DE10152136B4 - Process for the preparation of preparations of organic pigments and pigment preparations obtainable thereafter - Google Patents

Abstract

Process for the preparation of preparations of organic pigments, in which impact or impact milling of the pigments is carried out with a natural or chemically modified resin, characterized in that
A) the impact or impact milling of the pigments is carried out with a printing ink resin in the form of a natural or chemically modified resin, and
B) transferring the premilled pigment into a free-flowing, pasty or solid concentrate suitable for the production of oil printing in a shear-force process with the addition of water, which serves for washing and / or temperature control, wherein the kneading mass in step B) is conditioned in the presence of water such that the added amount of water is so high that a process temperature of 115 ° C is not exceeded by evaporation of the water or its azeotropically boiling mixtures or the boiling point given by the boiling point increase of added salt solutions,
in addition to the ink resin added in step A), another 2 to 35% of a resin is added ...

Description

The The invention relates to a process for the preparation of preparations organic pigments which are impact or impact milled the pigments with a natural or chemically modified resin.

in principle fall insoluble Colorants, such as colored pigment preparations, from the chemical Synthesis with the following properties: Particle size 1 to 100 μm, wide or irregular Distribution of grain size fractions, needle-shaped Crystallites (growth along a preferential direction), deficient shaping a desired one Modification of the crystal structure (polymorphism), lack of expression of the Parameter transparency or opacity, as well as poor compatibility with the Application matrix. Furthermore, there are often unwanted impurities, such as For example, residues of educts before.

application point on the other hand, particle sizes in a range of 0.01 are required to 0.1 μm, relative close or even Particle size distribution, isometric crystallites or, if transparency is required, also platelet form, uniform or at least 80% preferred crystal structure, compatibility with the application matrix and setting a desired Content of foreign components.

The customary for this suitable transfer methods involve breaking and crushing the crystallites by impact, Friction and / or shear, phase transformations (modifying the Crystal structure to procedural boundary conditions in a newly adjusting energy minimum) and adaptation of the training capacity by setting suitable surface properties. These steps have to achieved with an economical minimum of processing steps which requires a technical integration of operations.

Known is the dry milling of the crude pigment to adjust the particle size and subsequent heat treatment of the material with suitable organic solvents and surface-active additives the usually present phase / modification mixture in the desired crystal modification to convict. Prefers be for This case uses high-boiling alkyl-substituted aromatics, the the crystallization in the β structure peculiar "herringbone pattern" of the molecules their poorer residual solubility in the surrounding medium and electronic and van der Waals interactions between additionally favor the various aromatic groups of the system ("phase-directing solvents", phase-stabilizing Medium). The warming elevated here the mobility the crystal bricks at the required rearrangements, so the setting of a thermodynamically favored phase within practicable Times can be completed.

The Integration of both steps gives, for example, the "salt grinding method", in which the pigment with a grinding aid, usually sodium or calcium chloride, in the presence of one or more organic solvents in an appropriate one Temperature in the desired Particle sizes distribution and crystal structure is transferred; However, this is only a small gain: this step can be taken in the Practice only a few resins and surfactants, so that still further steps after the removal of any grinding aids and extensive isolation of an intermediate product required are.

However, the methods mentioned are associated with high costs as well as energy and disposal problems for the solvents and / or grinding aids. Numerous proposals from the prior art have the described disadvantages:
Thus the revelation of the EP 407 831 a wet pre-grinding of the crude pigment, for example with phenoxyethanol in ball or attritor mills, then the entry in a mixture of water and high-boiling solvent, preferably ethylene glycol polyalkyl ether and suitable additives. The process relates to the isolation of a suitable for various applications, granule-like accumulating high-purity β-copper phthalocyanine as a marketable intermediate. In a further step, the pigment is incorporated together with suitable binders, oils, solvents and stabilizing additives in the final matrix with further grinding.

After GB 1 224 627 The entire amount of resin required, ie, a 1- to 8-fold amount of resin, is ground with crude polycyclic pigment, which can lead to sticking of the mill even with crosslinked and cured resins. The millbase is then dispersed in a suitable solvent. However, in the case of β-copper phthalocyanine, the shades tend to have greenish to reddish hues, which suggests partial reversion to the α-phase. The general practicability of the procedure must therefore be called into question. The amount range specified in the examples for the ratio "resin: pig ment "involves a greater use of resins than is currently practiced, since larger amounts of resin either smear the grinding apparatus or the highest Duroplast shares must be used.

The prior art according to the EP 392,334 reduces the amount of resin additive to 0.5 to 11% for milling. After entry into the oil pressure matrix, it must still be ground via a stirred ball mill. Although a high gloss is achieved, but the basic condition of a not too high proportion α-modification of a maximum of 60% before the grinding step on insufficient potential for phase transformation can be concluded. The main disadvantage is that the addition of resin between 0.5 and 11% is set too low by the chosen process parameters, which must be compensated by an increased Mahlaufwand in the very expensive to operate agitator ball mills and beyond too high a proportion of oversize grains and overall leads to grinding hardness of the pigment. Further, it is uneconomic to run multiple passes through agitated ball mills with a low pigment (15%) finished ink rather than producing a concentrate that makes much better use of the agitator ball mills by both the lesser amount and the higher concentration.

The US Pat. No. 5,776,237 shows for such a process with 1 to 200% phenol-modified rosin another practical disadvantage, namely that an inert atmosphere or a reduced partial pressure of oxygen over the material to be ground is required. The approaches according to these documents, in addition to the described damage to the resin matrix by oxidative decomposition, a significant hazard potential by Selbstentzündlichkeit the withdrawn intermediate product, as well as too high oxygen partial pressure in the mill itself. After grinding, the millbase is stirred into an oil-resin matrix and this preparation is postmilled on a three-roll mill. If, for example, a β-modification of the phthalocyanine in the end product is preferred, this restricts the choice of solvent to the high-boiling substances mentioned above, which may result in incompatibilities in the choice of the later printing ink solvent. The disadvantage of the process, in addition to the decomposition, is that working in an oxygen-free atmosphere leads both to greatly increased costs of the process and, moreover, to the risk of explosion or fire in the event that the inertization is due to technical defects Practice is easy and often the case may be - is not guaranteed to the full extent.

The revelation of US 5,942,028 teaches, preferably for phthalocyanine pigments, to limit the proportion of hard ink resins to dry premilling to 16 to 56%, but solves the problem of complete conversion to the β-modification by heat treatment with suitable solvents such as high boiling aromatics in a downstream separate one Step, whereupon in a third stage in a micromedia mill, the oily ink concentrate is created. The process can achieve marketable products only as a result of the complex three-stage treatment of grinding, cooking and grinding, which in addition to economic disadvantages in the phase purity of the pigments in purchasing.

The relevant patent literature mentions with the US 4,548,968 another method in which quinacridone or copper phthalocyanine crude pigments are premilled with 10 to 75% of a thermoplastic resin or copolymer and optionally 10% salt as a modular substep of another process objective dry below the softening point of the resins. In the present case, however, cumbersome series of wet milling steps at high and heat treatments at low pH are connected downstream of the dry grinding step. The use of commercial nails and grinding media made of steel inevitably leads to increased metal abrasion, which is apparently eliminated in the acidic postheat treatment. Screening and filtration follow before the resinous pigment can be incorporated into a plastic matrix. Although the Vormahlschritt is used apart from the other process objective, but the process remains problematic as a toner for polyethylene-like fumed incorporations in thermoplastics due to the aqueous aftertreatment. A phase purity of the pigments, as required for printing inks, can not afford the process because of the pure beating Nachmahl treatment.

Also the US 4,478,968 describes the aqueous-alkaline remilling in the presence of polar solvents. The post-treatment in the heat in the partially acidic medium at 85 ° C, however, is not suitable for phthalocyanine pigments to rebuild the β-phase, which is damaged in the subsequent impact treatment.

The lesson after the US 5,964,929 refers to a process in which a raw pigment premixed only with a maximum of 33%, preferably 4.5 to 13%, hard resin in a vibrating or ball mill dry or with the addition of 0.2 to 20% long-chain alkanols or carboxylic acids in a dry mass becomes. The latter serve as a fluidization aid in the grinding process and bind a portion of the remaining water from previous steps via polar or hydrophilic groups. This polar additive is not separated during the following kneading step and thus provides at levels above 1%, for example in an offset printing ink for undesirable solubility and phase-promoting properties between oleophilic and oleophobic areas. The milling step achieves a reduction of the particle size to at most about 5 .mu.m with about 60% α-modification, so that a kneading step is followed, with the addition of up to 50% binder, depending on the intended printing polar or nonpolar solvent and with surface modifying substances, for example sulfonated phthalocyanines or salts of long-chain carboxylic acids at a pigmentation level of 20 to 80%, preferably 40 to 60%. It is worked in addition to shear at temperatures between 20 and 200 ° C and predominantly obtained copper phthalocyanine the β-phase. The described technique is based on a twin-screw extruder. However, even 0.5 to 10% aliphatic alcohols having a chain length of more than 12 carbon atoms and / or carboxylic acids having more than 4 Kohlenstoffato men are extremely disadvantageous, at least for offset printing process, since they lead to an interfacial mixing and high water absorption. The preferred described cetyl alcohol has also been for quite some time a fairly high market price.

