CA1116810A - Pigment compositions - Google Patents
Pigment compositionsInfo
- Publication number
- CA1116810A CA1116810A CA000299118A CA299118A CA1116810A CA 1116810 A CA1116810 A CA 1116810A CA 000299118 A CA000299118 A CA 000299118A CA 299118 A CA299118 A CA 299118A CA 1116810 A CA1116810 A CA 1116810A
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- Prior art keywords
- parts
- pigment
- water
- aniline
- added
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
- C09B67/00—Influencing the physical, e.g. the dyeing or printing properties of dyestuffs without chemical reactions, e.g. by treating with solvents grinding or grinding assistants, coating of pigments or dyes; Process features in the making of dyestuff preparations; Dyestuff preparations of a special physical nature, e.g. tablets, films
- C09B67/0071—Process features in the making of dyestuff preparations; Dehydrating agents; Dispersing agents; Dustfree compositions
- C09B67/0092—Dyes in solid form
- C09B67/0095—Process features in the making of granulates
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- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Chemistry (AREA)
- Inks, Pencil-Leads, Or Crayons (AREA)
- Pigments, Carbon Blacks, Or Wood Stains (AREA)
Abstract
Abstract of the Disclosure A process for producing a pigment or dyestuff composition in the form of dustless readily-dispersible granules which comprises contactin, with agitation, an aqueous dispersion of a pigment, and an amine compound which is liquid at temperatures below 100°C, insoluble in water at pH values below 7, and soluble in water at pH values above 7. the pH value being above 7, maintaining the temperature above the melting point of the amine compound, and reducing the pH to below 7 to render the amine compound soluble in water, and recovering the resulting granules.
Description
~16810 ~ he present invention relates to a process for the preparation of dustless, readily-dispersible pigment or dyestuff granules.
The preparation of pigment granules by a process which comprises stirring together an aqueous pigment dispersion and a solution of a water-insoluble organic carrier in a water-immiscible organic liquid is known. However, in the known processes the resulting product contains some solvent, and it is necessary to remove the organic solvent from the product by distillation. We have now discovered a process in which the product is obtained directly in a solvent free condition.
According to the present invention there is provided a process for producing a pigment or dyestuff composition in the form of dust-less readily-dispersible granules which process comprises contacting, with agitation, an aqueous dispersion of a pigment, and 0,1 to 2 parts by weight per part of pigment of an aniline compound which is liquid at temperatures below 100C, insoluble in water at pH values above 7, and soluble in water at pH values below 7, the pH value being above 7, maintaining the temperature above the melting point of the amine com-pound, and reducing the pH to below 7 to render the amine compound soluble in water, and recovering the resulting granules.
As anilines come into consideration mono- or di- alkyl anilines in which each alkyl group has 1 to 8 carbon atoms or a derivative there-of, such as aniline, N-methyl aniline, N-ethyl aniline, N-propyl aniline, N-butyl aniline, N,N-dimethyl aniline or N,N-diethyl aniline, N,N-dipropyl aniline, N-cyclohexyl aniline, N-cyclohexyl N-hydroxy-ethyl aniline, N-octyl aniline, N-methyl-o-toluidine, N-ethyl-p-toluidine, N-butyl-m-toluidine, N,N-diethyl-m-toluidine, N,N-dimethyl-m-toluidine, methyl anthranilate, but is preferably N,N-diethyl aniline.
' '~; 2 ~4 llif~810 The amount of amine compound used is from 0.1 to 2 parts, preferably 0.3 to 0.6 parts by weight per part of pigment.
The process may also be carried out in the presence of from 0,05 to 2 parts per weight per part of pigment of an organic carrier The organic carrier may be any organic compound which is soluble in, or at least softened by, the amine compound, and is insoluble or can be rendered insoluble in water throughout the pH range used in the process. The carrier can be a liquid if the ratio of pigment to carrier is high, for example at or above 90:10; at lower proportions of pigment it is preferably to have a compound having a melting point above 40C as carrier.
Suitable carriers include, for example, carboxylic acid esters derived from alkyl, aryl, aralkyl or cycloalkyl carboxylic acid or polyacids and alkyl, aryl, aralkyl, or cycloalkyl mono- or poly-hydroxy compounds, such as the fatty acid esters cetyl palmitate, glycerol tristearate, glycerol monostearate, glycerol tripalmitate, glycerol trioleate, ethylene glycol dilaurate, ethylene glycol di-stearate, diethylene glycol distearate or the benzoic acid esters, such as ethylene glycol dibenzoate, neopentyl glycol dibenzoate trimethylol ethane tribenzoate, trimethylol propane tribenzoate or the dicarboxylic acid esters, such as dibenzyl phthalate, dibutyl phthalate, dioctyl phthalate, dicyclohexyl phthalate, and similar esters of adipic, sebacic or azelaic acids; amides from the above carboxylic acids and ammonia, or alkyl aryl, aralkyl or cycloalkyl mono- or poly-amides, such as stearamide, oleamide, palmitamide, N-alkyl stearamides or oleamides, ethylene bis stearamide; phosphate esters such as triphenyl or tricresyl phosphate, resins such as hy-drocarbon resins, xylene-formaldehyde resins, coumarone, coumarone-indene and ketone resins; vinyl polymers, such as polyvinyl chloride ~116810 and vinyl chloride copolymers, acsylate and methacrylate palymers and copolymers, polyvinyl acetate and vinyl acetate copolymers; styrene homo and copolymers; polyolefines such as polyethylene, polypropylene and polyisobutylene; fatty alcohols which are water insoluble, such as, cetyl alcohol and stearyl alcohol; and fatty amines which themselves do not give water soluble salts, such as didodecyl amine and distearyl monomethyl amine; and fatty oxazolines; water insoluble carboxylic acids, for example C12 and greater fatty acids, such as lauric acit, stearic acid, behenic acid and the rosin derivatives, such as wood rosin or its hydrogenated or disproportionated versions. These acids may also be added to the pigment as their alkali metal or ammonium salt dissolved in water: in this case the process is preferably carried out in the presence of water soluble inorganic salts, e.g. sodium chloride or calcium chloride.
These acids are applied as their soluble salts and may also be combined with the non-water soluble carriers, especially the sorbitan esters as defined in British patent specification No. 2,008,601;such combinations give granules which are extremely useful for pigmentation of PVC.
The weight ratio of pigment or dyestuff to carrier may be up to 33.3:66.7, preferably from 95:5 to 50:50, more preferably from 90:10 to 6Q:40.
When the process is carried out in the presence of an organic carrier, the amount of amine compound used is that which will form a solution of or at least soften the carrier. When using high ratios of pigment to carrier or when using a carrier which is poorly soluble in the amine compound, higher proportions of the amine compound may be needed to form satisfactory granules.
The pigment and dyestuffs that can be used are those which are water insoluble and stable in the pH range required for granule ~ .
~16810 formation and isolation. Suitable pigments are azo, azomethine, an-thraquinone, phthalocyanine, nitro, perinone, perylene, dioxazine, thioindigo, isoindolinone, quinacridone, azo or azomethine metal salts or complexes; mixtures of pigments may also be used. Water insoluble dyestuffs are those such as the solvent soluble azo and phthalo-cyanine dyes. These dyes can also be used as mixtures and in admixture with the pigment.
The organic carrier may be added with the amine compound, either dissolved or dispersed in the amine or both may be added prior to any heating or at any point during the heating cycle. The carrier may also be added in the form of an aqueous dispersion, for example, an aqueous dispersion of a polymer or resin such as polyvinyl chloride, vinyl chloride copolymer or low molecular weight (oxidised) polyethylene.
As well as using pure pigments or dyestuffs, ready-for-use pig-ment preparations may be used i.e. preparations which contain, in addition to the pigment, for example S to 90 per cent, preferably from 10 to 40 per cent by weight of a carrier.
Preferably a protective colloid is added to the mixture to assist in the formation of granules and the production of granules of a more uniform size distribution. When used it is preferably mixed with an aqueous pigment slurry or an aqueous dispersion of the amine compound before the pigment and amine compound are brought together.
Suitable protective colloids include cellulose derivatives such as hydroxy ethyl cellulose, hydroxy propyl cellulose, polyvinyl alcohol, polyethylene oxide, polypropylene oxide, copolymers of ethylene oxide and propylene oxide, adducts of ethylene oxide or propylene oxide, polyvinyl pyrrolidone and its copolymers or mixtures of these com-pounds. The preferred compounds are those of the hydroxy ethyl cellu-lose type as exemplified by the Natrosol range of the Hercules Powder Company.
;810 The amount of protective colloid may be up to 15 per cent, but is preferably less than 5 per cent by weight of the pigment.
The process may be carried out at a selected temperature, at which the carrier is at least softened, but preferably dissolved in the amine derivative at the temperature used.
:~ ' The mixture is originally formulated at or adjusted to a pH
of at least that at which the amine compound is insoluble in water.
The mixture is stirred at least until the pigment has migrated from the aqueous phase to the organic phase. Sufficient stirring is used to keep the droplets (or granules) in suspension. The size of granule is controlled to ~ome extent by the speed of stirring. Increased stirring or turbulence gives a reduction in granule size. High turbulence and therefore small granules can be obtained by use of the modified mixed/
emulsifier outlined in 8ritish patent specification No. 2,008,601.
The granules may be from 0.1 to 5 mm. in diameter, but preferably from O.S to 2 mm. in diameter.
The time of the process can be varied depending on the pigment used and the desired properties of the product. For example some pigments, particularly azo pigments, are susceptible to crystal growth when maintained in contact with the aniline compound, the amount of growth being dependent on the time of contact and the temperature.
Increased crystal size gives a pigment having higher opacity. There-fore, in these cases and if a product with good opacity and improved rheology in the application system is required, the time of contact of the pigment with the amine compound can be increased. If, on the other hand, a pigment of this type is used but a product having good trans-parency is required, the process time can be shortened to that which is sufficient for the pigment to migrate into the organic phase. In these cases the addition of a carrier assists robust granule forma-tion, thereby further shortening the process time. Selection of amine can also affect the opacity/transparency: aliphatic amines have less ~ ' ~ ' .
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crystallising effect than aromatic amines and thus produce more transparent compositions.
With those pigments which show little or no tendency to crystal growth in the process, there is no benefit from increased time of contact of the pigment wieh the amine compound beyond that required to form granules. Granule formation in such instances is substantially assisted by the use of a carrier. In these cases granule formation is further assisted by the use of inorganic salts dissolved in the water during the contacting process. Especially typical of such pig-ments are those which have been treated with a crystallising solvent during a previous process stage, e.g. halogenated copper phthalocyanine (green).
The pH of the mixture is then reduced to below 7, preferably below 5, by the addition of an acid which will form a water-soluble salt with the amine compound. The preferred acids are hydrochloric acid and acetic acid. This causes the amine compound to dissolve in the water as a salt, leaving the organic carrier if used, and pigment granules in suspension. If necessary, e.g. to promote solution, or if desired for handling or product performance, the temperature of the mixture may be increased or decreased. The granules are then recovered by sieving, washing and drying. Any granules that are too small to be recovered in this way may be filtered off and re-used in a subsequent batch.
To recover the solvent, the pH of the filtrate is raised, to a pH above 7, e.g. 10, whereupon the solvent becomes insoluble, separates from the water and can be recovered fo sub-sequent use by decantation for example. The aniline derivative may be further purified, if necessary, by steam distillation.
~6810 It is also possible to combine the granulation process of the present invention with a pigment solvent treatment process, to im-prove those pigment properties known to be improved by a solvent treatment. The solvent treatment can be carried out before or during the granulation step. For example, a phthalocyanine in a highly ag8regated state of an ~/~ crystal form mixture, as produced by dry grinding may be de-aggregated and converted substantially to the ~-form using the amine compound as the solvent in a solvent treatment process.
The granules, especially those of < 1 millimetre diameter can be improved in free flowing nature initially and during storage by the addition of a small percentage for instance up to 2% by weight,of a finely divided inorganic or modified inorganic material conven-tionally used for imparting such properties, such as a finely divided silica or silicate; such materials may conveniently be added to the granules by simple mixing. Especially advantageous materials of this type are the finely divided silicas with surface modifications by organic groups such as the Aerosil R 972 ex. Degussa.
