of these are known as apolar high boiling ink solvents.
  • Particularly useful examples thereof are petroleum distillates and aliphatic alcohols having at least 12 C atoms, preferably dodecanol ortridecanol and isomeric or homologue mixtures comprising them.
  • diols and mono- or dialkyl ethers thereof also can be used.
  • Non-aromatic hydrocarbons or oxygen-comprising derivatives thereof are generally used in an amount of from 0.1 to 6% by weight, preferably from 0.2 to 4% by weight, most preferred from 0.5 to 2% by weight, based on the phthalocyanine.
  • the instant apolar high boiling ink solvents have a suitable low volatility, so that they do at least in part remain in the pigment dispersion and do not disappear from the slurry into the azeotropic, gazeous phase. If the apolar high boiling ink solvent forms a ternary azeotrope with the conditioning liquid and water and the conditioning step is run at reflux, then it is necessary to increase its minimal amount accordingly, while the amount remaining in the final product should stay below the instant upper limit.
  • non-aromatic, optionally substituted hydrocarbon is an essential point of the instant process; hence, it is critical it to be added sufficiently early before or during the conditioning process so that it can accomplish the desired effect. The best results are obtained when it is present throughout the solvent conditioning process. This is most easily obtained by adding the non-aromatic, optionally substituted hydrocarbon before the base, or eventually before the temperature reaches 50°C. Nevertheless, a minor but much weaker effect is still obtained by addition at a later stage, up to the azeotropic distillation of the neutral organic conditioning liquid.
  • the instant low amount of non-aromatic, optionally substituted hydrocarbon may also already be added before or upon pre-milling.
  • aromatic hydrocarbons which may if desired also be substituted.
  • aromatic hydrocarbons it is important that additional aromatic components do not signicantly alter the non-aromatic character of the mixture.
  • the optional aromatic hydrocarbons have suitably also at least 12 C atoms and a boiling point of from 150 to 350°C, preferably from 200 to 330°C, most preferred from 240 to 310°C.
  • Preferred aromatic hydrocarbons to be optionally added are such which are present in commercially available mixtures, which can therefore be used advantageously instead of non-aromatic hydrocarbons, provided their aromatic content is not higher than indicated above.
  • most suitable hydrocarbon mixtures should contain ⁇ 15% CA, preferably with >60% CP and from 0 to 40% CN, as determined by DIN 51378. More preferred, however, is not to add any additional aromatic hydrocarbons but to use essentially aromatic-free hydrocarbons containing ⁇ 3% CA (corresponding to about ⁇ 5% aromatic content), as determined by DIN 51378.
  • the aqueous medium is suitably adjusted to a pH value of > 9 by adding an adequate amount of a strong base to water.
  • Suitable bases are for example alkali, earth alkali or ammonium hydroxides, preferably sodium hydroxide or potassium hydroxide.
  • it is also suitable to add water and the adequate amount of base separately to the conditioning vessel.
  • the slurry to be conditioned may additionally further comprise any suitable amount of other components known for use in phthalocyanine compositions, such as in particular resins and /or phthalocyanine derivatives. It may also comprise water- soluble grinding auxiliaries, generally in partially or fully dissolved form.
  • Resins are suitably added in an amount of from 0.1 to 20% by weight, preferably from 1 to 15% by weight, most preferred from 2 to 5% by weight, based on the phthalocyanine.
  • Resins suitable for use in the process of the present invention are in particular rosin, the principal component of which is abietic acid; chemically modified rosins such as hydrogenated, dehydrogenated or disproportionated rosin; dimerised or polymerized rosin; partially esterified rosin; non-esterified rosin or partially esterified rosin; non-esterified or partially esterified maleic or phenolic modified rosin; nitrocellulose; polyamide; polystyrene or epoxy resin; thermoplastic resin and and mixtures thereof.
  • Illustrative rosins include such commercially available materials as StaybeliteTM resin (hydrogenated rosin), RecoldisTM A resin (disproportionated rosin) and DymerexTM resin (dimerised rosin).
  • Preferred resins for use in this invention are hydrogenated rosin and disproportionated rosin.