After EP 1 073 695 Rough copper phthalocyanine is wet or dry pre-ground with 1 to 15% resin and occasionally 2 to 15% salt or another grinding aid and then stirred with the addition of long-chain alcohols or aqueous emulsions present polar organic compounds or derivatives of carboxylic acids. This is carried out between 50 ° C and the boiling point of the solvent to achieve a quantitative transition of the remaining α-phase in the β-phase. The long-chain alcohols and other hydrophilic substances are, as mentioned above, also disadvantageous here. When salt is used in the pre-milling step, it is inevitable to prewash so as not to endanger the emulsion stability. The use of the method is therefore limited to special cases.

The US Pat. No. 6,031,030 precedes a milling or acid pasting step prior to the kneading step, which operates at 20 to 80% pigmentation level in a paint varnish or concentrate for its manufacture. The process has proven in our experience as not suitable for the production of printing ink concentrates, because for the claimed benefits, such as shortening the meal and saving on dispersion aids, lead to unusable products. Inks require, among other binder systems (such as in the EP 666 293 shown) a higher recipe fidelity and do not tolerate the usual deviations from the specification in the paint area. The resination of printing inks is lower than with paints, the fineness higher and in a narrower grain spectrum.

The EP 0 122 122 B1 relates to a process for producing a resinated pigment by converting a crude organic pigment into a highly aggregated low crystallinity pigment. Here, the crude organic pigment is dry pre-ground and the resulting product is then ground, wherein the pigment during the Trockenvermahlungs- and the subsequent grinding step, a water-insoluble thermoplastic resin in an amount of 10 to 75 wt .-%, based on the resinated pigment is incorporated , This process is to be further developed by carrying out the subsequent grinding step in the presence of water having a pH of 7 to 14 and a separate phase, this phase consisting of an organic liquid moistening the resin and the crystallinity of the pigment particles improved. The organic liquid can be dispensed with if the pigment is premilled in the presence of the thermoplastic resin. A resinated product of pigmentary quality is isolated. This known teaching requires mandatory after dry premilling another wet grinding.

Of the The above-described prior art shows that numerous process modifications are known to the complex process for the preparation of pigment preparations easier and cheaper too The goal is to reduce the cost of the overall process in a few cases is also achieved, but the quality is very high on a regular basis leaves something to be desired. at best will the quality the elaborate classic method achieved, but not surpassed. Thus, the technical teachings show a variety of disadvantages, so that it is an object of the invention, a method of the initially designated type available to provide that the disadvantages of the known methods avoids the costly handling of intermediates reduced or eliminated, overall is easier and less expensive and becomes a preparation with improved properties, the advantage in oil printing inks can be used.

This object is achieved by a method of the type described above in that A) the impact or impact milling of the pigments with an ink resin in the form of a natural or chemically-modified resin is performed and B) a transfer of the pre-milled pigment in a for the production of Oil-inks suitable free-flowing, pasty or solid concentrate in a shearing forces-carrying process with the addition of water, which serves the washing and / or the temperature control is performed, wherein the kneading material in step B) in the presence of water so conditioned is that the added amount of water is so high that a process temperature of 115 ° C is not exceeded by evaporation of the water or its azeotropic boiling mixtures or the boiling point by the boiling point increase of added salt solutions boiling temperature, in addition to that added in step A) 2 to 35% of a resin similar or compatible with that described in step A) is added to the printing ink resin, 5 to 35% of a mixture of oils is added to obtain the viscosity and the concentration of pigment in the kneading material is between 15 and 80 % is set.

Surprisingly it was found that by combining two process steps, i.e. a beating or butting of pigment and printing ink resin, followed by kneading with addition from water, similar a pigment "flushing", a 2-stage only and thus simplified process for the preparation of preparations organic pigments available which meets the above requirements. The invention relates Accordingly, a method for the preparation of preparations organic pigments by the combination of 2 process steps, optionally with the use of customary additives, in particular Printing ink lacquers, surface conditioning Aids, common Solvents, oils and / or Resins, comprising: A) impact or impact milling of the pigment with a natural one or chemically modified resin and B) transferring the milled pigment in a for the production of oil printing inks suitable free-flowing (i.e., free-flowing or flowable), pasty or solid concentrate in a shear stressing process below Addition of water, washing and / or temperature control serves.

The inventive method allows it, pigment preparations to provide a in use by about 10 to 20% higher color strength and have a purer, more brilliant color than previously in the state described the technique. This is done by the combination of grinding in step A) and then Kneading in the form of a kind of "Flushen" achieved in step B).

Of the inventive step A), an upstream grinding step with an ink resin, for example Hard resin, serves to preset the grain parameters, for example in a swing mill and the development of a defined, preconditioned mixed product.

The Organic pigments are not particularly within the scope of the invention limited. For example, you can polycyclic pigments, pigments from the group of phthalocyanine blue and / or green pigments, perinone, Quinacridone, indanthrone, anthanthrone, substituted anthraquinone, Dioxazine, anthrapyrimidine pigments, derivatives of a diketopyrrolopyrrole or flavanthrone pigments, azo pigments, preferably dirarylide pigments and Pigment Red 57 as well as mixtures and / or mixed phases thereof become. The pigment (s) can be used in finished form, but this is for achievement the objectives of the invention not necessarily required. The method is particularly effective in terms of by nature an elevated one Mahlaufwand, for example compared Azo pigments, requiring polycyclic pigments.

To the grinding according to the invention at step A) the usual suitable aggregates are used, in particular ball mills, vibrating mills or Attrition. The binder used is one or more printing ink resins, for the Examples include: thermoplastics, partially crosslinked resins partially thermosetting character, in particular rosins, esterified or substituted, preferably phenol-modified rosin resins, Alkyd resins, as well as by substitution or esterification with polyvalent Alcohol partially cross-linked derivatives and mixtures thereof.

hereupon the combined conditioning, fine grinding and adjustment takes place the crystal phase in step B) of the process according to the invention, being surprising was found that when adding and / or subsequent dosing of water in a kneader, the advantageous properties of the pigment preparations result. Here you can all commercial Kneading machines with sufficient shear force development, in particular Sigma kneader or twin-screw extruder and edge mill (edge running mills). However, it was found that For example, a batch kneader or pug mill with respect to a screw extruder offers advantages in the kneader step, for example, better control of the method possible is.

It is particularly advantageous if, in the kneader used, the kneading space or parts of the kneading space can be evacuated so that both air and volatile components can be withdrawn from the kneading mixture obtained in step B) by applying a suitable negative pressure. Conveniently, the kneading apparatus used has both in the fixed and in the movable part of double walls for the removal of process heat via suitable Thermostatisierflüssigkeiten to a correspond to ensure cooling.

According to the invention Pigment concentration in the kneading process to 15 to 80%, in particular 40 to 70%, discontinued.

In step B), the kneaded mass is conditioned in the presence of water such that the added amount of water is so high that a process temperature of about 115 ° C by evaporation of the water or its azeotropic boiling mixtures or the boiling point of saline solutions boiling point specified by boiling point is not exceeded. Therefore, it is preferable that water is added in an amount of 2 to 70% to the kneader during the kneading process in step A). The conditioning in the presence of water allows a novel targeted control and influence on the process and is as follows:
The presence of the water causes a sufficient process temperature of about 100 ° C (90 to 115 ° C) sets with sufficient evaporation from the aqueous phase at about 100 ° C and thus damage to the pigments, binders and additives by overheating in general is prevented. Furthermore, the presence of the water causes a leaching of the impurities still present in the pigment. These impurities are precipitated together with the water similar to the so-called "fluffing" in a kind of 'phase exchange', which corresponds approximately to the following procedure:

The thus achieved by the water cooling, optionally under additional External cooling, allows the main grinding in the kneading apparatus is temperature-controlled in the presence sufficient amounts, for example, high-boiling solvent and one for Inks in use Mixture or individual resins, preferably phenol or maleic acid or Alkylol-modified rosin and highly aromatic hydrocarbon resins, perform.

Preferably becomes by adding 10 to 70% water a temperature of about 100 ° C not exceeded. By additional indirect and / or internal cooling and adding water in the range of 10 to 50% is also possible, limit the process temperature to a range of 70 to 90 ° C. It is the skilled person readily possible, through some exploratory attempts to modify the amount of water in such a way that for the pigment preparation to be prepared suitable process temperature is obtained. To set a according to desired lower temperature can the water also short-chain aliphatic alcohols having a chain length of less than 4 carbon atoms are added.

By separating the water in a range of not less than about 60% of the total amount of water from the approach is therefore a Washing the pigment, this separation already above a Water content of about 30% can be carried out. The addition of water fulfilled in such cases a double benefit by temperature control with the wash preparation connected becomes.

