Chapter Three DEVELOPMENT OF ORGANIC PIGMENTS Organic Pigments are finally divided crystalline solids. They are insoluble in the medium in which they are used. Organic pigments are used in paints, printing Inks, rubber, plastics etc. Organic pigments have a high surface energy which is reduced during manufacture especially during drying of the pigments, press-cake and grinding process, by aggromeration and aggregation ‘The most important development of organic pigment technology isto improve colourstrengthandbrightness. of pigments. The colour increases with decreasing particle size. The shape of particle is also important factor for colour strength. It has been shown recently that particle shape is an importnat factor and acicular particle can give rise to surface imperfections larger than themselves. Bronzing is another surface defect, which is associated with particle size. ‘The physical condition is as important as its chemical constitution, The shade, colour strength, brightness, rheological properties and fastness to various agents ‘such as light, solvents and heat all affected by the physical condition of pigment. The effect on colour strenght and shade can be seen by comparing crude and pigmentary copper - phthalocyanine. A Vast range of anionic, cationic and nonionic surfactants and water soluble colloids are used in very small amounts with pigments during manufacturing process. Large amount of surfactants are undesirable during manufacturing as particle growth restrained so that filtration of pigment is difficult. Surfactants reduce the energy required for dispersion of pigments, choice of surface active agents for pigment dispersion is tedious, trial and error process because of the tremendous variety of pigment types, surfactants and vehicles, The HLB concept of surfactant classification can be quite useful in selecting surface active agents for pigmentdispersion. The HLBi.e. Hydrophilic-Lipophitic, Balance - system of surfactant classification is developed by Atlas Chemical Industries Inc. In the Allas system, surfactants are assigned HLB value according to their relative solubility in oil and water. Every pigment colour has a required HLB for optimum dispersion. Best resultsare obtained when surfactant blend with an HLB matching the required HLB of the pigment is used, TABLE 3.1 REQUIRED HLB VALUES - PIGMENT COLOURS Pigments Required HLB Organics BON Red dark 68 Toluidine red medium 840 Toluidine yellow on Phthalocyanine green (yellow shade) 12-14 Phthalocyanine green (blue shade) 10-12. Phthalocyanine blue (red shade) 11-43, Phthalocyanine blue 14-16 (intermediate shade) Phthalocyanine blue 14-16 (Intermediate shade) Phthalocyanine blue (green shade) 14-16. “Green-Gold” 11-13 Quinacridone violet 11-13, Quinacridone red 1244 High strength Azo yellow 13-15 Inorganics Lampblack 10-12 Red iron oxide 13-45 Molybdate orange 16-18 Rutile titanium dioxide 17-20 Chrome yellow medium 18-20 Yellow iron oxide 20+TABLE 3.2 II, Calculated or determined HLB for various surfactants used for universal and aqueous colour dispersions Surfactants Trade Name Mir Chemical Designation HLB Span 85 Fe Sorbitan trioleate 18 Span 65 4 one Sorbitan tristearate. 24 Centrol 3F 1 2 sue Natural lecithin .. 36 Arlacel C 1 une Sorbitan sesquioleate 87 Triton X-15 3 sno Octyl phenyl - EO 37 Span 80... 4 ce Sorbitan mono-oleate 43 Igepal CO-210...... se 4 son Non! phenyl = EQ sincnsnannnnnnnnnnnnnnnee 46 Span 60... 4 cn Sorbitan monostearate 47 Span 40. 1 on Sorbitan monostearate soe OT 6-672 1 en Glycerol sorbitan laurate 76 Tergitol NP - 14 5 ve» Nonyl phenyl - EO 78 Triton X = 35... cvs 3 nonne Octyl phenyl = EO 79 Hyonic PE - 30 1 6 sone Alkyl phenyl polyoxyethylene ..cccnnnnnnnnn 79 Span 20 1... Sorbitan monolaurate 86 Igepal CO-430 soe 4 nse NOnyl phenyl - EO “ 88 Glycosperse LA - 4. 7 sum Polyoxyethylene lauryl ether... 94 Renex 648 4 sue. Polyoxyethylene alkyl arylether 95 Igepal DM - 430... 4 ones Dinonyl phenyl — EO 95 Triton X = 45. 