The products of the invention may be used for the pigmentation of any system, such as surface coating media, e.g. paint and ink, or plastics. The carrier used will normally be selected so as to be compatible with the system to be pigmented. The product, when in-corporated into the system, releases the pigment from the granule to colour the material.
The invention is illustrated by the following Examples, wherein parts are parts by weight.
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Example l: 25.5 Parts C.I. Pigment Yellow 93 from a 30% w/w aqueous presscake were stirred with 600 parts water containing 0.5 parts hydroxyethyl cellulose for 10 minutes at room temperature. 13 Parts by volume diethyl aniline were added and the pH raised to 10.0;
1.5 parts sorbitan tristearate and 3.0 parts dicyclohexyl phthalate were added and the temperature raised to 85C. After stirring for a further 30 minutes at 85C the pH was lowered to 1.0 by the addition of 5N hydrochloric acid.
Stirring was continued for a further 60 minutes and the granules so formed were recovered by passing the mixture through a B.S. 60 mesh sieve and washing with, alternately, water at 50C and water at room temperature until chloride free. The granules, after drying at 40C in a drying cabinet with circulating air, gave a clear yellow film on incorporation in polyvinyl chloride and polyethylene.
Example 2: The procedure of Example 1 was repeated, except that 3.0 parts hydrocarbon resin under the trade mark Hercules A80 replaced the 3.0 parts dicyclohexyl phthalate. Similar results were obtained.
Example 3: The procedure as of Example 2 was repeated, except that 19 parts by volume diethylaniline were used as solvent. Similar re-sults were obtained. Temperature was raised to 85C and maintained for 30 minutes then 9.6 parts of hydrocarbon resin,(trade mark Hercules A80) was added. After a further 30 minutes stirring, the pH was lowered to 1.0 and, after stirring for a further 4 hours, the product was separated as in Example 1. The product could be incorporated into a thin lithographic ink to give a satisfactory dispersion.
~ "
~116810 Example 4: To 18.0 parts C.I. Pigment Yellow 13 in 600 parts water, obtained by a conventional acetate buffered aqueous coupling, was added 0.36 parts hydroxyethyl cellulose. The pH was raised to 10.0 by the addition of 2N sodium hydroxide and 2.4 parts sorbitan tri-itearate and 10 parts by volume diethylaniline were added.
Example 5: 0.2 Parts hydroxyethyl cellulose were dissolved in 200 parts water. 18 Parts C.I. Pigment Blue 15.3 slurried with 120 parts water were added with 3.7 parts in 200 parts water of the salt formed be-tween C.I. Direct Blue 86 and Rosin Amine D. To this mixture was added 10 parts diethylaniline and the pH adjusted to 10.0 by the addition of 2 N sodium hydroxide. The temperature was raised to 85C
and held at this temperature for 30 minutes. 20 Parts of a melt of a hydrocarbon resin under the trade mark Hercules A80 and cetyl alcohol in the ratio 2:1 were added and after a further 60 minutes the pH was lowered to 1.0 by the addition of 5 N hydrochlorid acid.
Stirring was continued for a further 6Q minutes and the resulting granules recovered as in Example 1. The pigmented granules thus produced could be readily dispersed in publication gravure medium.
Example 6: 0.2 Parts hydroxyethyl cellulose were dissolved in 200 parts water and to this was added 27 parts copper phthalocyanine (previously ground with 12~ w/w calcium chloride to an o/~ ratio of 60:40) in 150 parts water and 7.5 parts in 300 parts water of the salt formed between C.I. Direct Blue 86 and monomethyl di (hydro-genated tallow) amine. 10 parts diethylaniline were added and the pH
of the mixture then raised to 10.0 as in Example 5, and the process and quantities thereafter were again as in Example 5. The pigmented granules thus produced could be readily dispersed in publication gravure medium.
~, ^, 111tj810 Example 7: To a stirred aqueous slurry of 100 parts of pigment - C.I. Pigment Yellow 13 - there were added 2 parts of hydroxyethyl cellulose. The temperature was raised to 80C and the pH adjusted to 10 by the addition of 2 N sodium hydroxide. A solution of 20 parts dicyclohexyl phthalate in 50 parts diethyl aniline was then added and the mixture stirred until the pigment had migrated from the aqueous phase into the organic phase. The pH was then adjustad to 1 by addition of hydrochloric acid. Stirring was maintained at pHl for a further 15 minutes. The pigment composition - 120 parts - was then removed by sieving (60 mesh) and washed initially with water + acid (pH3) and then with water alone. The product was dried at 60~C. The resultant non-dusting composition was satisfactorily incorporated into a lithographic varnish.
Example 8: To a stirred aqueous slurry of 40 parts C.I. Pigment Blue 15.3 in 800 parts of water at pH10 there was added 10 parts of low molecular weight oxidised polyethylene in the form of a 20% w/w emulsion. 0.2 parts of hydroxyethyl cellulose was then added and the mixture agitated on a high energy mixer at 85C. The high energy mixer was then removed and a paddle stirrer inserted. 20 parts of diethyl aniline was addet and the mixture maintained for 30 minutes. The pH
was then adjusted to pHl by the addition ofHCl over 2 - 3 minutes and the mixture stirred for a further 30 minutes. The resultant granules were sieved off on a 60 mesh (B.S.) sieve, washed with dilute acid and then water, and then dried at 60C to give 50 parts of a product which could be dispersed into polyethylene.
Example 9: 10 Parts of hydrogenated wood rosin (trade mark Staybelite resin) and 22.5 parts of 50% aqueous potassium hydroxide solution were high speed stirred using a cavitation mixer in 100 parts of water at 50C until a smooth dispersion had formed (approximately 20 minutes).
f--lil681~
In a separate vessel, 15 parts of dicyclohexyl phthalate were dissolved in 30 parts of diethyl aniline with heating and 10 parts of the compound of average formula:
CuPc ~ S03 NCH3 (C12H25)2 ]
the preparation of which is described in Example 6 of British patent specification 1,541,599, added with stirring to form a smooth paste at 50-60C. This paste was added to the dispersion of Staybelite resin (trade mark for hydrogenated wood rosin) with the aid of a further 10 parts of diethyl aniline, and the whole high speed stirred until a smooth blue emulsion had formed (approximately 15 minutes).
92 Parts of crude copper phthalocyanine and 8 parts of phthalo-imide were ground in a ball mill until 55~ of the copper phthalo-cyanine was in the ~-crystal form. 97.8 Parts of this mixture, corres-ponding to 90 parts of copper phthalocyanine, were stirred in 200 parts of water at 50C until thoroughly weeted out. With high speed stirring, the above blue dispersion was poured into the wetted pigment and stirring maintained for 30 minutes, using external cooling as required to maintain the temperature of the mixture between 50 and 55C.
A paddle stirrer was substituted for the high speed stirrer.
While stirring at approximately 150 r.p.m., a solution of 5 parts calcium chloride and 71 parts concentrated hydrochloric acid in 500 parts of water was run in over 5 minutes. After a further 30 minutes stirring, the pigment composition thus formed was isolated by filtration, washed salt and acid free with warm water and dried at 50 - 60C.
There were obtained 120.8 parts of small, non-dusting granules having excellent rheology and colour strength in toluene based publication gravure inks.
Example 10: 20 Parts of a ~-copper phthalocyanine pigment and 0.3 partsof a nonyl phenol-ethylene oxide condensate (trade mark Synperonic NX) were stirred in S00 parts of water until the pigment had thoroughly wetted out. The pH was raised to 11 with dilute sodium hydroxide solu-tion and 0.5 part hydroxyethyl cellulose added prior to raising the temperature to 50C.
5 Parts of a coumarone-indene resin (trade mark Escores 11028) were dissolved in 10 parts of diethyl aniline with heating.
This solution was added to the pigment slurry while stirring with a paddle stirrer at approximately 150 r.p.m. and the mixture stirred at 50C for 30 minutes. While maintaining stirring, the pH was re-duced to 1 by the addition over 5 minutes of hydrochlorid acid.
After stirring for a further 30 minutes, the pigment composition so formed was recovered by pouring the reaction mixture onto a 100 mesh sieve, washing salt and acid free with warm water, and drying at 50 - 55C.
There were obtained 22.3 parts of evenly sized spherical granules of approximately 1 mm diameter, suitable for the preparation of lithographic inks.
Example 11: 48.9 Parts of the ground copper phthalocyanine mixture of Example 9, containing 45 parts of copper phthalocyanine, were stirred for S hours at reflux in 250 parts of isopropanol-water azeo-trope. 250 Parts of water were added and the isopropanol-water azeo-trope removed by distillation. A further 250 parts of water were added to reduce the temperature to 50C. 12.5 Parts of a hydrocarbon resin (trade mark Hercules A80) were dissolved in 25 parts of diethylaniline with heating and added to the stirring pigment slurry. 15 minutes later, S parts of the copper phthalocyanine sulphonic acid-tallow amine compound of Example 6 were added and the mixture stirred a 111~;81{) further 15 minutes. The reaction mixture was acidified by adding 30 ml of concentrated hydrochloric acid in 30 ml of water.
The pigment composition so formed was recovered on a 60 mesh sieve (B.S.), washed with hot water and dried at 50-55C.
There were obtained 58.2 parts of spherical granules 78% of which were in the range of 0.21 - 0.32 mm diameter.
Examples 12 - 18: 0.2 Parts of hydroxyethyl cellulose was added to 20 parts of C.I. Pigment Yellow 17 as present in an aqueous slurry from an azo coupling. The temperature was raised to 80C and the pH
adjusted to 10. 10 Parts of the alkyl aniline and varied amounts of di-isooctyl phthalate tDiOP) as shown in the Table below, were then addad. The mixture was stirred for 20 minutes at which time beads of 1 - 2 mm diameter had formed, the pH was then atjusted to ~ 1 with hydrochloric acid and stirring continued for 5 minutes. The beads were then filtered off, washed and dried at 50C. The resulting pro-ducts were evenly sized granules which could be incorporated into plasticised PVC to give a clear yellow film.
~1681~
Example AlkylanilineParts of DiOP
_ , 12 N,N-Diethyl aniline 2 13 N,N-Diethyl aniline 4 14 N,N-Diethyl aniline 6 lS N-ethyl aniline 2 16 N-butyl aniline 2 17 N-cyclohexyl aniline 2 18 N-hydroxyethyl-N- 2 cyclohexyl aniline .
Examples 19 - 23: 0.2 Parts of hydroxyethyl cellulose (trade mark Natrosol 250HR) was added to 20 parts C.I. Pigment Yellow 17 as present in an aqueous slurry from an azo coupling. The temperature was raised to 80C and pH adjusted to 10 by the addition of 2 N sodium hydroxide.
10 Parts of NN-Diethyl aniline and 2 parts of a carrier, as shown in the table below, were added. The mixture was stirred for 6Q minutes at which time granules of 1-2 mm had formed. The pH was then adjusted to 1 with hydrochloric acid and stirring continued for 5 minutes.
The granules were then filtered off, washed free of salts and dried at SOC. The resulting products were dispersed into lithographic ink media to give a printing ink concentrate.
_ .
Exa~ple Carrier 19 Hercules A80 (trade mark for a hydro-carbon resin) Cetyl palmitate 21 Crodamide O (oleamide) 22 Cellulose acetate proprionate 23 Kemamine 19701 (trade mark for monomethyl di-hydrogenated tallow amine) I
....~.
~116810 Example 24: ~0 Parts o~ C.I. Pigmen~ Yellow 17 as present in an aqueousslurry from an azo coupling and 0.2 parts hydroxyethyl cellulose (trade mark Natrosol 250HR) were adjusted to pH10 by the addition of 2 N
sodium hydroxide. 2 Parts of hydrogenated wood rosin (trade mark Stay-belite resin) as an aqueous solution of its potassium salt were added to the pigment slurry. After stirring for 10 minutes 1 part of calcium chloride dihydrate in 10 minutes 1 part of calcium chloride dihydrate in 10 parts of water was added and the temperature raised to 85C.