  • a phthalocyanine derivative may be added to the pigment slurry, filtercake or dry powder.
  • Suitable phthalocyanine derivatives used in this invention are in particular phthalocyanine derivatives having from 1 to 4 subsfrtuents comprising -N , -N- and /or -SO ⁇ - moieties in their molecule, for example dimethylaminomethyl phthalocyanine, phthalimido methyl phthalocyanine, aminomethyl phthalocyanine, sulfonated phthalocyanine, amine salts of sulfonated phthalocyanine and sulfonamides of phthalocyanine.
  • the phthalocyanine derivative's chromophore can optionally be further substituted by from 1 to 15 halogen atoms, especially chlorine and /or bromine, and can be either metal-free or metallized, for example with copper, nickel or zinc.
  • halogen atoms especially chlorine and /or bromine
  • Especially preferred derivatives are dialkylaminoalkyl copper phthalocyanine, phthalimidomethyl copper phthalocyanine and salts of sulphonated copper phthalocyanine, wherein the average number of such substituents per molecule of copper phthalocyanine is from 0.5 to 2.0.
  • Sulfonated phthalocyanines are preferably used in the form of their salts, especially their alkali or preferably ammonium salts, in particular their NH 4 ⁇ primary, secondary, tertiary or quaternary C ⁇ -C ⁇ 2 alkyl ammonium salts.
  • mono or bis di-C ⁇ -C4amino-C ⁇ -C 3 alkyl phthalocyanines in particular mono- and bis-dimethylaminomethyl and mono- and bis-diethylaminomethyl copper phthalocyanine.
  • the phthalocyanine derivatives are suitably used in amounts of from 0.1 to 20% by weight, preferably from 0.3 to 10% by weight, most preferred from 0.5 to 3% by weight, based on the phthalocyanine, and can be added as slurry, filtercake or dry powder at any stage of the process. However, they are preferably added only after heating to the conditioning temperature, most preferably upon or after azeotropic distillation of the neutral organic conditioning liquid, particularly just before isolation of the conditioned pigment composition.
  • resins and /or phthalocyanine derivatives provide some additional advantages to the final products.
  • Resins may be added at any stage, but adding a resin already for milling is preferable because it prevents reaggregation during milling and ensures a better homogeneity of the slurry then to be conditioned.
  • the phthalocyanine derivatives could in principle also be added already at the milling stage, it is much preferable to add them only during or after conditioning in order not to inhibit the desired particle growth.
  • the milled material is well wetted and dispersed into the solvent.
  • the resulting slurry is then heated to the desired conditioning temperature as disclosed hereafter.
  • the slurry is held in this temperature range for a sufficient time to allow conversion to the ⁇ crystal phase and achieve the required crystal ripening.
  • the neutral organic conditioning liquid is easily removed via azeotropic distillation with water.
  • the pigmentary ⁇ phthalocyanine is then isolated, for example via filtration or centrifugation before drying the resulting filtercake, or by spray-drying.
  • the heating temperature is adequately from 50 to 200°C, optionally under reduced or elevated pressure of about from 5 • 10 3 to 5 ⁇ 10 6 Pa.
  • the mixture is heated to a temperature from 60°C to 120°C, especially to a temperature range from 20°C below reflux temperature to reflux temperature, most preferred to reflux temperature.
  • the temperature may be kept constant during the whole conditioning step or follow any programmed scheme, such as continuously or stepwise heating and /or cooling.
  • the heating period depends on the desired result; from 10 minutes to 100 hours, preferably from 0.5 to 20 hours, are generally satisfactory for most purposes.
  • the process can be operated batchwise, or wholly or partially continuously (continuous operation is especially suitable for the heat conditioning step).
  • the conditioning step is suitably ended by decreasing the temperature of the mixture to 50°C or below, for example to from -20 to 40°C, preferably to from 0 to 30°C.
  • the phthalocyanine derivative may also advantageously be added at this stage. Active cooling by a heat exchanger may prove useful.
  • the pigmentary ⁇ phthalocyanine is then isolated and dried.