8 snes HS00etyt Phenyl = EO semen 104 TWEEN 65 scene 1 on, Sorbitan tristearate - EO 105 Igepal CO - 530 4 cone NORV PHENYL = EO ensnnnnnnnninnnnnnne 10.8 Tergitol NP - 27 5 se. Nonyl phenyl - EO svennee 10.9 Nonic 260 on. 8... Tertdodecy! thioether 110 Igepal DM-530 soe 4 snes Dinonyl phenyl = EQ nrsnnnnnnnnnnennnen 110 G-7076 - 1 une Sorbitan dilaurate - EO 112 MYRU - 45, 1 u. Polyoxyethylene stearate 11.2 Igepal CO - 610 7 4 so Nonyl phenyl - EO 120 Hyonic PE - 70 6... Fatty acid alkylolamide 12.4 Triton X= 114 3 snus Polyoxyethylated t-octylphenol 123 Renex 688 .. 4 une Polyoxyethylene alkyl aryl ether 124 Igepal CO - 630. 4 sane Nonyl phenyl - EO . 128 Hyonic PE - 90. + 6 sou. Fatty acid alkylolamide 13.0 Triton X-100 ++ 8 sone Polyoxyethylated T-octyliphendl ..ncnnnennss 182 Renex 698 4 cs Polyoxyethylene alkyl aryl ether 13.4 Nonic 218 Bu Polyethylene glycol tertdodecy! thioether... 138.5 Tergitol NPX soe 5 sues Nonyl phenyl = EO... 13.6 Hyonic PE-100 6 vn Fatty acid alkylolamide . 13.7 2 HANOBOOK OF SYNTHETIC DYES & PIGMENTS‘Surfactants Trade Name Mtr Chemical Designation GOMMBN Igepal CA -630 Triton X-102 G-TA26N.... Tween 60 CFB 96 on Igepal CO-730 MYRU-49, Renex 678 Tween 80... Tergitol NP - 35... Hyonic PE - 150 Triton X-165 Tween 40... Igepal CO-850 .... Hyonie PE-200. Tergitol NP-40 Triton X-208... G-7596-P . Sorbitan monooleate - EO .. Nonyl phenol - EO .... . Sorbitan monolaurate - EO. Sorbitan monooleate - EO 1so-Octoylphenol-EO Polyoxyethylated T-octylphenol Sorbitan monopalmitated - EO ... Sorbitan monostearate - EO Sorbitan monolaurate - EO. Nonyl phenol - EO Polyoxyethylene stearate Polyoxyethylene alkyl aryl ether Nonyl phenyl = EO sven Alkyl phenyl - EO. ctyl phenyl - EO Sorbitan monopalmitate - EO Alkyl phenyl - EO... Nony! phenyl - ctyl phenyl - Tween 20 Sorbitan monolaurate - EO. Glyoosperse LA-23 -nnn Lauryl ether - EO lgepal CO-880 Nonyl phenol - EO MyRU-52, .. Polyoxyethylene stearate - Renex 650 Polyoxyethylene alkyl aryl ether 474 Hyonic PE-300 ‘Alkyl phenyl ~ Triton X-308... Cctyl phenyl - EO : MYRU-5S, Polyoxyethylene stearate 179 Aiipal CO-436 Ammonium sulfate ester nonyl phenol» EO ...25.0 Alipal CO-433 ..... ‘Ammonium sulfate ester nonyl phenol - EO ....25.0 Surfynot 440 _ Nonyl phenyl = EO... Makon 4 ‘Alkyl phenyl polyoxyethylene Igepal CO-810 .. Nonyl phenyl = EO wn. Makon 14 Aikyl phenyl polyoxyethylene ‘Surtynol 485, 9 ss Nonyl phenyl - EO é Manufacturers (1) Allas Chemical Industries, Inc. (6) _Nopco Chemical Co. (2) Central Soya Co. Inc. (7) Giyco Chemicals, Inc. (3) Rohm & Haas Co. (8) Pennsalt Chemicals Corp. (4) Antara Chemicals Div., General Aniline & Film Corp. (8) Air Reduction Co. ne. (6) Union Carbide Corp., Chemicals Div. DEVELOPMENT OF ORGANIC PIGMENTS (10) Stepan Chemical Co.Polymorphism Polymorphismisa very common feature of he pigment chemistry. The characteristic colour of a pigment is, determined primarily by the chemical constitution of its molecules. Also the molecules are arranged in the crystal lattice can have important secondary effects, copper phthalocyanince Blue (C.I. pigment Blue 15) is the best example which can exist in many lattice arrangement, the cis reddish blue andthe Bis greenish blue. In both forms, the individual particles are made up of layers of flat phthalocyanine molecules but differ in the relation of individual layers as shown below. Copper phthalocyanine as synthesizedisin the Bform, with acicular crystals upto about 100 microns in length. It may be reduced to pigmentary size by acid pasting oF permutoid swelling in which case the « form is, produced. The « form is thermodynamically unstable and reverts to the B form on prolonged heating. Another important example of polymorphism is Quinacridone pigments (C.1. pigment violet 19), which exists in three main forms as follow : a= form a fed. B - form= vioiet y> form — red, Quinacridones that are substituted symmetrically at positions 2 and 9 or 3 and 10 are solvent stable and do not undergo crystal - phase modification. Fig. 1. Relation between two phthalocyanine molecules in neighbouring layers. HANDBOOK OF SYNTHETIC DYES & PIGMENTSGoup_ Crystal ‘Agglonerates 7 O Aagregete 9 B® te B e SS SSS Figure 2 