10 Parts of NN-diethyl aniline were then added and stirring continued for 1 hour at 85C. The pH was adjusted to 1 with hydrochlorid acid and the granules removed by filtration. They were then washed and dryed. The product was easily dispersed into lithographic varnish.
Example 25: To the pigment slurry as used in Example 24 were added 0.2 parts hydroxyethyl cellulose (trade mark Natrosol 250 HR) 2 g stearic acid and 0.6 parts calcium chloride dihydrate; the pH was ad-justed to 10 by the addition of 2N sodium hydroxide, the temperature raised to 85C and 10 parts l~N-diethyl aniline added. After stirring for 1 hour the pH was adjusted to 1 by the addition of 5 N hydro-chloric acid and the granules removed by filtration. They were then washed and dryed. The product could be dispersed into polyvinyl chloride.
Example 26: An aqueous slurry of 100 parts of C.I. Pigment Yellow 13 as formed in a conventional azo coupling and 2 parts of hydroxyethyl cellulose (trade mark Natrosol 250 HR) were stirred together for 20 minutes at 15C. The slurry pE was adjusted to 10 by the addition of
The preparation of pigment granules by a process which comprises stirring together an aqueous pigment dispersion and a solution of a water-insoluble organic carrier in a water-immiscible organic liquid is known. However, in the known processes the resulting product contains some solvent, and it is necessary to remove the organic solvent from the product by distillation. We have now discovered a process in which the product is obtained directly in a solvent free condition.
According to the present invention there is provided a process for producing a pigment or dyestuff composition in the form of dust-less readily-dispersible granules which process comprises contacting, with agitation, an aqueous dispersion of a pigment, and 0,1 to 2 parts by weight per part of pigment of an aniline compound which is liquid at temperatures below 100C, insoluble in water at pH values above 7, and soluble in water at pH values below 7, the pH value being above 7, maintaining the temperature above the melting point of the amine com-pound, and reducing the pH to below 7 to render the amine compound soluble in water, and recovering the resulting granules.
As anilines come into consideration mono- or di- alkyl anilines in which each alkyl group has 1 to 8 carbon atoms or a derivative there-of, such as aniline, N-methyl aniline, N-ethyl aniline, N-propyl aniline, N-butyl aniline, N,N-dimethyl aniline or N,N-diethyl aniline, N,N-dipropyl aniline, N-cyclohexyl aniline, N-cyclohexyl N-hydroxy-ethyl aniline, N-octyl aniline, N-methyl-o-toluidine, N-ethyl-p-toluidine, N-butyl-m-toluidine, N,N-diethyl-m-toluidine, N,N-dimethyl-m-toluidine, methyl anthranilate, but is preferably N,N-diethyl aniline.
' '~; 2 ~4 llif~810 The amount of amine compound used is from 0.1 to 2 parts, preferably 0.3 to 0.6 parts by weight per part of pigment.
The process may also be carried out in the presence of from 0,05 to 2 parts per weight per part of pigment of an organic carrier The organic carrier may be any organic compound which is soluble in, or at least softened by, the amine compound, and is insoluble or can be rendered insoluble in water throughout the pH range used in the process. The carrier can be a liquid if the ratio of pigment to carrier is high, for example at or above 90:10; at lower proportions of pigment it is preferably to have a compound having a melting point above 40C as carrier.
Suitable carriers include, for example, carboxylic acid esters derived from alkyl, aryl, aralkyl or cycloalkyl carboxylic acid or polyacids and alkyl, aryl, aralkyl, or cycloalkyl mono- or poly-hydroxy compounds, such as the fatty acid esters cetyl palmitate, glycerol tristearate, glycerol monostearate, glycerol tripalmitate, glycerol trioleate, ethylene glycol dilaurate, ethylene glycol di-stearate, diethylene glycol distearate or the benzoic acid esters, such as ethylene glycol dibenzoate, neopentyl glycol dibenzoate trimethylol ethane tribenzoate, trimethylol propane tribenzoate or the dicarboxylic acid esters, such as dibenzyl phthalate, dibutyl phthalate, dioctyl phthalate, dicyclohexyl phthalate, and similar esters of adipic, sebacic or azelaic acids; amides from the above carboxylic acids and ammonia, or alkyl aryl, aralkyl or cycloalkyl mono- or poly-amides, such as stearamide, oleamide, palmitamide, N-alkyl stearamides or oleamides, ethylene bis stearamide; phosphate esters such as triphenyl or tricresyl phosphate, resins such as hy-drocarbon resins, xylene-formaldehyde resins, coumarone, coumarone-indene and ketone resins; vinyl polymers, such as polyvinyl chloride ~116810 and vinyl chloride copolymers, acsylate and methacrylate palymers and copolymers, polyvinyl acetate and vinyl acetate copolymers; styrene homo and copolymers; polyolefines such as polyethylene, polypropylene and polyisobutylene; fatty alcohols which are water insoluble, such as, cetyl alcohol and stearyl alcohol; and fatty amines which themselves do not give water soluble salts, such as didodecyl amine and distearyl monomethyl amine; and fatty oxazolines; water insoluble carboxylic acids, for example C12 and greater fatty acids, such as lauric acit, stearic acid, behenic acid and the rosin derivatives, such as wood rosin or its hydrogenated or disproportionated versions. These acids may also be added to the pigment as their alkali metal or ammonium salt dissolved in water: in this case the process is preferably carried out in the presence of water soluble inorganic salts, e.g. sodium chloride or calcium chloride.
These acids are applied as their soluble salts and may also be combined with the non-water soluble carriers, especially the sorbitan esters as defined in British patent specification No. 2,008,601;such combinations give granules which are extremely useful for pigmentation of PVC.
The weight ratio of pigment or dyestuff to carrier may be up to 33.3:66.7, preferably from 95:5 to 50:50, more preferably from 90:10 to 6Q:40.
When the process is carried out in the presence of an organic carrier, the amount of amine compound used is that which will form a solution of or at least soften the carrier. When using high ratios of pigment to carrier or when using a carrier which is poorly soluble in the amine compound, higher proportions of the amine compound may be needed to form satisfactory granules.
The pigment and dyestuffs that can be used are those which are water insoluble and stable in the pH range required for granule ~ .
~16810 formation and isolation. Suitable pigments are azo, azomethine, an-thraquinone, phthalocyanine, nitro, perinone, perylene, dioxazine, thioindigo, isoindolinone, quinacridone, azo or azomethine metal salts or complexes; mixtures of pigments may also be used. Water insoluble dyestuffs are those such as the solvent soluble azo and phthalo-cyanine dyes. These dyes can also be used as mixtures and in admixture with the pigment.
The organic carrier may be added with the amine compound, either dissolved or dispersed in the amine or both may be added prior to any heating or at any point during the heating cycle. The carrier may also be added in the form of an aqueous dispersion, for example, an aqueous dispersion of a polymer or resin such as polyvinyl chloride, vinyl chloride copolymer or low molecular weight (oxidised) polyethylene.
As well as using pure pigments or dyestuffs, ready-for-use pig-ment preparations may be used i.e. preparations which contain, in addition to the pigment, for example S to 90 per cent, preferably from 10 to 40 per cent by weight of a carrier.
Preferably a protective colloid is added to the mixture to assist in the formation of granules and the production of granules of a more uniform size distribution. When used it is preferably mixed with an aqueous pigment slurry or an aqueous dispersion of the amine compound before the pigment and amine compound are brought together.
Suitable protective colloids include cellulose derivatives such as hydroxy ethyl cellulose, hydroxy propyl cellulose, polyvinyl alcohol, polyethylene oxide, polypropylene oxide, copolymers of ethylene oxide and propylene oxide, adducts of ethylene oxide or propylene oxide, polyvinyl pyrrolidone and its copolymers or mixtures of these com-pounds. The preferred compounds are those of the hydroxy ethyl cellu-lose type as exemplified by the Natrosol range of the Hercules Powder Company.
;810 The amount of protective colloid may be up to 15 per cent, but is preferably less than 5 per cent by weight of the pigment.
The process may be carried out at a selected temperature, at which the carrier is at least softened, but preferably dissolved in the amine derivative at the temperature used.
:~ ' The mixture is originally formulated at or adjusted to a pH
of at least that at which the amine compound is insoluble in water.
The mixture is stirred at least until the pigment has migrated from the aqueous phase to the organic phase. Sufficient stirring is used to keep the droplets (or granules) in suspension. The size of granule is controlled to ~ome extent by the speed of stirring. Increased stirring or turbulence gives a reduction in granule size. High turbulence and therefore small granules can be obtained by use of the modified mixed/
emulsifier outlined in 8ritish patent specification No. 2,008,601.
The granules may be from 0.1 to 5 mm. in diameter, but preferably from O.S to 2 mm. in diameter.
The time of the process can be varied depending on the pigment used and the desired properties of the product. For example some pigments, particularly azo pigments, are susceptible to crystal growth when maintained in contact with the aniline compound, the amount of growth being dependent on the time of contact and the temperature.
Increased crystal size gives a pigment having higher opacity. There-fore, in these cases and if a product with good opacity and improved rheology in the application system is required, the time of contact of the pigment with the amine compound can be increased. If, on the other hand, a pigment of this type is used but a product having good trans-parency is required, the process time can be shortened to that which is sufficient for the pigment to migrate into the organic phase. In these cases the addition of a carrier assists robust granule forma-tion, thereby further shortening the process time. Selection of amine can also affect the opacity/transparency: aliphatic amines have less ~ ' ~ ' .
~ B
i5 16~
crystallising effect than aromatic amines and thus produce more transparent compositions.
With those pigments which show little or no tendency to crystal growth in the process, there is no benefit from increased time of contact of the pigment wieh the amine compound beyond that required to form granules. Granule formation in such instances is substantially assisted by the use of a carrier. In these cases granule formation is further assisted by the use of inorganic salts dissolved in the water during the contacting process. Especially typical of such pig-ments are those which have been treated with a crystallising solvent during a previous process stage, e.g. halogenated copper phthalocyanine (green).
The pH of the mixture is then reduced to below 7, preferably below 5, by the addition of an acid which will form a water-soluble salt with the amine compound. The preferred acids are hydrochloric acid and acetic acid. This causes the amine compound to dissolve in the water as a salt, leaving the organic carrier if used, and pigment granules in suspension. If necessary, e.g. to promote solution, or if desired for handling or product performance, the temperature of the mixture may be increased or decreased. The granules are then recovered by sieving, washing and drying. Any granules that are too small to be recovered in this way may be filtered off and re-used in a subsequent batch.
To recover the solvent, the pH of the filtrate is raised, to a pH above 7, e.g. 10, whereupon the solvent becomes insoluble, separates from the water and can be recovered fo sub-sequent use by decantation for example. The aniline derivative may be further purified, if necessary, by steam distillation.
~6810 It is also possible to combine the granulation process of the present invention with a pigment solvent treatment process, to im-prove those pigment properties known to be improved by a solvent treatment. The solvent treatment can be carried out before or during the granulation step. For example, a phthalocyanine in a highly ag8regated state of an ~/~ crystal form mixture, as produced by dry grinding may be de-aggregated and converted substantially to the ~-form using the amine compound as the solvent in a solvent treatment process.
The granules, especially those of < 1 millimetre diameter can be improved in free flowing nature initially and during storage by the addition of a small percentage for instance up to 2% by weight,of a finely divided inorganic or modified inorganic material conven-tionally used for imparting such properties, such as a finely divided silica or silicate; such materials may conveniently be added to the granules by simple mixing. Especially advantageous materials of this type are the finely divided silicas with surface modifications by organic groups such as the Aerosil R 972 ex. Degussa.
The products of the invention may be used for the pigmentation of any system, such as surface coating media, e.g. paint and ink, or plastics. The carrier used will normally be selected so as to be compatible with the system to be pigmented. The product, when in-corporated into the system, releases the pigment from the granule to colour the material.
The invention is illustrated by the following Examples, wherein parts are parts by weight.
11~6~
Example l: 25.5 Parts C.I. Pigment Yellow 93 from a 30% w/w aqueous presscake were stirred with 600 parts water containing 0.5 parts hydroxyethyl cellulose for 10 minutes at room temperature. 13 Parts by volume diethyl aniline were added and the pH raised to 10.0;
1.5 parts sorbitan tristearate and 3.0 parts dicyclohexyl phthalate were added and the temperature raised to 85C. After stirring for a further 30 minutes at 85C the pH was lowered to 1.0 by the addition of 5N hydrochloric acid.
