Technical Bulletin The Use of SURFONAMINE Dispersant Intermediates. Amines as Pigment Modifiers and

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1 Technical Bulletin The Use of SURFONAMINE Dispersant Intermediates Amines as Pigment Modifiers and In an ink or coating formulation the pigment must be dispersed and stabilised to achieve good colour strength, gloss, transparency, and transfer efficiency. Stable, concentrated dispersions with small particles and narrow particle size distribution potentially can lead to higher gloss and colour strength per unit mass of pigment. The push towards water-based formulations and increasing pigment loading underline the needs for good dispersion and stabilisation properties. DESCRIPTION The SURFONAMINE B- and L- series contain primary groups attached to the ends of a polyether backbone. They are thus polyether monos. The polyether backbone is based on either propylene oxide (PO), ethylene oxide (EO), or mixed EO-PO. Thus the ratio of EO to PO in the backbone determines the propensity of a particular SURFONAMINE towards either hydrophilicity (the L-series) or hydrophobicity (the B-series). In order to achieve dispersion and stabilisation of a pigment concentrate, two broad approaches can be taken: Modify the surface properties of the pigment itself Use a dispersing agent in the ink formulation or coating Huntsman s line of SURFONAMINE s provide unique properties in terms of reactivity and compatibility that make these molecules useful for pigment modification and for the synthesis of unique dispersant molecules. FEATURES The functionality allows variety of reaction options as well as neutralisation Different EO/PO ratio (either block or mixed EO/PO) provide different HLB values (Table 1) Wide range of molecular weight Flexible polyether backbone Low viscosity liquids or waxy solids with low vapour pressures Table 1: Huntsman s line of SURFONAMINE s Product Name SURFONAMINE B-60 SURFONAMINE B-100 SURFONAMINE B-200 SURFONAMINE L-100 SURFONAMINE L-200 SURFONAMINE L-207 SURFONAMINE L-300 Structure Ratio EO/PO Approx. MW CH 3 -[OCH 2 CH 2 ] x -[OCH 2 CH(CH 3 )] y -NH 2 1/ HLB* value C 9 H 19 -φ-[och 2 CH(CH 3 )] OCH 2 CH(CH 3 )-NH 2-1,000 < 1.0 CH 3 -[OCH 2 CH 2 ] x -[OCH 2 CH(CH 3 )] y -NH 2 6/29 2, CH 3 -[OCH 2 CH 2 ] x -[OCH 2 CH(CH 3 )] y -NH 2 19/3 1, CH 3 -[OCH 2 CH 2 ] x -[OCH 2 CH(CH 3 )] y -NH 2 41/4 2, CH 3 -[OCH 2 CH 2 ] x -[OCH 2 CH(CH 3 )] y -NH 2 33/10 2, CH 3 -[OCH 2 CH 2 ] x -[OCH 2 CH(CH 3 )] y -NH 2 58/8 3, *The relationship used to calculate the HLB values is HLB = 20 x M H /(M H + M L ) where M H is the formula weight of the hydrophile and M L is the formula weight of the lipophile. HLB values give a measure of the surfactant s solubility in aqueous solution. Water solubility in general increases with increasing HLB value.

2 USE IN PIGMENT MODIFICATION The reactive functionality present on the SURFONAMINE provides a means to chemically graft these molecules onto a reactive site of the pigment particle: examples include carboxylic acid, reacting with to form polyalkoxy carboxamide, or sulfonic acid, reacting with to form polyalkoxy sulfonamide. The ethylene oxide/propylene oxide (EO/PO) chain of the SURFONAMINE molecule chemically linked to the pigment provides a better compatibility with the medium in which it is dispersed. This ultimately results in better dispersion and stability of the pigment when it is used in an ink formulation or in other applications such as paints and coatings. The ability to tailor the EO/PO ratio in the backbone of the SURFONAMINE allows the chemist to essentially dial-in the desired hydrophilicity. Figure 1: Effect of molecular weight and Ethylene Oxide on surface tension (measured at 100 ppm on molecular weight and weight % of ethylene oxide) BENEFITS Adsorption and Dispersion Efficiency The polyether monos do not show a distinct critical micelle concentration (cmc) even though they are surface active Surface tension and interfacial tension values decrease with decreasing ethylene oxide content of the polyether backbone (Figure 1 and 2) The polyether mono molecular weight has a slight effect on surface tension and interfacial tension, being more pronounced at high contents of ethylene oxide (Figure 1 and 2) The adsorption at air/liquid interface increases with increasing ethylene oxide and exhibits a maximum at 2000 molecular weight (Figure 2) Adsorption and contact angle measurements indicate that a polyether having a high ethylene oxide content and high molecular weight provides the best performance: the contact angle decreases with increasing ethylene oxide; the molecular weight has less pronounced effect (Figure 3) Figure 2: Effect of molecular weight and Ethylene Oxide on Adsorption at Air/Liquid Interface Figure 3: Effect of molecular weight and Ethylene Oxide on Water Contact Angle of dispersions