In a further preferred embodiment of the invention, the mixture in step B) is a salt or salt mixture as a crushing aid added with other impurities while the further method by directly added water in situ solved and can be washed out.

Of course you can adding and separating water to remove contaminants performed several times be, depending on the desired Requirement profiles.

In a variant of the method according to the invention can step B) precede a washing process with water, from a filter cake with about 10 to 70%, especially about 30 to 55%, water content is obtained. This can be for further processing be advantageous in the kneading step B), as already a corresponding Water content of the preparation is present.

Conventional additives can be included in the process according to the invention. Examples include: common solvents, oils, resins, antioxidants, surfactants such as nonionic or ionic surfactants, and the like. Also, in the milling step A), in the kneading step B) or in both steps, one or more additives may be added to the pigment, which flocculation and Absetzhem serve. These may be acid amide-substituted derivatives of a polycyclic pigment or dye, in particular a phthalocyanine act.

however are intended to monohydric alcohols having a chain length of more than 3 carbon atoms in quantities above 0.5%, based on the overall approach, are not used. Further are aliphatic alcohols having at least 12 carbon atoms and aliphatic carboxylic acids with at least 4 carbon atoms in any of the steps of the invention be used, since this has proven to be extremely disadvantageous.

object The invention also includes pasty ones Pigment preparations, obtained by the above-described method for incorporation in oil pressure paint systems.

following should the inventive method will be described in more detail:

A) milling step:

One Pigment, such as a polycyclic pigment or azo pigment preferably with a residual moisture content of about 0.5%, in particular between 0.1 and 0.3%, ground with an ink resin in a suitable mill. The amount of the resin is preferred 8 to 35%, especially 15 to 18%. For this purpose, the grain size offers a lot reducing impactor, such as a vibratory mill, the a grain size from 0.5 to 3 μm diagonal length achieved and at 1 micron Häufigkeitsmaximiert is. However, lead also other mills, like attritor mills and ball mills to satisfactory results. The result is a so-called "raw meal".

The for the Grinding process relevant temperature is essentially determined by the Melting / softening temperature of the resin and the temperature sensitivity the pigment used, e.g. an azo pigment, and its desired Phase (for example, phthalocyanines or quinacridones) co-determined.

By an additional, optional subsequent water wash with a single or renewed addition of water at the appropriate temperature, for example at about 70 ° C, can possible By-products and decomposition products, which are registered with the pigment were already washed out here. This will be a filter press cake which produced like that without upstream water wash Raw meal from step A) further processed in the following kneading step B) becomes.

B) kneading step:

To The grinding can be a direct entry of the resulting raw meal or Filterpresskuchens done in the kneader. The dry powder from the pre-grinding ("raw meal") as well as the filter press cake a possible Intermediate washing can be done directly in a suitable manner via a mechanical feeding aid to the kneading apparatus, the rest or added Water by phase separation and / or evaporation with or without vacuum brings to the separation.

simultaneously with the task of the pigment or moistened pigment may be appropriate Additives, such as a finished printing ink coating, for example of resins, oils, solvents, Dispersing aids and stabilizers are fed to the kneader, either together with the pigment or separated into other application areas of the kneading apparatus, so that the mixing in both the kneader and also in the dosing under Wärmeein effect or heat development can be done. This used oil-based resin-solvent mixture can doing a wetting, as well as crystal phase correcting, as well as softening-promoting To exert effect, but should not solve purely Act.

If a solvent is used, it should be selected from a range of higher boiling alkanes or alkyl substituted aromatic solvents, as experience has shown to favor the formation of the β-crystal modification, for example, in non-halogenated phthalocyanine pigments. Analogous considerations apply to other polycyclic aromatic pigments with different crystalline realizations. However, it is generally the case that the boiling point of the solvent should be above 100 ° C. under atmospheric pressure (1028 mbar), preferably above 130 ° C., since otherwise there is a risk that individual components of the binders, oils and resins present in the mixture become completely or completely partially decompose or vaporize, thereby disturbing the balance of the recipe. In extreme cases, this can lead to the approach "eating away", increasing the risk of fire and inflammation, and, in the case of an azeotrope formation with residual or added water, its boiling range Compatibility with the later field of application, so that not only aromatics are used. In contrast to US 5,964,929 According to the available knowledge, alcohol with a chain length of more than 3 carbon atoms in an amount above about 0.5% must not be added.

Prefers is a resin from the group of partially crosslinked modified rosin resins or highly aromatic substituted hydrocarbon resins used. According to the invention is next the regrind or filter press cake, based on the resin, again 2 to 35, preferably 14 to 20% of a resin added to that above in the milling step described or compatible with this is. Further, the approach for obtaining the viscosity becomes an amount from about 5 to 35% of a mixture of oils, preferably high boiling Mineral and / or linseed oil, added to the desired pigmentation adjust. According to the invention is a Pigmentation range of 15 to 80%, especially 40 to 70% pigment, kept in the kneading approach.

The Kneading and introduction of the shear forces, for example, by Batch Kneader done. If additional cooling is required, such as at different heat-sensitive Azo pigments, it is recommended to use apparatus with a double jacket and / or to use hollow shafts to provide indirect cooling Temperature also locally below 100 ° C to be able to lower. But there are also suitable twin-screw extruder, although the inner cooling due to the need for venting and washing through a more complicated separation of the released wash water less elegant runs.

Of the Kneader practices theoretically on any base surface a crystallite of the pigment thrust through one over one Preferred direction along a surface axis constructed force gradient per surface element out. The high surface pressure favored in the system here at the fracture surfaces and the deficits resulting from shifting the lattice planes the crystal order the fortune the primary by intermolecular interaction between aromatic groups certain crystal structure, foreign molecules to accumulate and near the surface into the structure, so to speak. The process is furthermore useful, because he is at the same time a disorder of further or reincorporating crystal growth, so that once set pigment phase compared to others Processes finally in their further use as relative stable. The hydrophobic or carbophilic property of Pigments is particularly evident, so that the present Water also in liquid Mold by tilting the kneader container can be decanted.

The entire at the beginning, at certain time intervals, or continuously over one certain amount of water to be used in the kneader with should the total solvent balance be matched to the kneading process, also by azeotrope formation during evaporation before the phase separation, a suitable temperature range between 60 and 120 ° C to be able to adjust. Any residual moisture content of the kneading entry must be added by the Amount of water to be deducted. This step is advantageous, because while the phase separation in the kneading apparatus, a washing out of the pigment from soluble Impurities or decomposition products takes place. Elevated temperatures and pressures give better solubility of the added salt. The discharge of unevaporated water with the ones dissolved in it Residuals take place, for example, by tilting the kneading apparatus.

Prefers runs therefore the kneading process in the temperature range between 60 and 120 ° C, maximum about 140 ° C, in particular at 80 to 110 ° C from.

Of the Kneader is preferred after 0.5 to 10, especially 1 to 5, hours Working at the set temperature cooled. Cooling to normal conditions should be done within 3 to 5 minutes, taking the kneader should continue to operate. A sufficiently rated heat exchange capacity the cooling device installed on the kneader Therefore, it makes sense to observe the crystallites in spite of the additives to prevent renewed growth.

The obtained product according to the invention is particularly suitable for Printing inks or inks based on oils or other viscous hydrophobic media.

With the teaching of the invention There are thus many advantages: It becomes a simplified and - what is special important - extremely robust Preparation method of an oil-based ink system provided being ready to be mixed pigment preparations be won, the manufacturer the most extensive automation allow its manufacture. The complex procedures from the State of the art in which, for example, inert gas atmosphere as well additional Work-up steps are required can be avoided. One Conditioning step is relocated to a production level, with the additional Advantage of a higher application quality at the end processor.

Of the targeted use of water leads to allow adjustment of the appropriate temperature, causing damage the pigments, binders and additives is generally prevented by overheating. Furthermore, leaching occurs due to the presence of the water the impurities still present in the pigment. The water serves thus for internal cooling, which at the same time the desired Phase reversal of the pigment is achieved without a separate heat treatment step, as usual in the art, provided.

The Method of the invention leads also significantly reducing the costs of extraction of the pigments, taking care with a minimum of treatment steps can get along.

With the method according to the invention therefore become pigment preparations provided at least 10% higher color strength and a purer, more brilliant Hue than previously described in the prior art. The product obtained by the process of the invention can therefore in smaller quantities than conventional be dosed for the production of printing inks, as it related to the color strength on the pigmentation level increased by at least about 10%.

Examples:

All Figures in% are% by mass. In the examples, the material balance listed in tabular form. The initial weight is calculated with a relative accuracy of 2%. Out The choice of substances is not subject to a material restriction of Invention, rather, the bandwidth of the applications is shown become.

Example 1:

In Pre-milled presence of modified rosin in a vibratory mill Indanthrone blue pigment (C.I. PB 60) is combined with calcium chloride in one thermostatable 40-L kneader with mineral oil with the addition of diisobutyl phthalate, little isobutanol and linseed oil entered. Then add more resin and some polyvinyl alcohol a mean relative molecular mass of 800-1000, small amounts of an antioxidant and small amounts of a nonionic surfactant and a substituted phthalocyanine as a stabilizer.