Stirring was continued for a further 60 minutes and the granules so formed were recovered by passing the mixture through a B.S. 60 mesh sieve and washing with, alternately, water at 50C and water at room temperature until chloride free. The granules, after drying at 40C in a drying cabinet with circulating air, gave a clear yellow film on incorporation in polyvinyl chloride and polyethylene.
Example 2: The procedure of Example 1 was repeated, except that 3.0 parts hydrocarbon resin under the trade mark Hercules A80 replaced the 3.0 parts dicyclohexyl phthalate. Similar results were obtained.
Example 3: The procedure as of Example 2 was repeated, except that 19 parts by volume diethylaniline were used as solvent. Similar re-sults were obtained. Temperature was raised to 85C and maintained for 30 minutes then 9.6 parts of hydrocarbon resin,(trade mark Hercules A80) was added. After a further 30 minutes stirring, the pH was lowered to 1.0 and, after stirring for a further 4 hours, the product was separated as in Example 1. The product could be incorporated into a thin lithographic ink to give a satisfactory dispersion.
~ "
~116810 Example 4: To 18.0 parts C.I. Pigment Yellow 13 in 600 parts water, obtained by a conventional acetate buffered aqueous coupling, was added 0.36 parts hydroxyethyl cellulose. The pH was raised to 10.0 by the addition of 2N sodium hydroxide and 2.4 parts sorbitan tri-itearate and 10 parts by volume diethylaniline were added.
Example 5: 0.2 Parts hydroxyethyl cellulose were dissolved in 200 parts water. 18 Parts C.I. Pigment Blue 15.3 slurried with 120 parts water were added with 3.7 parts in 200 parts water of the salt formed be-tween C.I. Direct Blue 86 and Rosin Amine D. To this mixture was added 10 parts diethylaniline and the pH adjusted to 10.0 by the addition of 2 N sodium hydroxide. The temperature was raised to 85C
and held at this temperature for 30 minutes. 20 Parts of a melt of a hydrocarbon resin under the trade mark Hercules A80 and cetyl alcohol in the ratio 2:1 were added and after a further 60 minutes the pH was lowered to 1.0 by the addition of 5 N hydrochlorid acid.
Stirring was continued for a further 6Q minutes and the resulting granules recovered as in Example 1. The pigmented granules thus produced could be readily dispersed in publication gravure medium.
Example 6: 0.2 Parts hydroxyethyl cellulose were dissolved in 200 parts water and to this was added 27 parts copper phthalocyanine (previously ground with 12~ w/w calcium chloride to an o/~ ratio of 60:40) in 150 parts water and 7.5 parts in 300 parts water of the salt formed between C.I. Direct Blue 86 and monomethyl di (hydro-genated tallow) amine. 10 parts diethylaniline were added and the pH
of the mixture then raised to 10.0 as in Example 5, and the process and quantities thereafter were again as in Example 5. The pigmented granules thus produced could be readily dispersed in publication gravure medium.
~, ^, 111tj810 Example 7: To a stirred aqueous slurry of 100 parts of pigment - C.I. Pigment Yellow 13 - there were added 2 parts of hydroxyethyl cellulose. The temperature was raised to 80C and the pH adjusted to 10 by the addition of 2 N sodium hydroxide. A solution of 20 parts dicyclohexyl phthalate in 50 parts diethyl aniline was then added and the mixture stirred until the pigment had migrated from the aqueous phase into the organic phase. The pH was then adjustad to 1 by addition of hydrochloric acid. Stirring was maintained at pHl for a further 15 minutes. The pigment composition - 120 parts - was then removed by sieving (60 mesh) and washed initially with water + acid (pH3) and then with water alone. The product was dried at 60~C. The resultant non-dusting composition was satisfactorily incorporated into a lithographic varnish.
Example 8: To a stirred aqueous slurry of 40 parts C.I. Pigment Blue 15.3 in 800 parts of water at pH10 there was added 10 parts of low molecular weight oxidised polyethylene in the form of a 20% w/w emulsion. 0.2 parts of hydroxyethyl cellulose was then added and the mixture agitated on a high energy mixer at 85C. The high energy mixer was then removed and a paddle stirrer inserted. 20 parts of diethyl aniline was addet and the mixture maintained for 30 minutes. The pH
was then adjusted to pHl by the addition ofHCl over 2 - 3 minutes and the mixture stirred for a further 30 minutes. The resultant granules were sieved off on a 60 mesh (B.S.) sieve, washed with dilute acid and then water, and then dried at 60C to give 50 parts of a product which could be dispersed into polyethylene.
Example 9: 10 Parts of hydrogenated wood rosin (trade mark Staybelite resin) and 22.5 parts of 50% aqueous potassium hydroxide solution were high speed stirred using a cavitation mixer in 100 parts of water at 50C until a smooth dispersion had formed (approximately 20 minutes).
f--lil681~
In a separate vessel, 15 parts of dicyclohexyl phthalate were dissolved in 30 parts of diethyl aniline with heating and 10 parts of the compound of average formula:
CuPc ~ S03 NCH3 (C12H25)2 ]
the preparation of which is described in Example 6 of British patent specification 1,541,599, added with stirring to form a smooth paste at 50-60C. This paste was added to the dispersion of Staybelite resin (trade mark for hydrogenated wood rosin) with the aid of a further 10 parts of diethyl aniline, and the whole high speed stirred until a smooth blue emulsion had formed (approximately 15 minutes).
92 Parts of crude copper phthalocyanine and 8 parts of phthalo-imide were ground in a ball mill until 55~ of the copper phthalo-cyanine was in the ~-crystal form. 97.8 Parts of this mixture, corres-ponding to 90 parts of copper phthalocyanine, were stirred in 200 parts of water at 50C until thoroughly weeted out. With high speed stirring, the above blue dispersion was poured into the wetted pigment and stirring maintained for 30 minutes, using external cooling as required to maintain the temperature of the mixture between 50 and 55C.
A paddle stirrer was substituted for the high speed stirrer.
While stirring at approximately 150 r.p.m., a solution of 5 parts calcium chloride and 71 parts concentrated hydrochloric acid in 500 parts of water was run in over 5 minutes. After a further 30 minutes stirring, the pigment composition thus formed was isolated by filtration, washed salt and acid free with warm water and dried at 50 - 60C.
There were obtained 120.8 parts of small, non-dusting granules having excellent rheology and colour strength in toluene based publication gravure inks.
Example 10: 20 Parts of a ~-copper phthalocyanine pigment and 0.3 partsof a nonyl phenol-ethylene oxide condensate (trade mark Synperonic NX) were stirred in S00 parts of water until the pigment had thoroughly wetted out. The pH was raised to 11 with dilute sodium hydroxide solu-tion and 0.5 part hydroxyethyl cellulose added prior to raising the temperature to 50C.
5 Parts of a coumarone-indene resin (trade mark Escores 11028) were dissolved in 10 parts of diethyl aniline with heating.
This solution was added to the pigment slurry while stirring with a paddle stirrer at approximately 150 r.p.m. and the mixture stirred at 50C for 30 minutes. While maintaining stirring, the pH was re-duced to 1 by the addition over 5 minutes of hydrochlorid acid.
After stirring for a further 30 minutes, the pigment composition so formed was recovered by pouring the reaction mixture onto a 100 mesh sieve, washing salt and acid free with warm water, and drying at 50 - 55C.
There were obtained 22.3 parts of evenly sized spherical granules of approximately 1 mm diameter, suitable for the preparation of lithographic inks.
Example 11: 48.9 Parts of the ground copper phthalocyanine mixture of Example 9, containing 45 parts of copper phthalocyanine, were stirred for S hours at reflux in 250 parts of isopropanol-water azeo-trope. 250 Parts of water were added and the isopropanol-water azeo-trope removed by distillation. A further 250 parts of water were added to reduce the temperature to 50C. 12.5 Parts of a hydrocarbon resin (trade mark Hercules A80) were dissolved in 25 parts of diethylaniline with heating and added to the stirring pigment slurry. 15 minutes later, S parts of the copper phthalocyanine sulphonic acid-tallow amine compound of Example 6 were added and the mixture stirred a 111~;81{) further 15 minutes. The reaction mixture was acidified by adding 30 ml of concentrated hydrochloric acid in 30 ml of water.
The pigment composition so formed was recovered on a 60 mesh sieve (B.S.), washed with hot water and dried at 50-55C.
There were obtained 58.2 parts of spherical granules 78% of which were in the range of 0.21 - 0.32 mm diameter.
Examples 12 - 18: 0.2 Parts of hydroxyethyl cellulose was added to 20 parts of C.I. Pigment Yellow 17 as present in an aqueous slurry from an azo coupling. The temperature was raised to 80C and the pH
adjusted to 10. 10 Parts of the alkyl aniline and varied amounts of di-isooctyl phthalate tDiOP) as shown in the Table below, were then addad. The mixture was stirred for 20 minutes at which time beads of 1 - 2 mm diameter had formed, the pH was then atjusted to ~ 1 with hydrochloric acid and stirring continued for 5 minutes. The beads were then filtered off, washed and dried at 50C. The resulting pro-ducts were evenly sized granules which could be incorporated into plasticised PVC to give a clear yellow film.
~1681~
Example AlkylanilineParts of DiOP
_ , 12 N,N-Diethyl aniline 2 13 N,N-Diethyl aniline 4 14 N,N-Diethyl aniline 6 lS N-ethyl aniline 2 16 N-butyl aniline 2 17 N-cyclohexyl aniline 2 18 N-hydroxyethyl-N- 2 cyclohexyl aniline .
Examples 19 - 23: 0.2 Parts of hydroxyethyl cellulose (trade mark Natrosol 250HR) was added to 20 parts C.I. Pigment Yellow 17 as present in an aqueous slurry from an azo coupling. The temperature was raised to 80C and pH adjusted to 10 by the addition of 2 N sodium hydroxide.
10 Parts of NN-Diethyl aniline and 2 parts of a carrier, as shown in the table below, were added. The mixture was stirred for 6Q minutes at which time granules of 1-2 mm had formed. The pH was then adjusted to 1 with hydrochloric acid and stirring continued for 5 minutes.
The granules were then filtered off, washed free of salts and dried at SOC. The resulting products were dispersed into lithographic ink media to give a printing ink concentrate.
_ .
Exa~ple Carrier 19 Hercules A80 (trade mark for a hydro-carbon resin) Cetyl palmitate 21 Crodamide O (oleamide) 22 Cellulose acetate proprionate 23 Kemamine 19701 (trade mark for monomethyl di-hydrogenated tallow amine) I
....~.
~116810 Example 24: ~0 Parts o~ C.I. Pigmen~ Yellow 17 as present in an aqueousslurry from an azo coupling and 0.2 parts hydroxyethyl cellulose (trade mark Natrosol 250HR) were adjusted to pH10 by the addition of 2 N
sodium hydroxide. 2 Parts of hydrogenated wood rosin (trade mark Stay-belite resin) as an aqueous solution of its potassium salt were added to the pigment slurry. After stirring for 10 minutes 1 part of calcium chloride dihydrate in 10 minutes 1 part of calcium chloride dihydrate in 10 parts of water was added and the temperature raised to 85C.
10 Parts of NN-diethyl aniline were then added and stirring continued for 1 hour at 85C. The pH was adjusted to 1 with hydrochlorid acid and the granules removed by filtration. They were then washed and dryed. The product was easily dispersed into lithographic varnish.
Example 25: To the pigment slurry as used in Example 24 were added 0.2 parts hydroxyethyl cellulose (trade mark Natrosol 250 HR) 2 g stearic acid and 0.6 parts calcium chloride dihydrate; the pH was ad-justed to 10 by the addition of 2N sodium hydroxide, the temperature raised to 85C and 10 parts l~N-diethyl aniline added. After stirring for 1 hour the pH was adjusted to 1 by the addition of 5 N hydro-chloric acid and the granules removed by filtration. They were then washed and dryed. The product could be dispersed into polyvinyl chloride.