Schematic representation af crystalline pigment particles of varying shape: 1 Compact and Isometric ul Compact and anisometric uw Not compact (a) spherical, (a) plates, fissured, (©) polyhedral (0) needles oF rods, irregular {c) irregular. (©) irregular. Single erystals and agglomerates of crystals and aggregates are spoken of as particles in a true dispersion or suspension of pigment. In borderline cases, the particles consist only of single crystals and agglomerates of crystals, or only of aggregates ‘and agglomerates of aggregates. Aggregation/Agglomeration Organic pigment powders consist of small crystals and arranged in various state of assembly. The smaller ‘crystals seldom exist as individual entities but instead as aggreagates or as less firmly bound agglomerates. The size of aggregates and small agglomerates relates to the colour strength. The geometric arrangements with in weaker agglomerates and air flocculates also affect the texture of the powder, its bulkiness and compressibility and influence its dispersibiliy. Aggregates consist of crystals that have grown together face to face, An agglomerate comprises a Clustersot aggregates and or single crystals that are joined together only at their comers and edges, that is over a very restricted surface area Aggregates/Agglomerates is liable to occur during the drying of aqueous presscakes. It does not allow the optimum colour strength by increasing the effective particle size. DEVELOPMENT OF ORGANIC PIGMENTS Aggregates and Agglomerates can be reduced by three processes as suggested below (1) Treatment of the pigment with solvents. (2) Treatment of the pigment with additives. (3) by mechanical means Additives are most effective in reducing aggregation! agglomeration if they are present when the pigment crystals are being formed. ‘Aggregates and Agglomeratescan occurduring storage and transport of pigment powders under the influences, of gravity vibration and uptake of moisture. It can also ‘occur when the pigment powder is being wetted and dispersed in liquid systems. Pigment Particles Pigments are produced in wet presscake froms which after drying, grinding or spray drying converted intofine dry powder. Pigment content of presscake is 20- 40% or a high solids 50 to 60%, which can be directly used{or flushed colours or aqueous pastes of pigments for different industry. The colour properties are influenced by particle size and particle size distribution. Phthalocyanine blue is first prepared commercially in a “Crude” pigment form having a large particle size upto 25m. Ithas very little colour value. After particle size reduction (0.03-0.15um) excellent pigment is obtained Dispersibility of organic pigments The purpose of dispersion is to break down pigment aggregates and agglomerates to their optimum pigmentary particle size so that the pigment should be {lly dispersed, the smallest the particle size the stronger the colour. In fluid systems such as inks and paints dispersion includes, wetting, separation of particles and stabilization of the dispersion formed. The dispersion of organic pigment decreases with decrease in mean particle size. If the dispersion has not been stabilised flocculation may occur, which is reversible process. Soto stabilise, dispersion, surfactant such as Anionic, Non-ionic etc, or polymeric dispersants or addition should be added. Flocculation can be reduced or eliminated by the use of additives. Effective additives can be adsorb to the surface of the primary pigment particles and it modity the interfacial properties namely electrostatic and steric stabilization. Additives may be used during pigment manufacture as preformed compounds, the mode and stage of addition being important to their effectiveness: During the precipitation of intermediate, surfactants are used to wetout and control the fineness of the precipitate and itactsas promoter to accelerate azo coupling. tis also used to control agglomeration. The process of dividing pigmentagglomeratesis called dispersion, it is done by the application of shearing forces. Typical apparatus, for dispersion