To Kneading for 30 min is a temperature of 135 ° C over a period of 100 min held. Then, with continued kneading over 20 min so much water is gradually added to the kneading mixture, so that the temperature to constant about 102-105 ° C with evaporation a part of the water. In addition, the supernatant the aqueous Phase as brine and wash water on the tilt-drainage the kneader several times separated. When the conductivity of the liquid separated Water below 650 μS / cm sinks, is kneaded again with water at the above temperature, until a water- and salt-free, pasty hyrophobic mass of the aqueous Phase separates. After again tipping off the remaining liquid, and Removing the remaining water in vacuo, the pasty ink concentrate be isolated.

Printing ink: A portion of the resulting pigment paste is reduced to a degree of pigmentation of 12% a built on oil ink matrix, consisting of 29% rosin resin (Albertol KP 172, Vianova Resins), 16% alkyd resin (Terlon), 38% mineral oil, 13% linseed oil 1.5% zinc stearate 0.5% methylhydroquinone 1.5% cobalt octoate 0.5% polyethylene wax with the help of a dissolver at about 70 ° C for 2 hours at a peripheral speed of 5 m / sec incorporated. The same experiment is repeated with 1/50 of the resulting pigment preparation and replenished to the original preparation amount by a white paste ("S-Viscose-Weiss N1305TR", Gebr. Schmidt Druckf.) Based on titanium dioxide; hereby color intensity and color are judged.

hereupon The ink is in one go at about 50 ° C below 10 bar pressure on a three-roll chair vented and at the same time for safety's sake to a maximum grain of 0.2 microns set. The previous kneading parameters require only a single one Passage. A magnetic separator is not in our experience more needed, but can be turned on in the process. You get a strongly reddish blue, outstandingly flowing printing ink of high color strength, Transparency and gloss with very good stability of the dispersion.

Example 1a:

In Pre-milled presence of modified rosin ester in a vibratory mill Indanthrone blue pigment (C.I.PB 60) is used as a slightly water-moistened "raw meal" in a thermostattable 40-L kneader with mineral oil with the addition of diisobutyl phthalate as plasticizer, a little isobutanol and linseed oil entered. Then another carboxylic acid-modified rosin resin is added to, further, a polyvinyl alcohol of average molecular weight from 800-1000, small amounts of an antioxidant, a nonionic surfactant Stoffes and a little substituted phthalocyanine as a stabilizer.

To Kneading for 30 min is a temperature of 102 ° C over a period of 100 min held. Then, with continued kneading over 20 min so much water is gradually added to the kneading mixture, so that the temperature to constant about 100-105 ° C with evaporation a part of the water. In addition, the supernatant as wash water over the tilt-drainage the kneader is separated several times until the conductivity of the liquid separated Water below 650 μS / cm sinks. After again tipping off the remaining liquid, and removing the remaining water in vacuo, the pasty ink concentrate be isolated.

Printing ink: A portion of the resulting pigment paste is converted to a degree of pigmentation of 12% into an oil-based ink matrix consisting of 29% rosin resin (Albertol KP 172, Vianova Resins), 16% alkyd resin (Terlon), 38% mineral oil, 13% linseed oil 1.5% zinc stearate 0.5% methylhydroquinone 1.5% cobalt octoate 0.5% polyethylene wax with the help of a dissolver at about 70 ° C for 2 hours at a peripheral speed of 5 m / sec incorporated. The same experiment is repeated with 1/50 of the resulting pigment preparation and replenished to the original preparation amount by a white paste ("S-Viscose-Weiss N1305TR", Gebr. Schmidt Druckf.) Based on titanium dioxide; hereby color intensity and color are judged.

hereupon The ink is in one go at about 50 ° C below 10 bar pressure on a three-roll chair vented and at the same time for safety's sake to a maximum grain of 0.2 microns set. The previous kneading parameters require only a single one Passage. A magnetic separator is not in our experience more needed, but can be turned on in the process. You get a strong reddish, blue, well-flowing ink of the highest color intensity, transparency and gloss with excellent stability of the dispersion.

Example 2:

In the presence of carboxylic acid modif. Colophonium resin ball-milled crude copper phthalocyanine blue pigment is pasted as raw meal with water and placed in a coat thermostatable 40-L kneader with mineral oil with the addition of toluene, linseed oil and a nonionic surfactant. Then, after premixing the components again carboxylic acid modif. Rosin resin, polyethylene glycol having an average molecular weight of 800-1000 and adjuvants:

To 30 minutes kneading is heated to a temperature of 120 ° C within 10 minutes, whereupon the temperature over a duration of 80 min is kept. This is again antioxidant (e.g., methylhydroquinone) and added with continued kneading over the cooling jacket and addition of plenty of water to about 100 ° C cooled. The setting of the conditions takes place within 4-6 Minutes. As a result, the fine crystalline grain structure of the pigment additionally stabilized. After about 2 hours, during which it is deposited in about 15-minute intervals liquid Water decanted and the water demineralized by several additions Replaced and processed water, you put a vacuum on and Removes residual water and the more volatile components of the mentioned Additions; while cooling the approach decreases with reduced mixer input power and can subsequently isolated.

Printing ink: A portion of the resulting pigment paste is converted to a degree of pigmentation of 12% into an oil-based ink matrix consisting of 29% rosin resin (Albertol KP 172, Vianova Resins), 16% alkyd resin (Terlon), 38% mineral oil, 13% linseed oil 1.5% zinc stearate 0.5% methylhydroquinone 1.5% cobalt octoate 0.5% polyethylene wax with the help of a dissolver at about 70 ° C for 2 hours at a peripheral speed of 5 m / sec incorporated. The same experiment is carried out with 1/50 of the pigment preparation obtained and, alternatively, to the original preparation amount by means of a white paste ("S-Viscose-Weiss N1305TR", Gebr. Schmidt Druck) on Ti filled with tandioxidbasis; hereby color intensity and color are judged.

hereupon The ink is in one go at about 50 ° C below 10 bar pressure on a three-roll chair vented and at the same time for safety's sake to a maximum grain of 0.2 microns set. The previous kneading parameters require only a single one Passage. A magnetic separator is not in our experience more needed, but can be turned on in the process. You get a greenish-blue, good flowing printing ink highest Color strength, Transparency and gloss with excellent stability of the dispersion.

Example 2a:

Commercially available β-copper phthalocyanine blue pigment (CIPB 15: 3) conditioned in the presence of xylene and surfactants by conventional methods is modified in a vibratory mill with a carboxylic acid modif. Grind rosin resin. Otherwise, the procedure is as in Example 2: The raw meal is made into a paste with water and introduced into a jacket-thermostatable 40-L kneader with mineral oil with the addition of toluene, linseed oil and a nonionic surfactant. Then, after premixing the components again carboxylic acid modif. Rosin resin, polyethylene glycol having an average molecular weight of 800-1000 and adjuvants:

To 30 minutes kneading is heated to a temperature of 120 ° C within 10 minutes, whereupon the temperature over a duration of 80 min is kept. This is again antioxidant added and with continued kneading over the cooling jacket and addition abundant Water at about 100 ° C cooled. The The conditions are set within 4-6 minutes. As a result, the finely crystalline grain structure of the pigment is additionally stabilized. After about 2 hours while which is deposited in about 15-minute intervals liquid Water decanted and the water demineralized by several additions Replaced and processed water, you put a vacuum on and Removes residual water and the more volatile components of the mentioned Additions; while cooling the approach decreases with reduced mixer input power and can subsequently isolated.

Printing ink: A portion of the resulting pigment paste is converted to a degree of pigmentation of 12% into an oil-based ink matrix consisting of 29% rosin resin (Albertol KP 172, Vianova Resins), 16% alkyd resin (Terlon), 38% mineral oil, 13% linseed oil 1.5% zinc stearate 0.5% methylhydroquinone 1.5% cobalt octoate 0.5% polyethylene wax with the help of a dissolver at about 70 ° C for 2 hours at a peripheral speed of 5 m / sec incorporated. The same experiment is repeated with 1/50 of the pigment preparation obtained and, alternatively, replenished to the original preparation amount by a white paste ("S-Viscose-Weiss N1305TR", Gebr. Schmidt Druck) based on titanium dioxide, with which color strength and color are assessed.

Then the ink is deaerated in a single pass at about 50 ° C under 10 bar pressure on a three-roll mill and at the same time set to a maximum grain size of 0.2 microns for safety's sake. The previous kneading parameters require only a single pass. A magnetic separator is in our experience no longer necessary, but can be turned on in the process. This gives a greenish-blue, good-flowing ink of the highest color strength and gloss with excellent stability of the dispersion.

One Difference from Example 2 is not detectable, however, prove the pigments post-treated in Example (2a) (i.e., the starting material for example 2) not universal for Purpose of oil printing inks usable.