Example 26: An aqueous slurry of 100 parts of C.I. Pigment Yellow 13 as formed in a conventional azo coupling and 2 parts of hydroxyethyl cellulose (trade mark Natrosol 250 HR) were stirred together for 20 minutes at 15C. The slurry pE was adjusted to 10 by the addition of
2 N sodium hydroxide, and a mixture of 10 parts dioctyl phthalate and 100 parts diethyl aniline were added. Stirring was continued for 90 minutes at 15C until granule formation was complete. The pH
was then adjusted to 1 by the addition of hydrochloric acid and the resultant granules, 100 parts, recovered by separation on a 60 mesh 11168~0 sieve, washing and drying at 50C. The product could be dispersed into lithographic ink media.
Example 27: 20 Parts of C.I. Pigment Green 7 in the form of a 30% w/w presscake were dispersed into 600 parts of water in which there was dissolved 30 parts sodium acetate and 10 parts sodium chloride. After raising the temperature to 85C 10 parts of NN-diethyl aniline were added and stirring continued for 2 hours at 85C. The pH was then reduced to just below 1 by the addition of 5N hydrochloric acid.
20 Parts of granules were removed on a 60 B.S. mesh sieve and after cax~fully washing to eliminate inorganic salts and acids, the product was dried at 55C. The resultant non-dusting granules could be dis-persed into lithographic ink media.
Example 28: 16 Parts of C.I. Pigment Green 7 in the form af a 30%
w/w presscake were dispersed into 300 parts water. To this dispersion were added 3 parts hydrogenated wood rosin (trade mark Staybelite resin) as an aqueous solution of its potassium salt. This mixture was stirred for 2 hours, then 0.2 parts of hydroxyethyl cellulose (trade mark Natrosol 250HR) and 3 parts sorbitan tristearate were added. This mixture now at pH 9 was heated to 85C, the pH was adjusted to 6 with 5N hydrochloric acid and 24 parts sodium acetate, 8 parts sodium chloride and 16 parts NN-diethyl aniline added. The mixture was stirred at 85C for 5 minutes, and the pH was then adjusted to just below 1 by the addition of 5N-hydrochloric acid. The resulting granules were filtered on a 60 B.S. mesh sieve, washed free of inorganic salts and acids and dried at 55C. The resulting product, 22 parts, could be dis-persed into plasticised P.V.C.
11~ti8~0 Examples 29 - 34: A series of bisarylamide azo pigments were prepared according to convention~ azo coupling techniques. To 20 parts of ehe various pigments as S~ w/w aqueous suspensions, as shown in the table, were added 0.2 parts hydroxyethyl cellulose (trade mark Natro-sol 250HR) and, after adjusting to pH 10 with 2N sodium hydroxide, 10 parts of NN-diethylaniline.
In each case the temperature was raised 85C and stirring con-tinued at this temperature for 2 hours; the pH was then adjusted to just below 1 by the addition of 5N hydrochloric acid and the granular product isolated by washing free of inorganic salts and acids followed by drying at 60C. The resulting products disper~ed into lithographic oil ink media.
Example Pigment 29 C.I.Pigment Yellow 13 C.I.Pigment Yellow 12 31 C.I.Pigment Yellow 14 32 C.I.Pigment Yellow 17 33 C.I.Pigment Yellow 55 34 C.I.Pigment Yellow 63.
Example 35: 20 Parts of C.I. Pigment Yellow 13, as a 5% w/w aqueous slurry prepared in a conventional aqueous azo coupling and 0.2 part hydroxyethyl cellulose (trade mark Natrosol 250 HR) are heated to 85C at pH 6. 10 Parts of NN-diethyl aniline were then added and stirring continued for a further 30 minutes. The pH was adjusted to just below 1 with 5N-hydrochloric acid and the granular product iso-lated by filtration, washing free of inorganic salts and acids and drying at 55C. The properties of this product were similar to those of Example 29.
.. ....
11168~) Example 36: lO0 Parts of an aqueous slurry of C.I.Pigment Yellow 13, prepared as for Example 35, was adjusted to pH 11 with 2N sodium hy-droxide and 1 part of hydroxyethyl cellulose (trade mark Natrosol 250HR) and 30 parts hydrogenated wood rosin, as an aqueous solution of its potassium salt, were added. The mixture was raised to 85C and held at this temperature for 15 minutes. The pH was then adjusted to 6.2 and 50 parts of NN-diethyl aniline added. Stirring was continued for 15 minutes and the pH was then reduced to just below 1 by the addition of 5 N hydrochloric acid. The regular spherical granules were recovered by filtration, washing free of inorganic salts and acids and drying at 55C. The resultant granules were dispersed into lithographic oil ink media to gi~e excellent gloss as a print.
Example 37: The procedure and quantities of Example 36 were repeated but the amount of hydrogenated wood rosin was reduced to 10 parts.
A similar product with like properties was obtained.
Example 38: 20 Parts of a 5% w/w aqueous suspension of a C.I.Pigment Yellow 13 composition, formed by treatment with a sulphonic acid dye-stuff and Rosin Amine D according to Example 109 of B.P. 1,356,253, was adjusted to pH 10 by the addition of 2N potassium hydroxide;
0.2 parts hydroxyethyl cellulose (trade mark Natrosol 250HR) and 2 parts hydrogenated wood rosin (trade mark Staybelite Resin), as aqueous solution of its potassium salt, were added and the mixture heated to 85C. 10 Parts of NN-diethyl aniline were then added and the mixture stirred for 1 hour at 85C before adjusting to just below pH 1 by the addition of 5N hydrochloric acid. The resul~ing spherical granules were filtered, washed free of inorganic salts and dried at 50C. This product could be dispersed into lithographic oil ink and showed greater transparency than the product of Example 37.
B
ill~i81(~
Example 39 The procedure and quantities of E~ample 37 were repeated but the amount of wood rosin was increased to 6 parts. A product similar in appearance and performance to that of Example 12 was ob-tained.
Example 40: 20 Parts of a 5% w/w aqueous slurry of C.I. Pigment Yellow 13, prepared as for Example 9, and 0.2 part hydroxyethyl cellulose (trade mark Natrosol 250~R) was adjustet to pH 10 by the addition of 2N
sodium hydroxide. 20 Parts of NN-diethyl aniline and 2 parts dioctyl phthalate were added and the mixture stirred for 45 minutes at 20C.
The pH was then adjusted to just less than 1 by the addition of 5N
hydrochloric acid. The granule composition was isolated by filtration, washing free of inorganic salts and acid and dried at 55C. The re-sultant granular product could be dispersed into lithographic ink.
Ecample 41: 20 Parts of C.I. Pigment Yellow 74 as a 5% w/w aqueous slurry, as prepared by conventional aqueous azo coupling, and 0.2 part hydroxyethyl cellulose (trade mark Natrosol 250HR) were adjusted to pH lO by the addition of 2N sodium hydroxide. 2 Parts hydrogenated wood rosin (trade mark Staybelite Resin), as an aqueous solution of its potassium salt, was then added, the temperature raised to 85C
and 10 parts NN-diethyl aniline added. Stirring was continued at 85C
for 2 hours, the pH adjusted to just less than 1 by the addition of 5N hydrochloric acid and the product isolated by filtration on a 6Q
B.S. mesh sieve, washed free of inorganic salts and acid and dried at 55C. The resulting generally Apherical granules could be dispersed into lithographic ink or decorative paint; in the latter application a very desirable opaque film could be achieved.
Example 42: 30 Parts of C.I. Pigment Yellow 83 as a 5% w/w aqueous slurry, as produced in a conventional aqueous azo coupling, was ad-justed to pH 7 by the addition of 2N potassium hydroxide, and 3 parts hydrogenated wood rosin (trade mark Staybelite Resin) were added as an ~116~0 aqueous soLution of its potassium salt. 0.3 Parts hydroxyethyl cellu-lose (trade mark Natrosol 250~R) was then added and the slurry now at pH 10 hea~ed to 85C and held at 85C for 10 minutes before ad-justing to pH 6 with 5N hydrochloric acid. 30 Parts of NN-diethyl aniline were then added and stirring continued at 85C for a further 10 minutes. The pH was then adjusted to less than 1 by the addition of SN hydrochlorid acid and the granules isolated by filtration on a 60 B.S. mesh sieve, washed free of inorganic salts and acid ant dried at 60C. The resulting product could be dispersed into oil ink to give a strong transparent ink film. In a nitrocellulose binder - alcohol solvent liquid ink excellent rheology was obtained and the resultant film showed excellend gloss and brightness.
Example 43: 30 Parts of an aqueous slurry of C.I. Pigment Yellow 83, as produced for Example 42, and 0.3 parts of hydroxyethyl cellulose (trade mark Natrosol 250MR) were atjusted to pH 7 and heatet to 85C.
30 Parts of NN-diethyl aniline were addet with stirring and contacting continuet for 3 hours at 85C. pH was then atjusted to just below 1 by addition of 5N hydrochloric acid and the generally spherical granules isolated by filtration on a 6Q B.S. mesh sieve, washed free of in-organic salts and acid and dried at 60C. The dry granules were free-flowing and robust to applied pressure. Incorporation into a lithogra-phic ink gave a film slightly more opaque than the product of Example 42; a nitrocellulose binder - alcohol solvent ink again exhibited goot rheology and a final film of excellent gloss as for Example 42.
Example 44: A mixture of 30 parts of an aqueous slurry of C.I. Pigment Yellow 83 as protuced for Example 42 and 0.2 parts of hydroxyethyl cellulose (trade mark Natrosol 250HR) was adjusted to pH 11 and 15 parts NN-diethylaniline added. The temperature was raiset to 95 and maintained at this temperature with constant stirring for 6 hours.
The pH was then retuced to 0.5 by the addition of 5N hydrochloric acid.
The product was then recovered by filtration on a 60 B.S. mesh sieve, , ~ ,j.
8~(~
washed free of inorganic salts and acid and dried at 55C.The resultant product was generally spherical granule of 0.5 - 1 mm average diameter.
Example 45: The procedure of Example 44 was repeated with an identical formulation and stirring conditions but omitting the hydroxyethyl cellulose: the resuleing product was granules of 3-5 mm diameter.
Example 46: 15 Parts of C.I. Pigment Red 38 in the form of a 5~ w/w aqueous slurry, ob~ained by a conventional aqueous coupling, was added to 400 parts water and the pH raised to 6.3.; 0.2 parts hydroxyethyl cellulose was added and heating commenced. When a temperature of 70C
was reached, 15 parts N,N-diethylaniline were added and the tempera-ture was raised to 80C. After stirring at 80C for a further 3 hours, the pH was lowered to just below 1.0 by the addition of 10 N hydro-chloric acid and the product separated and dried as in Example 45.
The resulting spherical granules could be readily dispersed in litho-graphic ink medium.
Example 47: 18 Parts of a ~-copper phthalocyanine pigment and 2 parts bis-cetyloxy-sulphanilide of copper phthalocyanine tthe preparation of which is described in US-patent specification 4,199,509) in the form of a 10~ w/w aqueous slurry were dispersed into 500 parts water in which there was dissolved 40 parts sodium chloride. To this dis-persion was added 0.2 parts hydroxyethyl cellulose (trade mark Natro-sol 250HR) and heating was commenced with stirring. At 70C, 5 parts dicyclohexyl phthalate dissolved in 15 parts N,N-diethyl aniline were added and the temperature taken to 80C and the stirring continued for 2 hours. The pH was then reduced to just below 1.0 by the addi-tion of lON hydrochloric acid. The rPsulting granules were separated by filtration and washed chloride free with water and dried at 40C
in a drying cabinet with circulating air. The product could be disper-sed into lithographic and publication gravure media.