3 USE IN PIGMENT MODIFICATION (Continued) Stability and transfer efficiency Grafting a polyether mono to a pigment improves flow properties and dispersibility: These results have important implications in terms of maximum pigment loading, storage stability, and colour density of fully formulated dispersions and finished inks. The literature reveals that this approach of reacting the SURFONAMINE s with pigments can be used for a variety of pigment classes so long as the pigment possesses functional sites with which to react the SURFONAMINE. Diarylide yellow pigments have been reacted with SURFONAMINE L-207 to result in pigments that gave superior storage stability in terms of colour shift and viscosity retention Monoazo pigments have been modified to give inks greater colour strength and lower viscosity Descriptions of the process have included a wide variety of colours and chemistries that are amenable to this type of modification. USE AS DISPERSANT INTERMEDIATE SURFONAMINE s can also be used as reactant building blocks to construct more complex dispersants. The choice of the appropriate polyether monos will determine the compatibilisation properties of the final molecule, depending on the hydrophilicity and length of the polyether backbone: By understanding the effect of each portion of the molecule on the physical properties and performance, new dispersants can be developed. In terms of molecular architecture, the final dispersant molecules may be linear, branched or comb-like (Figure 4). For example, SURFONAMINE s have been reacted with polyacrylic acids, styrenemaleic anhydride copolymers, polyurethanes and epoxies. The resulting copolymers were found to present superior dispersant properties resulting in better viscosity profiles, and better stability of both the ink dispersion and the formulated ink. SURFONAMINE Amine with terminal capped with BAB block functional groups functional groups at copolymer both ends JEFFSPERSE X3000 series ABA block Random copolymer Comb copolymer copolymer Figure 4: Types of dispersants

4 OTHER HUNTSMAN PRODUCTS FOR AQUEOUS DISPERSIONS Huntsman offers a range of alkylene carbonates which are suitable as coalescing aids for waterbased emulsions having a slightly acidic to neutral ph. Huntsman offers a range of specialty s that can be used as neutralisers: DIGLYCOLAMINE agent/dga agent, DMEA, MDEA, MMEA, DMAPA, APM. Huntsman offers one of the broadest ranges of anionic and nonionic surfactants to the global emulsion polymerisation market. These ranges are in continual research and development cycle - recent developments include speciality sulphosuccinates and novel technologies for APE replacement. BIBLIOGRAPHY Hugh M. Smith (Ed.), High Performance Pigments, Wiley-VCH Verglag-GmbH, Weinheim, Germany, 2002 US Patent 5,024,698, June 18, 1991, Monozao pigment compositions to Sun Chemical Corp. US Patent 6,228,942, May 8, 2001 Surface modified carbonaceous materials to Hydro-Quebec & Centre National de la Recherche Scientifique US Patent 5,766,268, June 16, 1998, Poly(oxyalkylene)-substituted colorant to Milliken Research Corporation US Patent 5,589,522, December 31, 1996, Ink composition to Lexmark International, Inc. US Patent 6,221,932, April 24, 2001, Covalent attachment of polymers onto macromolecular chromophores by nucleophilic substitution reaction for inkjet printing to Hewlett-Packard Co. US Patent 6,406,143, June 18, 2002, Ink jet printing method to Eastman Kodak Co. US Patent 7,265,197, September 4, 2007, ic Dispersant to Sun Chemical Corp. References to patent documents herein are provided as background information only, and should not be construed as a suggestion to make, use, or sell any invention claimed without authorization from the patent owner. AVAILABILITY Requests for samples can be made through any Huntsman sales office. PRODUCT SAFETY POLICY It is the policy of Huntsman to provide customers with information on the safe handling and use of our products. The Material Safety Data Sheet (MSDS) should always be read and understood thoroughly before handling the product and adequate safety procedures should be followed. Information on toxicity, environmental and industrial hygiene aspects of our products may be found in the MSDS, which is available upon request through any Huntsman office.