  • the amount of residual neutral organic conditioning liquid in the recovered aqueous conditioning liquid should in general be as low as economically achievable, depending on the capacity of the available sewage treatment plant. Part or all of the recovered neutral organic conditioning liquid may advantageously be recycled.
  • the ⁇ copper phthalocyanine product produced by the instant process has acicular or preferably rod-like crystals with an average particle length from 0.02 to 1 ⁇ m, preferably an average particle length of from 0.1 to 0.5 ⁇ m, and preferably with.an average aspect ratio of length to width of from 2 : 1 to 10 : 1 , most preferred from 3 : 1 to 7 : 1.
  • Figure 1 is a picture taken by transmission electron microscopy (TEM), showing a product as typically obtainable be the instant process.
  • compositions comprising:
  • the ingredients of the instant composition and all preferences are the same as above.
  • the instant composition can be used for any pigmenting purpose, preferably for coatings / paints and inks, most preferred for solvent based inks.
  • Printing inks comprise the pigment composition of the invention judiciously in a concentration of from 0.01 to 40% by weight, preferably from 1 to 25% by weight, with particular preference from 5 to 10% by weight, based on the overall weight of the printing ink. They may be used, for example, for gravure printing, flexographic printing, screen printing, offset printing, or continuous or dropwise inkjet printing on paper, board, metal, wood, leather, plastic or textiles, or else in special applications in accordance with formulations which are general knowledge, for example in publishing, packaging or freight, for marking purposes such as in logistics or in food, agro- chemical or pharmaceutical industry or on human or animal skin or medical equipment, in advertising, in security printing or else in the office sector for ballpoint, felt-tip or fibre-tip pens, inking pads, ink ribbons or inkjet printer cartridges.
  • Example 1 62.9 g crude copper phtalocyanine, 10.6 g sodium chloride and 1.8 g hydrogenated resin (StaybeliteTM resin) are dry-milled in a vibrating or rotating ballmill until the content of ⁇ phase reaches the range of from 45 to 65%.
  • 0.62 g of petroleum distillate having a boiling range 280-310°C (1% aromatics, ⁇ 1% CA, 25% CN, 74% CP) and 75.3 g dry-milled copper phtalocyanine obtained as described above are added to a mixture of 18.4 g n-butanol and 208 g of water.
  • 1.4 ml of 46% by weight caustic potash lye are further added before heating the mixture to reflux temperature (93°C) with agitation for a period of 4 hours.
  • 100 ml of cold water are added to the slurry, which is further cooled to about 30-35°C.
  • Example 2 It is proceeded according to example 1, with the difference that 1.24 g of the laurylamine salt of monosulphonated copper phthalocyanine are used instead of 0.62 g dimethylaminomethyl copper phthalocyanine.
  • Example 3 It is proceeded according to example 1 , with the difference that dimethylaminomethyl copper phthalocyanine is used in a double amount of 1.24 g.
  • Example 4 It is proceeded according to example 1, with the difference that 1.86 g phthalimidomethyl copper phthalocyanine are used instead of 0.62 g dimethylaminomethyl copper phthalocyanine.
  • Example 5 It is proceeded according to example 1, with the difference that 1.76 g copper phthalocyanine disulfonic acid and 0.72 g dimethylcocobenzyl ammonium chloride are finally added to the slurry instead of 0.62 g dimethylaminomethyl copper phthalocyanine.
  • Example 6 It is proceeded according to example 1 , with the difference that 1.23 g of the dimethylditallow ammonium salt of sulfonated copper phthalocyanine are used instead of 0.62 g dimethylaminomethyl copper phthalocyanine.
  • Example 7 It is proceeded accordihg to example 1 , with the difference that 0.62 g of dodecanol is used instead of 0.62 g of petroleum distillate.
  • Example 8 It is proceeded according to example 1 , with the difference that 1.8 g of fumarated resin (PinerezTM resin) is used instead of 1.8 g of hydrogenated resin (StaybeliteTM resin).