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1~16~
Example 48: 200 Parts of the aqueous pigment slurry of Example 47 were added ~o 500 parts water in which there was dissolved 20 parts sodium chloride. To this dispersion was added 0.5 parts of a primary fatty (tallow) amine (trade mark Crodamine IT) as the acetate in aqueous solution and 1.5 parts of an hydrogenated wood rosin (trade mark Staybelite Resin) as an aqueous solution of its potassium salt and 0.1 parts of hydroxyethyl cellulose. Heating was commenced and, at 70C, 15 parts N,N-diethyl aniline were added and the temperature taken to 80C and stirring continued for a further 80 minutes. The pH was then reduced as in Example 21 and the resulting product, which was composed of generally spherical granules, were separated on a B.S. 60 mesh sieve, washed free of chloride ions and dried at 40C as in Example 47.
Example 49: 27 Parts of copper phthalocyanine (previously ground to an o/~ ratio of 60:40) and 30 parts sodium chloride were dispersed into 700 partswater. 0.1 part hydroxyethyl cellulose was added and heating commenced. When a temperature of 70C was reached, 1.5 parts of a secondary fatty (coconut oil) amine (trade mark Armeen 2C) dissolved in 11.2 parts N,N-diethyl aniline were added. The temperature was raised to 80C and, 1 hour after the addition of the diethylaniline, 6 parts of a hydrogenated wood rosin (trade mark Staybelite Resin) as an aqueous solution of its potassium salt was added. This was followed by 3 parts of the bis-cetyloxysulphanilide of copper phthalocyanine of Example 21. After stirring for a further 15 minutes, the pH was lowered to just below 1.0 by the addition of lON hydro-chloric acid and the resulting generally spherical granules separated as in Example 28. The granules thus obtained could be readily dis-persed in lithographic ink medium.
Example 50: 30 Parts of copper phthalocyanine (previously ground to an o/~ ratio of 55:40) and 30 parts sodium chloride were dispersed into 700 parts water and 0.1 part hydroxyethyl cellulose added.
Heating was commenced and 7.5 parts of an hydrogenated wood rosin (trade mark Staybelite Resin) as an aqueous solution of its potassium salt added. At a temperature of 75C, 15 parts N,N-diethylaniline were added and the mixture stirred at 80C for a further 2 hours. The pH was lowered as in Example 47 and the resulting granules, after being separated and dried as in Example 48, could be readily dispersed in lithographic ink medium.
Example 51: ôl.O Parts of the pigment of Example 24, 90 parts sodium chloride and 9.0 parts of the bis cetyloxysulphanilide of copper phthalocyanine of Example 47 were dispersed in 1500 parts water.
Heating was commenced and 2.25 parts of a primary fatty (tallow) amine (trade mark Crodamine IT) as the acetate in aqueous solution and 20.25 parts of an hydrogenated wood rosin ( trade mark Staybelite Resin) as an aqueous solution of its potassium salt were added. Stirring was con-tinued for 1 hour and 70 parts N,N-diethylaniline were added to the slurry at 80C. After a further 15 minutes the pH was lowered as in Example 27 and the resulting granules, after being separated and dried as in Example 48 could be readily dispersed in lithographic and publi-cation gravure ink media.
Example 52: 24 Parts of C.I. Pigment Orange 34 in the form of a 5%
W/'d aqueous slurry, obtained by a conventional acetate buffered aqueous coupling was dispersed with 100 parts water and the pH raised to 7.0 by the addition of 2N potassium hydroxide solution. 12 parts N,N-diethylaniline were added and the temperature raised to 80C over 45 minutes. After stirring at 80C for a further 15 minutes, the pH
was lowered to just below 1.0 by the addition of lON hydrochloric acid.
The resulting granules were separated by filtration and washed chloride free and dried as in Example 47. The granules of 0.5-4 mm diameter could be readily dispersed into lithographic ink medium.
Example 53: 120 Parts of C.I. Pigment Orange 34 in the form of 5% w/w aqueous slurry, obtained by a conventional acetate buffered aqueous coupling was added to 500 parts water and the pH raised to 8.0 by the additicn of 2M sodium hydroxide solution; 0.6 parts hydroxyethyl 11~681~:) - 25 ~
c~llulose was added and heating commenced. When a temperature of 60C
was reached 120 parts N,N-diethylaniline were added and the temperature raised to 80C. After stirring at 80C for 2 hours the pH was lowered to just below 1.0 by the addition of lON hydrochloric acid and the product separated and dried as in Example 48. The resulting spherical granules of 0.3 - 1 mm diameter could be readily dispersed into litho-graphic ink medium.
Example 54: 15 Parts of C.I. Pigment Red 3 in the form of a 5% w/w aqueous slurry, obtained by a conventional aqueous coupling, was dis-persedwith 400 parts water and the pH raised to 8.0 by the addition of 2N sodium hydroxide. 0.3 Parts hydroxy ethyl cellulose was added and heating commenced. When a temperature of 80C was reached 10 parts N,N diethylaniline was added and the mixture stirred for a further 2 hours at 80C. The pH was then reduced to 1.0 by the addition of lON hydrochloric acid and the product separated and dried as in Example 47. The resulting granules could be readily dispersed into lithographic ink medium.
Examples 55-6Q: The procedure of Example 36 was repeated except that the N,N'-diethyl aniline was replaced by an equal amount of the amines listed below. Product appearance and performance was equivalent to that of Example 36.
Example Amine N,N'-dimethyl-3-methylaniline 56 N,N'-dipropyl-aniline 57 N-ethyl-2-methylaniline 58 N,N'-dibutylaniline 59 2,5-dimethylaniline methyl-anthranilate ~3 ~116~
_ . , ~3 ~
~ ~ # , ~ ~ C ~; X~
C r1 0 ~ C ~
was then adjusted to 1 by the addition of hydrochloric acid and the resultant granules, 100 parts, recovered by separation on a 60 mesh 11168~0 sieve, washing and drying at 50C. The product could be dispersed into lithographic ink media.
Example 27: 20 Parts of C.I. Pigment Green 7 in the form of a 30% w/w presscake were dispersed into 600 parts of water in which there was dissolved 30 parts sodium acetate and 10 parts sodium chloride. After raising the temperature to 85C 10 parts of NN-diethyl aniline were added and stirring continued for 2 hours at 85C. The pH was then reduced to just below 1 by the addition of 5N hydrochloric acid.
20 Parts of granules were removed on a 60 B.S. mesh sieve and after cax~fully washing to eliminate inorganic salts and acids, the product was dried at 55C. The resultant non-dusting granules could be dis-persed into lithographic ink media.
Example 28: 16 Parts of C.I. Pigment Green 7 in the form af a 30%
w/w presscake were dispersed into 300 parts water. To this dispersion were added 3 parts hydrogenated wood rosin (trade mark Staybelite resin) as an aqueous solution of its potassium salt. This mixture was stirred for 2 hours, then 0.2 parts of hydroxyethyl cellulose (trade mark Natrosol 250HR) and 3 parts sorbitan tristearate were added. This mixture now at pH 9 was heated to 85C, the pH was adjusted to 6 with 5N hydrochloric acid and 24 parts sodium acetate, 8 parts sodium chloride and 16 parts NN-diethyl aniline added. The mixture was stirred at 85C for 5 minutes, and the pH was then adjusted to just below 1 by the addition of 5N-hydrochloric acid. The resulting granules were filtered on a 60 B.S. mesh sieve, washed free of inorganic salts and acids and dried at 55C. The resulting product, 22 parts, could be dis-persed into plasticised P.V.C.
11~ti8~0 Examples 29 - 34: A series of bisarylamide azo pigments were prepared according to convention~ azo coupling techniques. To 20 parts of ehe various pigments as S~ w/w aqueous suspensions, as shown in the table, were added 0.2 parts hydroxyethyl cellulose (trade mark Natro-sol 250HR) and, after adjusting to pH 10 with 2N sodium hydroxide, 10 parts of NN-diethylaniline.
In each case the temperature was raised 85C and stirring con-tinued at this temperature for 2 hours; the pH was then adjusted to just below 1 by the addition of 5N hydrochloric acid and the granular product isolated by washing free of inorganic salts and acids followed by drying at 60C. The resulting products disper~ed into lithographic oil ink media.
Example Pigment 29 C.I.Pigment Yellow 13 C.I.Pigment Yellow 12 31 C.I.Pigment Yellow 14 32 C.I.Pigment Yellow 17 33 C.I.Pigment Yellow 55 34 C.I.Pigment Yellow 63.
Example 35: 20 Parts of C.I. Pigment Yellow 13, as a 5% w/w aqueous slurry prepared in a conventional aqueous azo coupling and 0.2 part hydroxyethyl cellulose (trade mark Natrosol 250 HR) are heated to 85C at pH 6. 10 Parts of NN-diethyl aniline were then added and stirring continued for a further 30 minutes. The pH was adjusted to just below 1 with 5N-hydrochloric acid and the granular product iso-lated by filtration, washing free of inorganic salts and acids and drying at 55C. The properties of this product were similar to those of Example 29.
.. ....
11168~) Example 36: lO0 Parts of an aqueous slurry of C.I.Pigment Yellow 13, prepared as for Example 35, was adjusted to pH 11 with 2N sodium hy-droxide and 1 part of hydroxyethyl cellulose (trade mark Natrosol 250HR) and 30 parts hydrogenated wood rosin, as an aqueous solution of its potassium salt, were added. The mixture was raised to 85C and held at this temperature for 15 minutes. The pH was then adjusted to 6.2 and 50 parts of NN-diethyl aniline added. Stirring was continued for 15 minutes and the pH was then reduced to just below 1 by the addition of 5 N hydrochloric acid. The regular spherical granules were recovered by filtration, washing free of inorganic salts and acids and drying at 55C. The resultant granules were dispersed into lithographic oil ink media to gi~e excellent gloss as a print.
Example 37: The procedure and quantities of Example 36 were repeated but the amount of hydrogenated wood rosin was reduced to 10 parts.
A similar product with like properties was obtained.
Example 38: 20 Parts of a 5% w/w aqueous suspension of a C.I.Pigment Yellow 13 composition, formed by treatment with a sulphonic acid dye-stuff and Rosin Amine D according to Example 109 of B.P. 1,356,253, was adjusted to pH 10 by the addition of 2N potassium hydroxide;
0.2 parts hydroxyethyl cellulose (trade mark Natrosol 250HR) and 2 parts hydrogenated wood rosin (trade mark Staybelite Resin), as aqueous solution of its potassium salt, were added and the mixture heated to 85C. 10 Parts of NN-diethyl aniline were then added and the mixture stirred for 1 hour at 85C before adjusting to just below pH 1 by the addition of 5N hydrochloric acid. The resul~ing spherical granules were filtered, washed free of inorganic salts and dried at 50C. This product could be dispersed into lithographic oil ink and showed greater transparency than the product of Example 37.
B
ill~i81(~
Example 39 The procedure and quantities of E~ample 37 were repeated but the amount of wood rosin was increased to 6 parts. A product similar in appearance and performance to that of Example 12 was ob-tained.
Example 40: 20 Parts of a 5% w/w aqueous slurry of C.I. Pigment Yellow 13, prepared as for Example 9, and 0.2 part hydroxyethyl cellulose (trade mark Natrosol 250~R) was adjustet to pH 10 by the addition of 2N
sodium hydroxide. 20 Parts of NN-diethyl aniline and 2 parts dioctyl phthalate were added and the mixture stirred for 45 minutes at 20C.
The pH was then adjusted to just less than 1 by the addition of 5N
hydrochloric acid. The granule composition was isolated by filtration, washing free of inorganic salts and acid and dried at 55C. The re-sultant granular product could be dispersed into lithographic ink.
Ecample 41: 20 Parts of C.I. Pigment Yellow 74 as a 5% w/w aqueous slurry, as prepared by conventional aqueous azo coupling, and 0.2 part hydroxyethyl cellulose (trade mark Natrosol 250HR) were adjusted to pH lO by the addition of 2N sodium hydroxide. 2 Parts hydrogenated wood rosin (trade mark Staybelite Resin), as an aqueous solution of its potassium salt, was then added, the temperature raised to 85C
and 10 parts NN-diethyl aniline added. Stirring was continued at 85C
for 2 hours, the pH adjusted to just less than 1 by the addition of 5N hydrochloric acid and the product isolated by filtration on a 6Q
B.S. mesh sieve, washed free of inorganic salts and acid and dried at 55C. The resulting generally Apherical granules could be dispersed into lithographic ink or decorative paint; in the latter application a very desirable opaque film could be achieved.