Example 3:

In Presence of 15% of a carboxylic acid-modified Rosin resin in a vibratory mill milled, α-copper phthalocyanine blue pigment (C.I.PB 15: 1, degree of chlorination about 1.5) are in a thermostatable 40-L kneader in mineral oil with the addition of linseed oil, Alkyd resin and the aforementioned Carboxylic acid modif. Rosin resin registered. Furthermore, stabilizers, antioxidant and a nonionic surfactant Added substance.

Within 30 minutes kneading is thermostated to a temperature of 120 ° C after which the Temperature over a duration of 80 min is kept. This is under continued tem Knead over a forced jacket cooling set at a temperature of 103-110 ° C, which by successively adding plenty of water to Knetansatz and its evaporation over 60 minutes supported becomes; not evaporated aqueous Phase is repeatedly decanted.

Printing ink: A portion of the resulting pigment paste is converted to a degree of pigmentation of 12% into an oil-based ink matrix consisting of 29% rosin resin (Albertol KP 172, Vianova Resins), 16% alkyd resin (Terlon), 38% mineral oil, 13% linseed oil 1.5% zinc stearate 0.5% methylhydroquinone 1.5% cobalt octoate 0.5% polyethylene wax with the help of a dissolver at about 70 ° C for 2 hours at a peripheral speed of 5 m / sec incorporated. The same experiment is repeated with 1/50 of the resulting pigment preparation and replenished to the original preparation amount by a white paste ("S-Viscose-Weiss N1305TR", Gebr. Schmidt Druckf.) Based on titanium dioxide; hereby color intensity and color are judged.

hereupon The ink is in one go at about 50 ° C below 10 bar pressure is vented on a three-roller chair and at the same time for safety's sake to a maximum grain of 0.2 microns set. The previous kneading parameters require only a single one Passage.

One Magnetic separator is no longer necessary in our experience, however, it can be turned on in the process. You get one reddish blue, good-flowing ink of highest color strength, transparency and gloss with excellent stability of the dispersion.

Example 4:

Purified dioxazine violet (CIPV 23) pre-ground with maleic acid resin in a ball mill is added as a "raw meal" to a thermostatable 40-L kneader together with mineral oil with addition of Cal cium chloride, plasticizers and linseed oil registered. Then, phenol-modified rosin resin is added, as well as polyvinyl alcohol having an average molecular weight of 800-1000, and a nonionic surfactant and an antioxidant.

To Kneading for 30 minutes is carried out at a temperature of 135 ° C within another 10 minutes after which this temperature was maintained for a period of 90 minutes becomes. This is followed by continued kneading over a forced cooling of Kneading jacket to approx. 100 ° C cooled. The setting of the conditions takes place within approx. 200 seconds, supported by adding plenty of water that partially evaporates, taking then kneaded for a further 2 hours, at least until the phase separation from the wss. Brine. Water addition and the phase separation of the hydrophobic Knetteig are repeated several times; the residual conductivity decanted water should be less than 700 μS / cm.

Printing ink: A portion of the resulting pigment paste is converted to a degree of pigmentation of 12% into an oil-based ink matrix consisting of 29% rosin resin (Albertol KP 172, Vianova Resins), 16% alkyd resin (Terlon), 38% mineral oil, 13% linseed oil 1.5% zinc stearate 0.5% methylhydroquinone 1.5% cobalt octoate 0.5% polyethylene wax with the help of a dissolver at about 70 ° C for 2 hours at a peripheral speed of 5 m / sec incorporated. The same experiment is repeated with 1/50 of the resulting pigment preparation and replenished to the original preparation amount by a white paste ("S-Viscose-Weiss N1305TR", Gebr. Schmidt Druckf.) Based on titanium dioxide; hereby color intensity and color are judged.

hereupon The ink is in one go at about 50 ° C below 10 bar pressure on a three-roll chair vented and at the same time for safety's sake to a maximum grain of 0.2 microns set. The previous kneading parameters require only a single one Passage. A magnetic separator is not in our experience more needed, but can be turned on in the process. You get a violet, well-flowing ink of the highest color intensity and Gloss with excellent stability of the dispersion.

Example 5

A carboxylic acid-modified rosin resin is pre-ground with 2,9-dimethylquinacridone red pigment (CI PR 122) and a little salt mixture to a "raw meal". This is mixed with twice the amount of water and filtered off from the brine. The press filter cake then contains 56% water. The cake is introduced in a 40-L kneader with mineral oil with the addition of sodium dodecyl sulfonate, alkyd resin and linseed oil. Then you give more modif. Rosin resin, stabilizer, polyvinyl alcohol having an average molecular weight of 800-1000 and a nonionic surfactant and an antioxidant.

To Kneading for 30 min, the reached temperature of 110 ° C over a Duration of another 65 min held. This will be continued under Knead over the jacket cooling to about 100 ° C cooled. Separating brine is decanted off and successively through replaced demineralized water, which partially evaporated and partially liquid again until a residual conductivity of 700 μS / cm decanted or last deducted by applying a vacuum becomes.

Printing ink: A portion of the resulting pigment paste is converted to a degree of pigmentation of 12% into an oil-based ink matrix consisting of 29% rosin resin (Albertol KP 172, Vianova Resins), 16% alkyd resin (Terlon), 38% mineral oil, 13% linseed oil 1.5% zinc stearate 0.5% methylhydroquinone 1.5% cobalt octoate 0.5% polyethylene wax with the help of a dissolver at about 70 ° C for 2 hours at a peripheral speed of 5 m / sec incorporated. The same experiment is repeated with 1/50 of the resulting pigment preparation and replenished to the original preparation amount by a white paste ("S-Viscose-Weiss N1305TR", Gebr. Schmidt Druckf.) Based on titanium dioxide; hereby color intensity and color are judged.

hereupon The ink is in one go at about 50 ° C below 10 bar pressure on a three-roll chair vented and at the same time for safety's sake to a maximum grain of 0.2 microns set. The previous kneading parameters require only a single one Passage. A magnetic separator is not in our experience more needed, but can be turned on in the process. You get a red, well-flowing ink of the highest color intensity and Gloss with excellent stability of the dispersion.

Example 6

In Presence of a carboxylic acid-modified Rosin resin vibrated azo-barbituric acid metal complex yellow pigment (C.I. PY 150) is stirred with water and thermostated in a jacket 40-L kneader with mineral oil added with the addition of a little dodecyl alcohol, plasticizer and linseed oil. Then you give more modif. Rosin to, further polyvinyl alcohol a mean relative molecular mass of 800-1000, toluene and a nonionic surfactants Material.

To For 30 minutes kneading, a temperature of 105-115 ° C. should be reached or set after which this temperature is exceeded a duration of 150 minutes and a toluene-water azeotrope evaporated. Toward the end, sufficient additional water is added and kneading continued with dehydration; the non-evaporating Water is decanted off. After 3 hours, the cooling is amplified and A vacuum is applied to the remaining water along with lighter volatile Solvent components subtract and through this forced evaporation on the approach about 85 ° C to cool. Through this fast cooling the receipt of the finely crystalline grain structure of the pigment is additionally favored.

Printing ink: A portion of the resulting pigment paste is converted to a degree of pigmentation of 12% into an oil-based ink matrix consisting of 29% rosin resin (Albertol KP 172, Vianova Resins), 16% alkyd resin (Terlon), 38% mineral oil, 13% linseed oil 1.5% zinc stearate 0.5% methylhydroquinone 1.5% cobalt octoate 0.5% polyethylene wax with the help of a dissolver at about 70 ° C for 2 hours at a peripheral speed of 5 m / sec incorporated. The same experiment is repeated with 1/50 of the resulting pigment preparation and replenished to the original preparation amount by a white paste ("S-Viscose-Weiss N1305TR", Gebr. Schmidt Druckf.) Based on titanium dioxide; hereby color intensity and color are judged.

hereupon The ink is in one go at about 50 ° C below 10 bar pressure on a three-roll chair vented and at the same time for safety's sake to a maximum grain of 0.2 microns set. The previous kneading parameters require only a single one Passage. A magnetic separator is not in our experience more needed, but can be turned on in the process. You get a yellowish green, good-flowing ink with a surprising for this type of pigment high color strength and shine with good stability the dispersion.

Example 6a:

Azo barbituric metal complex yellow pigment (C.I. PY 150) is in the presence of acid-modified. rosin and low salt mixture in a vibratory mill for 2 hours to a "raw meal" premilled. This is mixed with 14 L of water and filtered off from the brine. The press filter cake then contains about 45% water. The cake is set in a 40-L kneader with a mineral oil Addition of sodium dodecyl sulfonate and linseed oil registered. Then you give another carboxylic acid-modified rosin resin to, furthermore, polyvinyl alcohol of average molecular weight from 800-1000 and a nonionic surfactant Material.