  • Example 9 It is proceeded according to example 1 , with the difference that 1.8 g of dimerised resin (Poly paleTM resin) is used instead of 1.8 g of hydrogenated resin (StaybeliteTM resin).
  • Example 10 It is proceeded according to example 1, with the difference that a double amount (1.24 g) of petroleum distillate is used and 0.62 g of dodecylamine salt of monosulphonated copper phthalocyanine is used instead of 0.62 g of dimethylaminomethyl copper phthalocyanine.
  • Example 11 75.3 g crude copper phthalocyanine dry-milled according to example 1 are added with agitation to a mixture of 106.7 g 81 % aqueous n-butanol (recycled upper layer of azeotrope), 110 g water and 0.62 g of petroleum distillate having a boiling range 280-310°C (1% aromatics, ⁇ 1% CA, 25% CN, 74% CP).
  • Example 12 It is proceeded according to example 1 , with the difference that the 0.62 g of dimethylaminomethyl copper phthalocyanine is added after 2 hours at reflux. After a further 2 hours conditioning is complete, 100 ml of cold water are added to the slurry, which is further cooled to about 30-35°C. The slurry is then acidified with hydrochloric acid, filtered, washed salt and solvent free, and dried at 75°C.
  • Examples 13-16 It is proceeded according to example 1 , with the difference that 0.62 g of dodecylamine salt of monosulphonated copper phthalocyanine is used instead of 0.62 g of dimethylaminomethyl copper phthalocyanine, and the following amounts of solvents are used:
  • the neutral organic conditioning liquid is distilled azeotropically before cooling down.
  • the neutral organic conditioning liquid is diluted before cooling down. 0.62 g of dodecylamine salt of monosulphonated copper phthalocyanine is then added and the slurry is stirred for a short period of time, then acidified with hydrochloric acid, filtered, washed salt and solvent free, and dried at 75°C.
  • Example 17 It is proceeded according to example 1 , with the difference that 0.62 g of petroleum distillate having a boiling range 240-270°C (20% aromatics, 12% CA, 22% CN, 66% CP) is used instead of 0.62 g of aromatic free petroleum distillate.
  • Example 18 (comparative): 75.3 g crude copper phthalocyanine dry-milled according to example 1 are added with agitation to a mixture of 18.4 g n-butanol and 208 g water. 1.4 ml of 46% potassium hydroxide solution are added and the slurry heated to reflux temperature of 93°C for a period of 4 hours. 100 ml cold water are added in order to cool the slurry, which is then acidified using hydrochloric acid, filtered, washed salt and solvent free, and dried at 75°C.
  • Example 19 It is proceeded according to exampje 5, with the difference that no petroleum distillate is used.
  • Example 20 (evaluation in a typical oil ink application) 20 g of pigment composition obtained according to examples 1-19 are each premixed with 80 g of a heatset oil ink varnish containing a blend of modified phenolic resin, alkyd resin, petroleum distillate and from 0-5% of auxiliaries. 100 g of the premix are dispersed on a B ⁇ hler SDY- 200TM three roll mill at 23°C for 5 minutes. The ink base is then given two dispersion passes on the mill at 10 6 Pa (10 bar). The ink properties are assessed by reducing the 2 nd pass from 20% to 14% pigmentation with the above varnish. The final ink is then printed using a Prufbau printing machine to give prints of differing film weights.
  • the print density for each print is measured using a densitometer (Gretag D19C).
  • the gloss is measured at equal film weight using an Erichsen mini glossmaster at 60°.
  • the millbase viscosity is measured on the millbase ink using a Laray falling bar viscosi- meter.
  • the low shear flow is measured on the final ink and defined as the distance travelled by the ink down an inclined plate at 60°. The results are as follows (standard 100% set for comparative example 18):
  • the pigment compositions of examples 1 to 17 all have a much better millbase viscosity, as compared with the pigment compositions of comparative examples 18 and 19.
  • the pigment compositions of examples 1 to 17 also have a much better low shear flow, as compared with the pigment compositions of comparative example 18.
  • the pigment compositions of examples 1 to 4 and 6 to 17 also have a better gloss than both pigment compositions of comparative examples 18 and 19.