Example 42: 30 Parts of C.I. Pigment Yellow 83 as a 5% w/w aqueous slurry, as produced in a conventional aqueous azo coupling, was ad-justed to pH 7 by the addition of 2N potassium hydroxide, and 3 parts hydrogenated wood rosin (trade mark Staybelite Resin) were added as an ~116~0 aqueous soLution of its potassium salt. 0.3 Parts hydroxyethyl cellu-lose (trade mark Natrosol 250~R) was then added and the slurry now at pH 10 hea~ed to 85C and held at 85C for 10 minutes before ad-justing to pH 6 with 5N hydrochloric acid. 30 Parts of NN-diethyl aniline were then added and stirring continued at 85C for a further 10 minutes. The pH was then adjusted to less than 1 by the addition of SN hydrochlorid acid and the granules isolated by filtration on a 60 B.S. mesh sieve, washed free of inorganic salts and acid ant dried at 60C. The resulting product could be dispersed into oil ink to give a strong transparent ink film. In a nitrocellulose binder - alcohol solvent liquid ink excellent rheology was obtained and the resultant film showed excellend gloss and brightness.
Example 43: 30 Parts of an aqueous slurry of C.I. Pigment Yellow 83, as produced for Example 42, and 0.3 parts of hydroxyethyl cellulose (trade mark Natrosol 250MR) were atjusted to pH 7 and heatet to 85C.
30 Parts of NN-diethyl aniline were addet with stirring and contacting continuet for 3 hours at 85C. pH was then atjusted to just below 1 by addition of 5N hydrochloric acid and the generally spherical granules isolated by filtration on a 6Q B.S. mesh sieve, washed free of in-organic salts and acid and dried at 60C. The dry granules were free-flowing and robust to applied pressure. Incorporation into a lithogra-phic ink gave a film slightly more opaque than the product of Example 42; a nitrocellulose binder - alcohol solvent ink again exhibited goot rheology and a final film of excellent gloss as for Example 42.
Example 44: A mixture of 30 parts of an aqueous slurry of C.I. Pigment Yellow 83 as protuced for Example 42 and 0.2 parts of hydroxyethyl cellulose (trade mark Natrosol 250HR) was adjusted to pH 11 and 15 parts NN-diethylaniline added. The temperature was raiset to 95 and maintained at this temperature with constant stirring for 6 hours.
The pH was then retuced to 0.5 by the addition of 5N hydrochloric acid.
The product was then recovered by filtration on a 60 B.S. mesh sieve, , ~ ,j.
8~(~
washed free of inorganic salts and acid and dried at 55C.The resultant product was generally spherical granule of 0.5 - 1 mm average diameter.
Example 45: The procedure of Example 44 was repeated with an identical formulation and stirring conditions but omitting the hydroxyethyl cellulose: the resuleing product was granules of 3-5 mm diameter.
Example 46: 15 Parts of C.I. Pigment Red 38 in the form of a 5~ w/w aqueous slurry, ob~ained by a conventional aqueous coupling, was added to 400 parts water and the pH raised to 6.3.; 0.2 parts hydroxyethyl cellulose was added and heating commenced. When a temperature of 70C
was reached, 15 parts N,N-diethylaniline were added and the tempera-ture was raised to 80C. After stirring at 80C for a further 3 hours, the pH was lowered to just below 1.0 by the addition of 10 N hydro-chloric acid and the product separated and dried as in Example 45.
The resulting spherical granules could be readily dispersed in litho-graphic ink medium.
Example 47: 18 Parts of a ~-copper phthalocyanine pigment and 2 parts bis-cetyloxy-sulphanilide of copper phthalocyanine tthe preparation of which is described in US-patent specification 4,199,509) in the form of a 10~ w/w aqueous slurry were dispersed into 500 parts water in which there was dissolved 40 parts sodium chloride. To this dis-persion was added 0.2 parts hydroxyethyl cellulose (trade mark Natro-sol 250HR) and heating was commenced with stirring. At 70C, 5 parts dicyclohexyl phthalate dissolved in 15 parts N,N-diethyl aniline were added and the temperature taken to 80C and the stirring continued for 2 hours. The pH was then reduced to just below 1.0 by the addi-tion of lON hydrochloric acid. The rPsulting granules were separated by filtration and washed chloride free with water and dried at 40C
in a drying cabinet with circulating air. The product could be disper-sed into lithographic and publication gravure media.
B
1~16~
Example 48: 200 Parts of the aqueous pigment slurry of Example 47 were added ~o 500 parts water in which there was dissolved 20 parts sodium chloride. To this dispersion was added 0.5 parts of a primary fatty (tallow) amine (trade mark Crodamine IT) as the acetate in aqueous solution and 1.5 parts of an hydrogenated wood rosin (trade mark Staybelite Resin) as an aqueous solution of its potassium salt and 0.1 parts of hydroxyethyl cellulose. Heating was commenced and, at 70C, 15 parts N,N-diethyl aniline were added and the temperature taken to 80C and stirring continued for a further 80 minutes. The pH was then reduced as in Example 21 and the resulting product, which was composed of generally spherical granules, were separated on a B.S. 60 mesh sieve, washed free of chloride ions and dried at 40C as in Example 47.
Example 49: 27 Parts of copper phthalocyanine (previously ground to an o/~ ratio of 60:40) and 30 parts sodium chloride were dispersed into 700 partswater. 0.1 part hydroxyethyl cellulose was added and heating commenced. When a temperature of 70C was reached, 1.5 parts of a secondary fatty (coconut oil) amine (trade mark Armeen 2C) dissolved in 11.2 parts N,N-diethyl aniline were added. The temperature was raised to 80C and, 1 hour after the addition of the diethylaniline, 6 parts of a hydrogenated wood rosin (trade mark Staybelite Resin) as an aqueous solution of its potassium salt was added. This was followed by 3 parts of the bis-cetyloxysulphanilide of copper phthalocyanine of Example 21. After stirring for a further 15 minutes, the pH was lowered to just below 1.0 by the addition of lON hydro-chloric acid and the resulting generally spherical granules separated as in Example 28. The granules thus obtained could be readily dis-persed in lithographic ink medium.
Example 50: 30 Parts of copper phthalocyanine (previously ground to an o/~ ratio of 55:40) and 30 parts sodium chloride were dispersed into 700 parts water and 0.1 part hydroxyethyl cellulose added.
Heating was commenced and 7.5 parts of an hydrogenated wood rosin (trade mark Staybelite Resin) as an aqueous solution of its potassium salt added. At a temperature of 75C, 15 parts N,N-diethylaniline were added and the mixture stirred at 80C for a further 2 hours. The pH was lowered as in Example 47 and the resulting granules, after being separated and dried as in Example 48, could be readily dispersed in lithographic ink medium.
Example 51: ôl.O Parts of the pigment of Example 24, 90 parts sodium chloride and 9.0 parts of the bis cetyloxysulphanilide of copper phthalocyanine of Example 47 were dispersed in 1500 parts water.
Heating was commenced and 2.25 parts of a primary fatty (tallow) amine (trade mark Crodamine IT) as the acetate in aqueous solution and 20.25 parts of an hydrogenated wood rosin ( trade mark Staybelite Resin) as an aqueous solution of its potassium salt were added. Stirring was con-tinued for 1 hour and 70 parts N,N-diethylaniline were added to the slurry at 80C. After a further 15 minutes the pH was lowered as in Example 27 and the resulting granules, after being separated and dried as in Example 48 could be readily dispersed in lithographic and publi-cation gravure ink media.
Example 52: 24 Parts of C.I. Pigment Orange 34 in the form of a 5%
W/'d aqueous slurry, obtained by a conventional acetate buffered aqueous coupling was dispersed with 100 parts water and the pH raised to 7.0 by the addition of 2N potassium hydroxide solution. 12 parts N,N-diethylaniline were added and the temperature raised to 80C over 45 minutes. After stirring at 80C for a further 15 minutes, the pH
was lowered to just below 1.0 by the addition of lON hydrochloric acid.
The resulting granules were separated by filtration and washed chloride free and dried as in Example 47. The granules of 0.5-4 mm diameter could be readily dispersed into lithographic ink medium.
Example 53: 120 Parts of C.I. Pigment Orange 34 in the form of 5% w/w aqueous slurry, obtained by a conventional acetate buffered aqueous coupling was added to 500 parts water and the pH raised to 8.0 by the additicn of 2M sodium hydroxide solution; 0.6 parts hydroxyethyl 11~681~:) - 25 ~
c~llulose was added and heating commenced. When a temperature of 60C
was reached 120 parts N,N-diethylaniline were added and the temperature raised to 80C. After stirring at 80C for 2 hours the pH was lowered to just below 1.0 by the addition of lON hydrochloric acid and the product separated and dried as in Example 48. The resulting spherical granules of 0.3 - 1 mm diameter could be readily dispersed into litho-graphic ink medium.
Example 54: 15 Parts of C.I. Pigment Red 3 in the form of a 5% w/w aqueous slurry, obtained by a conventional aqueous coupling, was dis-persedwith 400 parts water and the pH raised to 8.0 by the addition of 2N sodium hydroxide. 0.3 Parts hydroxy ethyl cellulose was added and heating commenced. When a temperature of 80C was reached 10 parts N,N diethylaniline was added and the mixture stirred for a further 2 hours at 80C. The pH was then reduced to 1.0 by the addition of lON hydrochloric acid and the product separated and dried as in Example 47. The resulting granules could be readily dispersed into lithographic ink medium.
Examples 55-6Q: The procedure of Example 36 was repeated except that the N,N'-diethyl aniline was replaced by an equal amount of the amines listed below. Product appearance and performance was equivalent to that of Example 36.
Example Amine N,N'-dimethyl-3-methylaniline 56 N,N'-dipropyl-aniline 57 N-ethyl-2-methylaniline 58 N,N'-dibutylaniline 59 2,5-dimethylaniline methyl-anthranilate ~3 ~116~
_ . , ~3 ~
~ ~ # , ~ ~ C ~; X~
C r1 0 ~ C ~
3 ~ ~ 1 o z ~ e P~ I
'O S S
to ~ O _I
~ ~ SO ~ SO ~Iq ~ C ~ ~
.,~ ~ u ~ u ~a ~ - - - - - U ~ U :C
~ ~ ~C
_ ~ I 5 3 3 3 ~4 .5 C C ~ C
Oao P~ ~ ~ ~ ~ ~ ~' .~ C~ i _ C
~D C~
a ~
X ~ O ~ O `O ~
Example 70: 20 parts of CI Pigment Yellow 13 as an aqueous slurry as prepared according to Example 35, 0.2 parts hydroxyethyl cellulose (trade mark Natrosol 250HR) and 5 parts dicyclohexylphthalate were heated at pH 8 from 15C to 85C and 15 parts of 2 ethyl hexylamine was then added. The mixture was maintained at 85C for 1 hour, then ad-justed to pHl.5 with lON hydrochloric acid and the granules covered by filtration, washing and drying at 55C. The product could be dispersed into a lithographic varnish.
Example 71: 10 parts of Solvent Yellow 48 was dispersed in 200 parts of water and 0.1 parts potassium resinate and 0.1 part hydroxyethyl cellulose (trade mark Natrosol 250HR). The mixture was adjusted to pH7 and 5 parts N,N'-diethylaniline added. The mixture was heated to 80 and held for 30 minutes, before adjusting to pH 1 with lON hydro-chloric acid. The resulting granules were recovered by filtration washing and drying at 30C.
Example 72: An aqueous slurry of 20 parts of a CI Pigment Red 57:
resin composition (16:4 part ratio by formation of tha pigment metal salt in the presence of Staybelite resin, (trade mark) 0.5 parts hydroxyethyl cellulose (trade mark Natrosol 250HR) and 3.3 parts abietyl amine, added as its water soluble acetate salt, were heated to 95C at pH 10. 10 parts N,N'-diethylaniline were then added the pH adjusted to 7 and stirring continued for 2 hours at 95C. The pH
was then adjusted to 3.2 by the addition of glacial acetic acid.*
The granules were isolated, washed and dried at 90C. The product could be dispersed into lithographic ink varnish.