To 30 min kneading, a temperature of 108-110 ° C to be reached, after which the Temperature over one Duration of 80 min is kept. Then water is added and kneading with dehydration at a temperature of about 102 ° C continued. After 3 hours, the cooling is reinforced and a vacuum applied to the remaining water along with lighter volatile Solvent components subtract and through this forced evaporation the approach quickly to about 80 ° C to cool. This will preserve the fine crystalline grain structure of the pigment additionally favored. The decanted water should last a conductivity of well below 700 μS / cm exhibit. The last "kneading-wash" should therefore with demineralized Water done.

Printing ink: A portion of the resulting pigment paste is converted to a degree of pigmentation of 12% into an oil-based ink matrix consisting of 29% rosin resin (Albertol KP 172, Vianova Resins), 16% alkyd resin (Terlon), 38% mineral oil, 13% linseed oil 1.5% zinc stearate 0.5% methylhydroquinone 1.5% cobalt octoate 0.5% polyethylene wax with the help of a dissolver at about 70 ° C for 2 hours at a peripheral speed of 5 m / sec incorporated. The same experiment is made up with 1/50 of the pigment preparation obtained and, alternatively, replenished to the original preparation amount by a white paste ("S-Viscose-Weiss N1305TR", Gebr. Schmidt Druckf.) Based on titanium dioxide; hereby color intensity and color are judged.

hereupon The ink is in one go at about 50 ° C below 10 bar pressure on a three-roll chair vented and at the same time for safety's sake to a maximum grain of 0.2 microns set. The previous kneading parameters require only a single one Passage. A magnetic separator is not in our experience more needed, but can be turned on in the process. You get a yellowish green, good-flowing ink with a surprising for this type of pigment high color strength and shine with good stability the dispersion.

Example 7:

perchlorinated Copper phthalocyanine green pigment (C.I. PG 7) is modified in the presence of a carboxylic acid. rosin in a swing mill pre-ground and the raw meal together with anhydrous calcium chloride in a thermostatable 40-L kneader together with further resin and Mineral oil registered. Further, a premix mineral oil with the addition of plasticizer, Alkyd resin, low polyvinyl alcohol of average molecular weight from 800-1000 and a nonionic surfactant Stoffes added to the kneader. After an hour becomes a mixture Substituted phthalocyanines added for surface conditioning.

To 30 minutes kneading, the temperature has been adjusted to about 125 ° C. Thereupon, water is added several times within 30 minutes and with continued kneading together with the internal evaporation of the water as well as over the forced jacket cooling set at a temperature of 103-108 ° C, which by addition of additional water over about 60 minutes to Knetansatz supports becomes. The unevaporated water is after phase separation on the usual Drainage channels of a Flush kneader pulled off by tilting (decanted). The process is repeated until a conductivity of 650 μS the decanted aqueous Phase is undershot. After a total of 4 hours of kneading will the product by means of vacuum of water and other volatile Components freed and then further cooled externally.

Printing ink: A portion of the resulting pigment paste is converted to a degree of pigmentation of 12% into an oil-based ink matrix consisting of 29% rosin resin (Albertol KP 172, Vianova Resins), 16% alkyd resin (Terlon), 38% mineral oil, 13% linseed oil 1.5% zinc stearate 0.5% methylhydroquinone 1.5% cobalt octoate 0.5% polyethylene wax with the help of a dissolver at about 70 ° C for 2 hours at a peripheral speed of 5 m / sec incorporated. The same experiment is repeated with 1/50 of the resulting pigment preparation and replenished to the original preparation amount by a white paste ("S-Viscose-Weiss N1305TR", Gebr. Schmidt Druckf.) Based on titanium dioxide; hereby color intensity and color are judged.

hereupon The ink is in one go at about 50 ° C below 10 bar pressure on a three-roll chair vented and at the same time for safety's sake to a maximum grain of 0.2 microns set. The previous kneading parameters require only a single one Passage. A magnetic separator is not in our experience more needed, but can be turned on in the process. You get a green, good flowing ink highest color strength and gloss with excellent stability of the dispersion.

Example 8:

raw Copper phthalocyanine blue pigment (C.I.PB 15) is dissolved in a jacketed, thermostatable 40 liter kneader with mineral oil with the addition of plasticizer, toluene, linseed oil and a nonionic surfactants Stoffes registered. Then you give after premixing of the components coarse-grained Sodium chloride, anhydrous calcium chloride and carboxylic acid modif. Rosin to, further polyethylene glycol of a medium relative Molecular mass of 600-800 and as a phase catalyst a mixture of low alkylated aromatics (Toluene, xylene).

To For 30 minutes kneading, the temperature is maintained at 125 ° C. for a period of 80 minutes. Then again antioxidant (e.g., methylhydroquinone) and Added mixture of substituted phthalocyanines as stabilizers and with continued kneading over the jacket cooling and cooled by repeated addition of water in 4 minutes to about 105 ° C. To about 2 hours while You can get there in about 15 minutes intervals liquid separated saline water by tilting the kneader decanted has and after 45 min again enough water for cooling and Has added phase separation, and wherein the discharged water last a conductivity of not more than 650 μS / cm you should put a vacuum on and remove any remaining water as well as the more volatile Components of said additives. It cools the approach decreases with reduced mixer input power and can subsequently isolated.

Printing ink: A portion of the resulting pigment paste is converted to a degree of pigmentation of 12% into an oil-based ink matrix consisting of 29% rosin resin (Albertol KP 172, Vianova Resins), 16% alkyd resin (Terlon), 38% mineral oil, 13% linseed oil 1.5% zinc stearate 0.5% methylhydroquinone 1.5% cobalt octoate 0.5% polyethylene wax with the help of a dissolver at about 70 ° C for 2 hours at a peripheral speed of 5 m / sec incorporated. The same experiment is repeated with 1/50 of the resulting pigment preparation and replenished to the original preparation amount by a white paste ("S-Viscose-Weiss N1305TR", Gebr. Schmidt Druckf.) Based on titanium dioxide; hereby color intensity and color are judged.

hereupon The ink is in one go at about 50 ° C below 10 bar pressure on a three-roll chair vented and at the same time for safety's sake to a maximum grain of 0.2 microns set. The previous kneading parameters require only a single one Passage. A magnetic separator is not in our experience more needed, but can be turned on in the process. You get a greenish-blue, sufficient flowable Printing ink with a color intensity appropriate to the starting pigment, gloss and for normal applications of sufficient stability of the dispersion.

Example 8a:

raw Copper phthalocyanine blue is suspended in a vibration mill with the addition of sodium chloride, anhydrous calcium chloride and carboxylic acid modif. rosin with minor additives of xylene as a phase stabilizer, antioxidant and stabilizer Pre-grind for 220 minutes. The raw meal is slurried in water, filtered and the filter cake washed with water. The low-salt filter cake has a solids content from 49% up.

This Filter cake is placed in a jacketed thermostatable 40 liter kneader with mineral oil with the addition of a little toluene as phase stabilizer, linseed oil, plasticizer and a nonionic surfactant entered. Then, after starting the kneader again antioxidant to, furthermore, some polyethylene glycol (PEG) of a middle relative Molecular mass of 600-800.

To The temperature is maintained at 105-108 ° C for a period of 80 minutes for 30 minutes kneading. This is followed by continuous kneading over the jacket cooling as well Add sufficient water at 15 minute intervals about 100 ° C cooled. After about 2 hours while one in 15 minutes intervals the separated from the hydrophobic Knetteig water by tilting the Kneters has decanted and after 90 min added again water has, and where the discharged water last a conductivity significantly less than 650 μS / cm has to put on vacuum and removes residual water and the lightest volatile Components of said additives. It cools the approach decreases with reduced mixer input power and can subsequently isolated.

Printing ink: A portion of the resulting pigment paste is converted to a degree of pigmentation of 12% into an oil-based ink matrix consisting of 29% rosin resin (Albertol KP 172, Vianova Resins), 16% alkyd resin (Terlon), 38% mineral oil, 13% linseed oil 1.5% zinc stearate 0.5% methylhydroquinone 1.5% cobalt octoate 0.5% polyethylene wax with the help of a dissolver at about 70 ° C for 2 hours at a peripheral speed of 5 m / sec incorporated. The same experiment is repeated with 1/50 of the resulting pigment preparation and replenished to the original preparation amount by a white paste ("S-Viscose-Weiss N1305TR", Gebr. Schmidt Druckf.) Based on titanium dioxide; hereby color intensity and color are judged.

hereupon The ink is in one go at about 50 ° C below 10 bar pressure is vented on a three-roller chair and at the same time for safety's sake to a maximum grain of 0.2 microns set. The previous kneading parameters require only a single one Passage. A magnetic separator is not in our experience more needed, but can be turned on in the process. You get a greenish, blue, well-flowing printing ink of high color strength, good Shine and good stability the dispersion.