5 REGULATORY INFORMATION Technical bulletins on individual products are available upon request through any Huntsman office or on our website. Table 2 summarizes regulatory information for Huntsman s SURFONAMINE product range: this information is accurate at the time of printing- please contact your Huntsman representative if you have any questions or need additional details. All listed SURFONAMINE s have been preregistered for REACH. Table 2: SURFONAMINE s regulatory information SURFONAMINE s B-60 B-100 B-200 L-100 L-200 L-207 L-300 DOT/DTG Classification See MSDS regulated See MSDS regulated regulated regulated regulated HMIS Code CAS Number Proprietary US, TSCA Canada, WHMIS Classifications D1B, D2B D2B D1B, D2B regulated regulated regulated regulated Canada, DSL European Union, EINECS/ELINCS Australia, AICS Korea, ECL Japan, METI China, IECSC Copyright 2007, 2009 Huntsman Corporation or an affiliate thereof. All rights reserved. SURFONAMINE-0609 Warning: Products manufactured from these chemicals may present a fire hazard if improperly used. Each manufacturer and user of such products should determine whether there are potential hazards in a specific application and take the necessary precautions. Huntsman Petrochemical Corporation warrants only that its products meet the specifications stated in the sales contract. Typical properties, where stated, are to be considered as representative of current production and should not be treated as specifications. While all the information presented in this document is believed to be reliable and to represent the best available data on these products, NO GUARANTEE, WARRANTY, OR REPRESENTATION IS MADE, INTENDED, OR IMPLIED AS TO THE CORRECTNESS OR SUFFICIENCY OF ANY INFORMATION, OR AS TO THE MERCHANTABILITY OR SUITABILITY OR FITNESS OF ANY CHEMICAL COMPOUNDS FOR ANY PARTICULAR USE OR PURPOSE, OR THAT ANY CHEMICAL COMPOUNDS OR USE THEREOF ARE NOT SUBJECT TO A CLAIM BY A THIRD PARTY FOR INFRINGEMENT OF ANY PATENT OR OTHER INTELLECTUAL PROPERTY RIGHT. EACH USER SHOULD CONDUCT A SUFFICIENT INVESTIGATION TO ESTABLISH THE SUITABILITY OF ANY PRODUCT FOR ITS INTENDED USE. Liability of Huntsman Petrochemical Corporation and its affiliates for all claims is limited to the purchase price of the material. Products may be toxic and require special precautions in handling. For all products listed, user should obtain detailed information on toxicity, together with proper shipping, handling and storage procedures, and comply with all applicable safety and environmental standards. DIGLYCOLAMINE, DGA and SURFONAMINE are registered trademarks of Huntsman Corporation or an affiliate thereof in one or more, but not all countries. Main Offices US: Huntsman Corporation / Woodloch Forest Drive / The Woodlands, Texas / Technical Service US: 8600 Gosling Road / The Woodlands, Texas / Main Offices Europe: Huntsman Belgium BVBA / Everslaan 45 / B-3078 Everberg, Belgium / Technical Service Europe: Technical Services Representative / Everberg Office / Main Offices Asia Pacific Offices: Huntsman Singapore PTE / 150 Beach Road, #37-00 Gateway West / Singapore / Technical Service Asia Pacific: Huntsman Chemistry R&D Center/455 Wen Jing Road, Shanghai /P.R.China/