  • the pigment composition of example 5 has a better gloss than the pigment composition of comparative example 19.
  • Examples 21 -38 It is proceeded according to examples 1 - 17, with the difference that only 0.15 g of petroleum distillate are each time used.
  • Examples 39-56 It is proceeded according to examples 1 - 17, with the difference that petroleum distillate is each time used in an increased amount of 2.0 g.
  • Examples 57-109 It is proceeded according to examples 1 - 17 and 21 -56, with the difference that the petroleum distillate is mixed with the alcohol before adding the dry-milled crude and water.
  • Examples 110- 136 It is proceeded according to examples 1 - 17, with the difference that the phthalocyanine derivatives are added after 2% hours at reflux.
  • Examples 137- 153 It is proceeded according to examples 1 - 17, with the difference that the resin is only added after 214 hours at reflux.
  • Examples 154-303 It is proceeded according to examples 1 - 17 and 21 - 153, with the difference that no resin is used.
  • Examples 304 -453 It is proceeded according to examples 1 - 17 and 21 - 153, with the difference that crude copper phthalocyanine is wet-milled in a pearl-mill with the resin and water, filtered then used as a wet presscake for the instant conditioning step.
  • Examples 454 - 1011 It is proceeded according to examples 1 - 17 and 21 -453, with the difference that the following amounts of following solvents are used:
  • Examples 3154-5303 It is proceeded according to examples 1 - 17, 21 -903 and 1804-3153, with the difference that the conditioning temperature is set to 80°C for a period of 10 hours and the neutral organic conditioning liquid is distilled azeotropically by reducing the pressure adequately.
  • Examples 5304-6203 It is proceeded according to examples 904- 1803, with the difference that the conditioning temperature is set to 100°C for a period of 1 hour under 4 • 10 5 Pa nitrogen pressure, and the neutral organic conditioning liquid is distilled azeotropically after cooling down to about the boiling point of the azeotrope and then releasing the pressure.
  • Examples 6204- 12403 It is proceeded according to examples 1 - 17 and 21 -6203, with the difference that a mixture of Ci2-C ⁇ 6 alcohols is used instead of the petroleum distillate or pure dodecanol.
  • Examples 12404-24603 It is proceeded according to examples 1 - 17 and 21 - 12203, with the difference that 5.0 g of sodium formate are used as a grinding auxiliary instead of 10.6 g of sodium chloride.
  • Examples 24604-85603 It is proceeded according to examples 12204-24403, with the differences that crude copper phthalocyanine is replaced by crude Colour Index Pigment Blue 15:1, Pigment Blue 16, Pigment Green 7, Pigment Green 36 or zinc phthalocyanine, respectively, which instead of dry-milling are each wet-milled in a pearl mill with an aqueous medium and zirconium oxide balls of 0.3-0.4 mm diameter but without other grinding auxiliary and are used as wet filtercake, the quantity of added water ist adjusted according to the moisture in the filtercake, and the corresponding amount of finely divided resin is added at about 20-40°C just before starting to heat for conditioning.