*Adjustment to pH 1 with concentrated hydrochloric acid is to be avoided as it results in a product of poor performance, presumably due to breakdown of the metal salt at this pH.
Example 73: 100 parts of C.I. Pigment Green 7 as a 35% parts by weight presscake were dispersed i~ 2000 parts of water using a modi-fied mixer/emulsifier head as described in the text. After 20 minutes "~
~, , ,~, mixing a solution of 30 parts of Staybelite resin as its a~monium salt was added and ~i~ing continued for a further 60 minutes. 0.4 parts hydroxyethyl cellulose (trade mark Natrosol 250 HR) and 20 parts sorbi-tan tristearate were then added and the temperature raised to 85C.
~ith continued mixing 30 parts of N,N'-diethylaniline, dispersed in 100 parts ofwater and 0.5 parts of dissolved potassium resinate, was added. ~he modified mixer/emulsifier stirring was continued for 1 minute, the pH adjusted to 6 ant stirring continued for a further 5 minutes before adjusting to pH 1 by the addition of 5N hydrochloric acid. The granules were removed by filtration on a 200 mesh BS sieve, washed free of acid and salts and dried at 45C. The resultant granules, all of < 0.5 mm diameter could be readily dispersed into a plasticised P.V.C. compound.
The addition of 1~ by weight of Aerosil R 972 (trade mark) to the above granules gave a product of improved free 1Owing properties especially after storage.
Example 74: The procedure of Example 73 was repeated except that the solution of Staybelite resin was replaced by a solution 30 parts of Ennesin A 100 (trade mark) as its potassium salt. A product of similar properties was produced.
B
'O S S
to ~ O _I
~ ~ SO ~ SO ~Iq ~ C ~ ~
.,~ ~ u ~ u ~a ~ - - - - - U ~ U :C
~ ~ ~C
_ ~ I 5 3 3 3 ~4 .5 C C ~ C
Oao P~ ~ ~ ~ ~ ~ ~' .~ C~ i _ C
~D C~
a ~
X ~ O ~ O `O ~
Example 70: 20 parts of CI Pigment Yellow 13 as an aqueous slurry as prepared according to Example 35, 0.2 parts hydroxyethyl cellulose (trade mark Natrosol 250HR) and 5 parts dicyclohexylphthalate were heated at pH 8 from 15C to 85C and 15 parts of 2 ethyl hexylamine was then added. The mixture was maintained at 85C for 1 hour, then ad-justed to pHl.5 with lON hydrochloric acid and the granules covered by filtration, washing and drying at 55C. The product could be dispersed into a lithographic varnish.
Example 71: 10 parts of Solvent Yellow 48 was dispersed in 200 parts of water and 0.1 parts potassium resinate and 0.1 part hydroxyethyl cellulose (trade mark Natrosol 250HR). The mixture was adjusted to pH7 and 5 parts N,N'-diethylaniline added. The mixture was heated to 80 and held for 30 minutes, before adjusting to pH 1 with lON hydro-chloric acid. The resulting granules were recovered by filtration washing and drying at 30C.
Example 72: An aqueous slurry of 20 parts of a CI Pigment Red 57:
resin composition (16:4 part ratio by formation of tha pigment metal salt in the presence of Staybelite resin, (trade mark) 0.5 parts hydroxyethyl cellulose (trade mark Natrosol 250HR) and 3.3 parts abietyl amine, added as its water soluble acetate salt, were heated to 95C at pH 10. 10 parts N,N'-diethylaniline were then added the pH adjusted to 7 and stirring continued for 2 hours at 95C. The pH
was then adjusted to 3.2 by the addition of glacial acetic acid.*
The granules were isolated, washed and dried at 90C. The product could be dispersed into lithographic ink varnish.
*Adjustment to pH 1 with concentrated hydrochloric acid is to be avoided as it results in a product of poor performance, presumably due to breakdown of the metal salt at this pH.
Example 73: 100 parts of C.I. Pigment Green 7 as a 35% parts by weight presscake were dispersed i~ 2000 parts of water using a modi-fied mixer/emulsifier head as described in the text. After 20 minutes "~
~, , ,~, mixing a solution of 30 parts of Staybelite resin as its a~monium salt was added and ~i~ing continued for a further 60 minutes. 0.4 parts hydroxyethyl cellulose (trade mark Natrosol 250 HR) and 20 parts sorbi-tan tristearate were then added and the temperature raised to 85C.
~ith continued mixing 30 parts of N,N'-diethylaniline, dispersed in 100 parts ofwater and 0.5 parts of dissolved potassium resinate, was added. ~he modified mixer/emulsifier stirring was continued for 1 minute, the pH adjusted to 6 ant stirring continued for a further 5 minutes before adjusting to pH 1 by the addition of 5N hydrochloric acid. The granules were removed by filtration on a 200 mesh BS sieve, washed free of acid and salts and dried at 45C. The resultant granules, all of < 0.5 mm diameter could be readily dispersed into a plasticised P.V.C. compound.
The addition of 1~ by weight of Aerosil R 972 (trade mark) to the above granules gave a product of improved free 1Owing properties especially after storage.
Example 74: The procedure of Example 73 was repeated except that the solution of Staybelite resin was replaced by a solution 30 parts of Ennesin A 100 (trade mark) as its potassium salt. A product of similar properties was produced.
B
Claims (14)
PROPERTY OR PRIVILEGE IS CLAIMED ARE DEFINED AS FOLLOWS:
1. A process for producing a pigment composition in the form of dustless readily-dispersible granules which comprises contacting, with agitation, an aqueous dispersion of a pigment, and 0.1 to 2 parts by weight of an aniline or a mono- or di-alkyl-aniline, in-soluble in water at pH values above 7, and soluble in water at pH
values below 7, the pH value being above 7, maintaining the temper-ature above the melting point of the aniline compound, and reducing the pH to below 7 to render the aniline compound soluble in water, and recovering the resulting granules.
values below 7, the pH value being above 7, maintaining the temper-ature above the melting point of the aniline compound, and reducing the pH to below 7 to render the aniline compound soluble in water, and recovering the resulting granules.
2. A process as claimed in claim 1, in which is used aniline or a mono- or di-alkyl-aniline in which each alkyl group has 1 to 8 carbon atoms.
3. A process as claimed in claim 1, in which the amount of aniline compound is from 0.1 to 2 parts by weight per part of pigment.
4. A process as claimed in claim 1, in which the amount of aniline compound is from 0.3 to 0.6 parts by weight per part of pigment.
5. A process as claimed in claim 1, which is carried out in the presence of from 0.05 to 2 parts by weight per part of pigment of an organic carrier which has a melting point above 40°C and which is soluble in, or at least softened by the aniline compound and is insoluble or can be rendered insoluble in water throughout the pH range used in the process.
6. A process as claimed in claim 5, in which the carrier is a carboxylic acid ester, a carboxylic acid amide, a phosphate ester, a resin, a vinyl polymer, a styrene polymer, a polyolefine, a fatty alcohol, a fatty amine which does not give water soluble salts, a fatty oxazoline, a water insoluble carboxylic acid or a resin derivative.
7. A process as claimed in claim 6, in which the amount of carrier is from 0.1 to 0.7 parts by weight per part of pigment.
8. A process as claimed in claim 1, which is carried out in the presence of up to 15% by weight of the pigment of a protective colloid.
9. A process as claimed in claim 8, in which the protective colloid is mixed with an aqueous pigment slurry or an aqueous dispersion of the aniline compound before the pigment or dyestuff and amine are brought together.
10. A process as claimed in claim 8, in which the protective colloid is a cellulose derivative.
11. A process as claimed in claim 8, in which the amount of protective colloid is less than 5% by weight of the pigment.
12. A process as claimed in claim 1, in which the mixture is stirred at least until the pigment has migrated from the aqueous phase to the organic phase.
13. A process as claimed in claim 1, in which the stirring is such as will produce granules of a size from 0.1 to 5 mm in diameter.
14. A process as claimed in claim 1, in which the stirring is such as will produce granules of a size from 0.5 to 2 mm in diameter.
Applications Claiming Priority (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| GB11633/77 | 1977-03-18 | ||
| GB11633/77A GB1563969A (en) | 1977-03-18 | 1977-03-18 | Pigment compositions |
| GB48062/77 | 1977-11-18 | ||
| GB4806277 | 1977-11-18 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1116810A true CA1116810A (en) | 1982-01-26 |
Family
ID=26248408
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA000299118A Expired CA1116810A (en) | 1977-03-18 | 1978-03-16 | Pigment compositions |
Country Status (11)
| Country | Link |
|---|---|
| JP (1) | JPS53115741A (en) |
| AU (1) | AU3424578A (en) |
| BR (1) | BR7801661A (en) |
| CA (1) | CA1116810A (en) |
| DE (1) | DE2811294C2 (en) |
| DK (1) | DK153327C (en) |
| ES (1) | ES467980A1 (en) |
| FR (1) | FR2384004A1 (en) |
| IT (1) | IT1113168B (en) |
| NL (1) | NL7802831A (en) |
| SU (1) | SU791254A3 (en) |
Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CH637155A5 (en) * | 1977-11-18 | 1983-07-15 | Ciba Geigy Ag | Treatment of azo pigments and amines |
| GB1589159A (en) * | 1978-05-31 | 1981-05-07 | Ciba Geigy Ag | Process for producing pigment and dyestuff compositions |
| US4373962A (en) * | 1981-06-08 | 1983-02-15 | Basf Wyandotte Corporation | Surface treated alkali blue pigment |
| EP0363322B1 (en) * | 1988-10-06 | 1995-02-08 | Ciba-Geigy Ag | Process for the manufacture of pigment preparations |
| GB9125114D0 (en) * | 1991-11-23 | 1992-01-22 | Ciba Geigy Ag | Production of pigment compositions |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CH368883A (en) * | 1958-07-01 | 1963-04-30 | Geigy Ag J R | Process for the production of finely divided pigments of the phthalocyanine series |
| FR1538270A (en) * | 1966-10-01 | 1968-08-30 | Bayer Ag | Pigment preparations |
| CH517821A (en) * | 1968-04-17 | 1972-01-15 | Bayer Ag | Process for the production of a pigment preparation |
| DK260575A (en) * | 1974-06-19 | 1975-12-20 | Ciba Geigy Ag | PROCEDURE FOR THE PREPARATION OF ARYLAMID YELLOW PIGMENTS |
-
1978
- 1978-03-15 NL NL7802831A patent/NL7802831A/en not_active Application Discontinuation
- 1978-03-15 DE DE2811294A patent/DE2811294C2/en not_active Expired
- 1978-03-16 CA CA000299118A patent/CA1116810A/en not_active Expired
- 1978-03-17 SU SU782593447A patent/SU791254A3/en active
- 1978-03-17 FR FR7807746A patent/FR2384004A1/en active Granted
- 1978-03-17 ES ES467980A patent/ES467980A1/en not_active Expired
- 1978-03-17 DK DK121678A patent/DK153327C/en not_active IP Right Cessation
- 1978-03-17 IT IT7821347A patent/IT1113168B/en active
- 1978-03-17 BR BR7801661A patent/BR7801661A/en unknown
- 1978-03-17 AU AU34245/78A patent/AU3424578A/en active Pending
- 1978-03-18 JP JP3161878A patent/JPS53115741A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| FR2384004A1 (en) | 1978-10-13 |
| DK121678A (en) | 1978-09-19 |
| DE2811294C2 (en) | 1986-09-25 |
| SU791254A3 (en) | 1980-12-23 |
| IT7821347A0 (en) | 1978-03-17 |
| IT1113168B (en) | 1986-01-20 |
| ES467980A1 (en) | 1979-09-01 |
| FR2384004B1 (en) | 1980-05-16 |
| AU3424578A (en) | 1979-09-20 |
| BR7801661A (en) | 1978-12-19 |
| JPS53115741A (en) | 1978-10-09 |
| NL7802831A (en) | 1978-09-20 |
| DE2811294A1 (en) | 1978-09-21 |
| DK153327C (en) | 1988-11-14 |
| DK153327B (en) | 1988-07-04 |
| JPS6239182B2 (en) | 1987-08-21 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| MKEX | Expiry |