Example 9:

In the presence of a carboxylic acid modif. Colophonium resin stirred ball-ground, chlorinated-brominated copper phthalocyanine green pigment (CI PG 36) are introduced into a thermostatable 40-L kneader in mineral oil. Furthermore, premixed mineral oil with the addition of sodium dodecylsulfonate, toluene and a nonionic surfactant linseed oil are added to the kneader:

To Kneading for 30 minutes, the temperature has been adjusted to about 120 to 130 ° C. Then plenty of water is added and continued Kneading together with the inner evaporation of the water and over the cooling of the kneader shell set to a temperature of 103-110 ° C, which by adding more water over about 60 minutes is supported for kneading. The not evaporated Water will be after the usual Phase separation of the hydrophobic Knetteig on the usual drainage options of a flush-kneader decanting by tilting. After a total of 6 Hours of kneading the product by means of vacuum of volatile Ingredients free and additional cooled before discharging.

Printing ink: A portion of the resulting pigment paste is converted to a degree of pigmentation of 12% into an oil-based ink matrix consisting of 29% rosin resin (Albertol KP 172, Vianova Resins), 16% alkyd resin (Terlon), 38% mineral oil, 13% linseed oil 1.5% zinc stearate 0.5% methylhydroquinone 1.5% cobalt octoate 0.5% polyethylene wax with the help of a dissolver at about 70 ° C for 2 hours at a peripheral speed of 5 m / sec incorporated. The same experiment is repeated with 1/50 of the resulting pigment preparation and replenished to the original preparation amount by a white paste ("S-Viscose-Weiss N1305TR", Gebr. Schmidt Druckf.) Based on titanium dioxide; hereby color intensity and color are judged.

hereupon The ink is in one go at about 50 ° C below 10 bar pressure on a three-roll chair vented and at the same time for safety's sake to a maximum grain of 0.2 microns set. The previous kneading parameters require only a single one Passage. A magnetic separator is not in our experience more needed, but can be turned on in the process. You get a slightly yellowish green, good-flowing ink of high color strength and gloss with good stability of the dispersion.

Example 10:

monochorinated Copper phthalocyanine (C.I. PB 15: 1) is mixed with a mixture of sodium and calcium chloride in a thermostatable 40-L kneader with mineral oil added with the addition of dodecyl alcohol, toluene and linseed oil. Then you give a phenol-modified Rosin to, furthermore little polyvinyl alcohol of a middle relative molecular mass of 800-1000, toluene, plasticizer, and a nonionic surfactant and an antioxidant.

To Kneading for 30 minutes is carried out at a temperature of 130 ° C within another 10 minutes adjusted, after which the temperature over a period of 180 min is held. This is followed by continued kneading over the Add sufficient water and cool the jacket to about 105-108 ° C. The Setting the conditions is done by successive additions of Water that evaporates on the one hand and on the other hand, a hydrothermal Washing the Salzknet approach makes, which is why the kneading process only ends when the decanted water has a conductivity below 650 μS / cm maintains. Thereafter, with the aid of a vacuum in the kneader room remaining Water and volatile Components deducted.

Printing ink: A portion of the resulting pigment paste is converted to a degree of pigmentation of 12% into an oil-based ink matrix consisting of 29% rosin resin (Albertol KP 172, Vianova Resins), 16% alkyd resin (Terlon), 38% mineral oil, 13% linseed oil 1.5% zinc stearate 0.5% methylhydroquinone 1.5% cobalt octoate 0.5% polyethylene wax with the help of a dissolver at about 70 ° C for 2 hours at a peripheral speed of 5 m / sec incorporated. The same experiment is repeated with 1/50 of the resulting pigment preparation and replenished to the original preparation amount by a white paste ("S-Viscose-Weiss N1305TR", Gebr. Schmidt Druckf.) Based on titanium dioxide; hereby color intensity and color are judged.

hereupon The ink is in one go at about 50 ° C below 10 bar pressure on a three-roll chair vented and at the same time for safety's sake to a maximum grain of 0.2 microns set. The previous kneading parameters require only a single one Passage.

One Magnetic separator is no longer necessary in our experience, however, it can be turned on in the process. A magnetic separator is not required in our experience, but can be for safety be turned on. You get a reddish blue, stable and well-flowable ink.

Example 10a:

raw Copper phthalocyanine is used in a thermostatable 40-kneader with mineral oil added with the addition of dodecyl alcohol, toluene and linseed oil. Then you give a modified rosin, further little polyvinyl alcohol an average molecular weight of 800-1000, toluene, plasticizer, and a nonionic surfactant and an antioxidant.

After kneading for 30 minutes, the temperature rises after evaporation of a large part of the water from 100-102 ° C to about 130 ° C, after which by means of the jacket thermostats this temperature is maintained over a period of 180 min. This is cooled with continued kneading on the additional addition of sufficient water and the jacket cooling to about 105-108 ° C. Setting the conditions is done here by further additions of demineralized water, which evaporates in small amounts and on the other hand makes a hydrothermal washing of the kneading approach of residues from the synthesis before the phase separation, which is why the kneading process is terminated only when the decanted water maintains a conductivity below 500 μS / cm , which according to experience after the fourth addition of demineralized water is the case. Thereafter, with the aid of a vacuum in the kneader room residual water and volatile components are removed.

Printing ink: A portion of the resulting pigment paste is converted to a degree of pigmentation of 12% into an oil-based ink matrix consisting of 29% rosin resin (Albertol KP 172, Vianova Resins), 16% alkyd resin (Terlon), 38% mineral oil, 13% linseed oil 1.5% zinc stearate 0.5% methylhydroquinone 1.5% cobalt octoate 0.5% polyethylene wax with the help of a dissolver at about 70 ° C for 2 hours at a peripheral speed of 5 m / sec incorporated. The same experiment is repeated with 1/50 of the resulting pigment preparation and replenished to the original preparation amount by a white paste ("S-Viscose-Weiss N1305TR", Gebr. Schmidt Druckf.) Based on titanium dioxide; hereby color intensity and color are judged.

hereupon The ink is in one go at about 50 ° C below 10 bar pressure on a three-roll chair vented and at the same time for safety's sake to a maximum grain of 0.2 microns set. The previous kneading parameters require only a single one Passage. A magnetic separator is not in our experience more needed, but can be turned on in the process. A magnetic separator is not required in our experience, however, it can be turned on for safety. You get one greenish blue, sufficiently flowable printing ink with a color strength appropriate to the starting pigment, and Shine and for the usual Applications sufficient stability of the dispersion.

Example 11:

Green, copper-free Mixing pigment preparations: One in the presence of a carboxylic acid-modified rosin resin and indanthrone blue pigment (C.I.PB 60) in a vibration mill for 1 hour premilled mixture of aminoanthraquinone yellow pigment (C.I.PY 123) and little anthrapyrimidine yellow pigment (C.I.PY 108) is in a thermostatable 40 L kneader together with calcium chloride (anhydrous) in mineral oil entered. Furthermore, with the addition of dodecyl alcohol and linseed oil, a nonionic surfactants Fabric with linseed oil next to further resin and subst. Phthalocyanines as stabilizer added to the kneader.

To 30 minutes kneading, the temperature has been set to about 125 ° C; cooling prevents the further increase in temperature that the yellow pigments damage can. Then enough water is added to the approach below continued kneading together with the internal evaporation of the water and about the jacket cooling to adjust to a temperature of 100-105 ° C, which by repeated addition of each water over about 60 minutes to Knetansatz supports becomes, whereby a watery Phase separates. The unevaporated aqueous phase is over the drainage of the Flush Kneader is repeatedly decanted by tilting. After total 6 hours of kneading, the product is vacuumed to the last Milling zones of volatile Ingredients free and additional cooled before discharging.

Printing ink: A portion of the resulting pigment paste is converted to a degree of pigmentation of 12% into an oil-based ink matrix consisting of 29% rosin resin (Albertol KP 172, Vianova Resins), 16% alkyd resin (Terlon), 38% mineral oil, 13% linseed oil 1.5% zinc stearate 0.5% methylhydroquinone 1.5% cobalt octoate 0.5% polyethylene wax with the help of a dissolver at about 70 ° C for 2 hours at a peripheral speed of 5 m / sec incorporated. The same experiment is repeated with 1/50 of the resulting pigment preparation and replenished to the original preparation amount by a white paste ("S-Viscose-Weiss N1305TR", Gebr. Schmidt Druckf.) Based on titanium dioxide; hereby color intensity and color are judged.

hereupon The ink is in one go at about 50 ° C below 10 bar pressure on a three-roll chair vented and at the same time for safety's sake to a maximum grain of 0.2 microns set. The previous method kneading parameters require only a single passage. A magnetic separator is ours Experience is no longer required, but can be turned on in the process become. You get a well-flowing green Printing ink highest color strength and gloss with excellent dispersibility.

Example 11a:

Green copper-free Mixing pigment preparations: One in the presence of a carboxylic acid-modified rosin resin and indanthrone blue pigment (C.I.PB 60) in a vibration mill for 1 hour premilled mixture of aminoanthraquinone yellow pigment (C.I.PY 123) and little anthrapyrimidine yellow pigment (C.I.PY 108) are in registered a thermostatable 40-L kneader in mineral oil. Furthermore, with the addition of dodecyl alcohol and linseed oil, a nonionic surfactants Fabric next to further resin and subst. Phthalocyanines as stabilizer added to the kneader.