are roller mills, kneaders, ball mills, atrition mills, sand mills and dissolvers, Destruction of aggregates or even crystallites of organic pigments takes place in exceptional cases only. The resistance put up by an organic pigment towards dispersion, i.e, mainly wetting and comminution of agglomerates, is a measure ofits dispersibilty. The dispersion of organic pigments fluctuates within wide limits; as a rule pigments consisting of smaller or medium-sized particles are more difficult to disperse than those of large particle size; however, exceptions are possible because the mean particle size of a pigment constitutes an integrated magnitude and does ‘not indicate the particle size distribution which plays a decisive part in the dispersibilty. fa pigment is not pertectly dispersed in the medium in which it is applied, various kinds of trouble are to be expected. In printing inks, bad ink transport and premature destruction of the printing block during the printing process has to be reckoned with, in paints a reduction in gloss and worsening of the weathering resistance, in plastics films, holes during vacuum forming, just to mention a few of the disturbances to be expected. Besides, if a pigment is not properly dispersed, its surface that has a colouring effect is not completely exposed so that the appropriate tinctorial strength is only partially attained. From this it follows that the economy of pigments is improved by good dispersion. A dispersion brings out the optimum colour properties, of the pigment in terms os colour strength, gloss, transparency, and rheology and when it is completely dispersedit contains alarge number of primary particles. Easily dispersible pigments Easily dispersible pigments help to cut down dispersion costs and at the same time make pigmentation more economical by increasing the colour yield. Pigment can be converted into E.D.P. by following methods (1) Pigmentis predispersedin suitable media during manufacturing process. An example is the dispersion of pigments at approx 40% Concentrationina plasticiser-soluble PVC/PVAC Copolymer medium. Pigment preparations of thistype are used orcolouration of PVG masses and spread Coating compounds. (2) Thesurfacetreatmentof organic pigments during their manufacture gives E.D pigments. Small Quantities of suitable substances is added during manufacture of pigments, and.coating the surface of pigment crystallites so that no agglomerates formed during subsequent drying and grinding, ‘The pigments thus obtained are EDP in certain media. To achieve good result by this method, the pigment manufacturer should influence the Particle size distribution towards the formation of crystallites of uniform size to minimise the extent of agglomeration. The surface treatment 6 HANDBOOK OF SYNTHETIC OYES & PIGMENTSof organic pigments with primary aliphaticamine salts, di and tr-amines and abietylamines improve the dispersibility and also increase the flocculation stability of the pigments in aromatic hydrocarbon systems. Besides the use of amines, PVC plasticisers of the phthalic acid ester type can be used for the surface treatment of organic pigments during manufacturing process for E.D.P. The pigments enveloped with the plasticiser have considerably less tendency to agglomerate and are much easier to disperse in unplasticised and plasticised PVC compounds, ‘Several methods of manufacturingE.D. pigments involve the processingof aqueous pigment press- DEVELOPMENT OF ORGANIC PIGMENTS @) cakes with various copolymer dispersions. The state of extremely fine division is stabilised by enveloping the pigment crystallites immediately after their formation with the copolymer particles. In recent times E.D. pigments have been obtained by influencing the particle size distribution during the manufacture and finishing of organic pigments. The dispersibilty of some of these pigments is considerably increased in all applications media ‘example : Pigment yellow 13, phthalocyanine. ‘The E.D. pigments are gaining increasing importance in an industry which is geared to rational production