  • crude Copper phthalocyanine is replaced by crude Colour Index Pigment Blue 15:1, Pigment Blue 16, Pigment Green 7, Pigment Green 36 or zinc phthalocyanine, respectively, which instead of dry-milling are each wet-milled in a pearl mill with an aqueous medium and zirconium oxide balls of 0.3-0.4 mm diameter but without other grinding

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Chemistry (AREA)
  • Inks, Pencil-Leads, Or Crayons (AREA)

Abstract

La présente invention concerne un procédé pour préparer un pigment de phtalocyanine, qui consiste à chauffer à une température comprise entre 50 et 200 °C une suspension comprenant une phtalocyanine constituée de particules primaires présentant une taille particulaire moyenne d'au maximum 0,5 νm, de préférence une taille particulaire moyenne allant de 0,01 à 0,3 νm; de 4 à 500 % en poids, sur la base du poids de la phtalocyanine, d'un liquide de conditionnement organique neutre capable de former avec de l'eau un mélange azéotrope qui présente un point d'ébullition inférieur à celui de l'eau et comprend de 4 à 96 % en poids d'eau dans la phase gazeuse à pression standard; de 0,1 à 5 % en poids, sur la base du poids de la phtalocyanine, d'un ou de plusieurs des composés choisis dans le groupe formé par des hydrocarbures non aromatiques non substitués ou substitués par 1 ou 2 groupes hydroxy et/ou éther, ces composés présentant au moins 12 atomes de C et un point d'ébullition allant de 150 à 350 °C, de préférence de 200 à 330 °C, au mieux de 240 à 310 °C; éventuellement jusqu'à 30 % en poids, sur la base du poids des hydrocarbures non aromatiques non substitués ou substitués, d'un ou plusieurs hydrocarbures aromatiques non substitués et/ou éventuellement substitués qui présentent au moins 12 atomes de C et un point d'ébullition allant de 150 à 350 °C, de préférence de 200 à 330 °C, au mieux de 240 à 310 °C; ainsi que de 1 à 50 parties en poids, par partie en poids de liquide de conditionnement organique neutre, d'une solution aqueuse basique présentant un pH = 9, de préférence un pH situé entre 10 et 13. La présente invention concerne également les compositions résultantes, contenant de préférence aussi des quantités minoritaires d'une résine et/ou d'un dérivé de phtalocyanine. Ces compositions permettent d'obtenir une excellente aptitude à l'écoulement, notamment à faible cisaillement dans des encres à l'huile.
EP05707798A 2004-01-29 2005-01-19 Composition de phtalocyanine de cuivre du type beta et procede de conditionnement de cette composition Withdrawn EP1720948A1 (fr)

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PCT/EP2005/050195 WO2005075577A1 (fr) 2004-01-29 2005-01-19 Composition de phtalocyanine de cuivre beta et procede de conditionnement pour la produire
EP05707798A EP1720948A1 (fr) 2004-01-29 2005-01-19 Composition de phtalocyanine de cuivre du type beta et procede de conditionnement de cette composition

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WO2006048388A2 (fr) 2004-11-01 2006-05-11 Ciba Specialty Chemicals Holding Inc. Composition de pigments fluide extremement concentree et son procede de fabrication
JP5664834B1 (ja) * 2013-07-31 2015-02-04 Dic株式会社 フタロシアニン顔料組成物の製造方法

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US2857400A (en) * 1955-09-19 1958-10-21 Du Pont Pigment production
US4853039A (en) * 1987-11-23 1989-08-01 Basf Corporation Process for making a phthalocyanine pigment dispersion
DE3922734A1 (de) * 1989-07-11 1991-01-24 Basf Ag Verfahren zur herstellung von farbstarken, transparenten und leicht dispergierbaren kupferphthalocyaninpigmenten der ss-modifikation
JPH06336556A (ja) * 1993-05-28 1994-12-06 Toyo Ink Mfg Co Ltd ポリハロゲン化銅フタロシアニン顔料の製造方法
JPH0753889A (ja) * 1993-08-10 1995-02-28 Toyo Ink Mfg Co Ltd 銅フタロシアニン顔料の製造方法および該製造方法より得られる銅フタロシアニン顔料を含む印刷インキもしくは塗料組成物
JP3477810B2 (ja) * 1994-05-16 2003-12-10 大日本インキ化学工業株式会社 β型銅フタロシアニン顔料の製造法
US5534055A (en) * 1994-08-24 1996-07-09 Bayer Corporation Process for alpha-phase metal phthalocyanine pigments
JP3139396B2 (ja) * 1996-02-05 2001-02-26 東洋インキ製造株式会社 印刷インキの製造方法
JPH09291223A (ja) * 1996-04-26 1997-11-11 Toyo Ink Mfg Co Ltd β型銅フタロシアニン顔料の製造方法
JPH1160982A (ja) * 1997-08-28 1999-03-05 Dainippon Ink & Chem Inc β型銅フタロシアニン顔料の製造方法
GB9808169D0 (en) * 1998-04-20 1998-06-17 Ciba Sc Holding Ag Production process

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