To 30 minutes kneading, the temperature has been set to about 110 ° C; cooling prevents the further increase in temperature that the yellow pigments damage can. Then enough water is added and the approach below continued kneading together with the internal evaporation of the water and about the jacket cooling adjusted to a temperature of 100-105 ° C. The water should evaporate completely, z.T. under education appropriate Azeotropes. A temperature increase indicates that you need to add water again. After a total of 5 Hours of kneading, the product is vacuumed at the last grinding zones of volatile Ingredients free and additional cooled before discharging.

Printing ink: A portion of the resulting pigment paste is converted to a degree of pigmentation of 12% into an oil-based ink matrix consisting of 29% rosin resin (Albertol KP 172, Vianova Resins), 16% alkyd resin (Terlon), 38% mineral oil, 13% linseed oil 1.5% zinc stearate 0.5% methylhydroquinone 1.5% cobalt octoate 0.5% polyethylene wax with the help of a dissolver at about 70 ° C for 2 hours at a peripheral speed of 5 m / sec incorporated. The same experiment is repeated with 1/50 of the resulting pigment preparation and replenished to the original preparation amount by a white paste ("S-Viscose-Weiss N1305TR", Gebr. Schmidt Druckf.) Based on titanium dioxide; hereby color intensity and color are judged.

hereupon The ink is in one go at about 50 ° C below 10 bar pressure on a three-roll chair vented and at the same time for safety's sake to a maximum grain of 0.2 microns set. The previous method kneading parameters require only a single passage. A magnetic separator is ours Experience is no longer required, but can be turned on in the process become. You get a well-flowing green Printing ink of high color strength and gloss with excellent dispersibility and stability of the dispersion.

Example 12:

Yellow Mixing pigment preparations: In the presence of a pentaerythritol ester of carboxylic acid modif. Rosin resin as well as flavanthrone yellow pigment (C.I.PY 24) pre-ground Aminoanthraquinone yellow pigment (C.I.PY 123) and anthrapyrimidine yellow pigment (C.I.PY 108, as partially soluble or "non-solvent-resistant" yellow pigment for Crystal conditioning) are made into a thermostatable with calcium chloride 40-L kneader into one Matrix of mineral oil and linseed oil entered. Further, dodecyl alcohol, isobutanol and a nonionic surfactants Substance besides further carboxylic acid modif. Rosin resin, antioxidant and some alkyd resin added to the kneader.

To Kneading for 20 minutes, the temperature has been set to about 120 ° C. Then as much water is added and with continued kneading along with the internal evaporation of the water, the jacket cooling and if necessary, cooling the kneader shafts adjusted to a temperature of 105-110 ° C, which by multiple Add more water over about 60 minutes is supported for kneading. Not evaporating Water must separate from the hydrophobic kneading dough and is called saline solution decanted by tilting the Flush Kneader, before heating again added water. After a total of 2 hours of kneading, the Product by means of an applied vacuum of volatile Ingredients free and in addition cooled to discharge.

Printing ink: A portion of the resulting pigment paste is converted to a degree of pigmentation of 12% into an oil-based ink matrix consisting of 29% rosin resin (Albertol KP 172, Vianova Resins), 16% alkyd resin (Terlon), 38% mineral oil, 13% linseed oil 1.5% zinc stearate 0.5% methylhydroquinone 1.5% cobalt octoate 0.5% polyethylene wax with the help of a dissolver at about 70 ° C for 2 hours. The same experiment is repeated with 1/50 of the resulting pigment preparation and replenished to the original preparation amount by a white paste ("S-Viscose-Weiss N1305TR", Gebr. Schmidt Druckf.) Based on titanium dioxide; hereby color intensity and color are judged.

hereupon The ink is in one go at about 50 ° C below 10 bar pressure on a three-roll chair vented and at the same time for safety's sake to a maximum grain of 0.2 microns set. The previous kneading parameters require only a single one Passage. A magnetic separator is not in our experience more needed, but can be turned on in the process. You get a well-flowing yellow ink of the highest color intensity and Gloss with excellent dispersibility.

Claims (25)

Process for the preparation of preparations of organic pigments, in which the pigments are impacted or impact-milled with a natural or chemically modified resin, characterized in that A) the impact or impact milling of the pigments with a printing ink resin in the form of a natural or chemical -modified resin is carried out; and B) a transfer of the premilled pigment into a free-flowing, pasty or solid concentrate suitable for the production of oil inks is carried out in a shearing-force-adding process with addition of water serving for washing and / or temperature control, wherein the dough is conditioned in step B) in the presence of water so that the added amount of water is so high that a process temperature of 115 ° C by evaporation of the water or its azeotropic boiling mixtures or pre-added by the boiling point increase of salt solutions given boiling point is not exceeded, in addition to the ink resin added in step A), another 2 to 35% of a resin similar or compatible with that described in step A) is added to maintain the viscosity of 5 to 35% of a mixture of oils and the concentration Pigment in the play dough is adjusted between 15 and 80%. Method according to claim 1, characterized in that that step A) in ball mills, Vibrating mills or Attritors performed becomes. Method according to claim 1 or 2, characterized that step B) with kneading machines of sufficient shear force development carried out becomes. Method according to claim 3, characterized that kneading machines Sigmakneter or twin screw extruder be used. Method according to one of claims 1 to 4, characterized in step B), the kneading space or parts of the kneading space of the kneading machine be evacuated. Method according to at least one of the preceding Claims, characterized in that the kneader in step B) during the Kneading water is added in an amount of 2 to 70%. Method according to at least one of the preceding Claims, characterized in that the pigment concentration in step B) is set to 40 to 70%. Method according to at least one of the preceding Claims, characterized in that by additional indirect and / or inner cooling and adding water in the range of 10 to 50% of the process temperature to a range of 70 to 90 ° C is limited. Method according to at least one of the preceding Claims, characterized in that by the separation of the water from not less than about 60% of the total water from the batch a washing of the pigment takes place and this separation already above a total water content of about 30% is carried out. Method according to at least one of the preceding Claims, characterized in that adding and separating water is repeatedly performed to remove contaminants. Method according to at least one of the preceding claims 3 to 10, characterized in that the one used in step B) Kneading machine in both the fixed and the movable part double walls to Removal of process heat via suitable Thermostatisierflüssigkeiten having. Method according to at least one of the preceding Claims, characterized in that the step B) a washing process with Water is preceded, from which a filter cake with 10 to 70 % Water content is obtained. Method according to claim 12, characterized in that that the water content is set between 30 and 55%. Method according to at least one of the preceding Claims, characterized in that the organic pigment is selected phthalocyanine blue or green pigments, perinone, quinacridone, Indanthrone, anthanthrone, substituted anthraquinone, dioxazine, Anthrapyrimidine pigments, derivatives of a diketopyrrolopyrrole or flavanthrone pigments existing group and mixtures or mixed phases hereof. Method according to at least one of the preceding claims 1 to 13, characterized in that as organic pigments azo pigments in the form of diarylide pigments and Pigment Red 57, wherein by addition of 10 to 70% water, a temperature of about 100 ° C not exceeded becomes. Method according to at least one of the preceding Claims, characterized in that the organic pigment is a polycyclic Pigment is used in finished form. Method according to at least one of the preceding claims, characterized in that the Water for adjusting lower temperatures in step B), short chain aliphatic alcohols having a chain length of less than 4 carbon atoms are added. Method according to at least one of the preceding Claims, characterized in that in step A) as a resin thermoplastics or a partially crosslinked resin with partially thermosetting Character, in particular rosin resins, esterified or substituted, in particular phenol-modified rosin resins, alkyd resins, by Substitution or esterification with polyhydric alcohols partially crosslinked Derivatives and mixtures thereof are used. Method according to at least one of the preceding Claims, characterized in that the additives are selected from common solvents, oils, resins, Antioxidants and / or surface-active Means existing group. Method according to claim 19, characterized that the additives from the range of nonionic or ionic surfactants Fabrics selected become. Method according to at least one of the preceding Claims, characterized in that the pigment in step A), in step B) or an additive is added in both steps, the Flokkulations- and Absetzhemmung serves and / or an acid amide-substituted Derivative of a polycyclic pigment or dye, in particular a phthalocyanine, may be. Method according to at least one of the preceding Claims, characterized in that the kneading composition obtained in step B) by applying a suitable negative pressure both air and volatile components be withdrawn. Method according to at least one of the preceding Claims, characterized in that the mixture in step B) is a salt or salt mixture is added as a comminution aid, the with other impurities during the further method by directly added water in situ solved and washed out. Method according to at least one of the preceding Claims, characterized in that added to obtain the viscosity Mixture of oils contains high-boiling mineral and / or linseed oil. Pigment preparation, obtained according to the method according to at least one of the claims 1 to 24 for incorporation into oil pressure ink systems.