Rosin fumarates

A folding carton ink is composed of a hard non-film forming styrene acrylic emulsion vehicle and a styrene acrylic solution vehicle. As an alternative, a film forming styrene acrylic emulsion vehicle and rosin fumarate ester solution vehicle are used. 

A pre-print corrugated ink is composed of a styrene acrylic emulsion colloid vehi-de and a rosin fumarate ester resin and/or styrene acrylic resin solution vehide. The physical properties of emulsions and resins used in pre-print corrugated ink are listed in Tabs 5.4 and 5.5 for. 

Paste rosin sizes are supplied as viscous pastes containing 60—80% solids. These sizes may contain unmodified or fortified rosin that has reacted (ie, been fortified) with either maleic anhydride [108-31-6] or fumaric acid [110-17-8] (see Fig. 3). In either case, the unmodified or fortified rosin is treated with aqueous alkaH so that the degree of neutralization, ie, saponification, varies from 75—100% depending on the physical state desired for the commercial product. Before use, the paste size must be converted to a stable, dilute rosin size emulsion by careful sequential dilution with warm water foUowed by cold water, with good agitation. 

Fig. 3. Resin acids in rosin sizes, R = CH(CH2)2- The rosin acids are represented here as abietic acid [514-10-3] (1) and levopimaric acid [79-54-9] (2). In rosin there are other isomers and disproportionation products. The product of reaction with fumaric acid (3) is levopimaric acid— fumaric acid adduct...

Maleic acid and fumaric acid can also be, and are often, incorporated in alkyd resins in the form of the Diels-Alder adduct of rosin. The adducts are tribasic acids which provide pendent carboxyl groups in the resin molecules, which can be saponified to give ionic, and, in turn, water-soluble characteristics to the resin. However, the resultant alkyds often have poorer color retention, toughness, gloss retention, and exterior durabiUty. 

Rosin is commonly modified with maleic or fumaric acid to improve efficiency. Since the 1970s, dispersions of unsaponifted rosin have become more popular as a result of their improved sizing efficiency, lower alum requirements, and reduced pH sensitivity vs saponified rosins. Cationic dispersed rosin size, which can be effective at near-neutral and neutral papermaking conditions, is also available (63—65). Commercially available rosin sizes include Pexol, Neuphor, and Hi-pHase (Hercules Inc.), Plasmine and NeuRos (Plasmine), Stafor (Westvaco), Novaplus, and Novasize (Georgia Pacific), and NeuRos and Roscol (Akzo Nobel). 

Rosin Modifications. This class includes modifications with phenolics, phthalic alkyds, maleic alkyds, and fatty acids and oils. Rosin modifications can be broken out roughly into rosin and rosin esters, unmodified, and rosin and rosin esters, modified. The unmodified classification can be broken down into esters esterified with glycerol and esters esterified with other alcohols. The rosin and rosin esters, modified can then be broken down to those modified with phenolic and other tar acid condensates, those modified with phthalic alkyds, and those modified with maleic or fumaric alkyds. This is a very complicated classification and great care must be exercised in order to keep the classes consistent and comparable over a period of years. 

Perhaps one of the greatest changes in technology witnessed since the last edition is the decline in the use of anionic rosin size in Europe. Imparting hydrophobicity to paper by the use of rosin modified by maleic anhydride or fumaric acid and stabilised by casein at pH 4.5-5.0 is now seldom seen. 

Rosin is a non-reaclive prodnct and is retained on the anionic fibre by either attaching itself to a cationic source in the case of rosin soap, or anionic rosin emulsion or by having a cationic surface charge. The main requirement is that it requires a source of aluminium species to form the actual sizing agent, aluminium rosinate. Rosin is normally modified with maleic anhydride or fumaric acid to increase its reactivity with aluminium species and improve its efficiency at higher pH. The method by which this aluminium species is formed and retained in the wet-end of the paper/ board machine differs between anionic and cationic rosin sizes. 

In the THM-GC profile of the printing ink resin,dimethyl fumarate (peak 6) is detected, suggesting the presence of maleic or fumaric acid. Pentaerythritol is indicated by the presence of the tetra- and trimethyl ethers (peaks 7 and 8, respectively). Tertiary butyl phenol and methyl and dimethyl tertiary butyl phenols are detected as their methyl ethers (peaks 9, 10, and 11, respectively). Rosin acid methyl esters are detected with dehydroabietic acid and abietic acid methyl esters predominating (peaks 15 and 16, respectively). This resin is therefore diagnosed... 

Furfuryl alcohol phenolic resin comonomer Bisphenol A phenolic resin mfg. p-t-Amylphenol Tall oil rosin phenolic resin modifier Cumyl phenol Fumaric acid phenolic resins Phenol... 

Dimethyl terephthalate rope, high performance Liquid crystal polymer ropes, strapping Polyethylene terephthalate rose oil, synthetic Phenethyl alcohol rose water Rose oil rosin adducts Fumaric acid rosin ester gum mfg. 

The most important rosin derivatives used in printing ink formulations are rosin oligomers and their esters, metal resinates, modified phenolic and alkyd resins, ester gums, maleic and fumaric acid adducts and their esters. Practically all types of printing inks can be manufactured with rosin-based components, because they provide good miscibility and compatibility with most film formers and other ink additives. 

Fumaric resin A synthetic, hard resin formed by the reaction of fumaric acid and rosin. Ash M, Ash I (1982-1983) Encyclopedia of plastics polymers, and resins, vols 1-3. Chemical Publishing Co., New York. 

Modified rosins, however, are of greater importance now than the non-modified material. Typical modifications are hydrogenation-disproportionation, esterification, dimerization, and maleic/fumaric adducts. 

Maleic and fumaric acids often are combined with rosin by the Diels-Alder reaction, and tribasic adducts such as the one shown in the following reaction are formed ... 

Alkyds with either rosin-maleic acid, maleic anhydride, or fumaric acid adducts as the polybasic acids are used in many low-cost coating applications, but the films from these resins do not have the color retention, toughness, adhesion, gloss retention, or exterior durability that the phthalic anhydride alkyds have. 

Unmodified rosins combine with fumaric acid and maleic anhydride in accordance with the Diels-Alder reaction to form tribasic adducts. The resulting polybasic acids are often used instead of phthalic anhydride in the production of alkyd resins for low-cost coatings. These rosin-derived, nonphthalate alkyds are used to improve gloss and other properties and are suitable mainly for interior coalings. They do not possess the high degree of outdoor durability characteristic of alkyd resins derived solely from phthalic anhydride. 

Maleic modified rosin is a commercial product and widely used as a binder in the printing ink industry. Levopimaric acid with its conjugated doubie bonds can undergo a Diels-Aider reaction with maleic anhydride, maleic acid or fumaric acid to produce maleic... 

Fortified size Rosin size that has been reacted with fumaric acid or maleic anhydride to form the Diels-Alder adduct The reaction product contains extra carboxyl groups and produces more eflident sizing response than the unreacted resin acids. It is used as a starting material for other size products. 

A fumarated rosin polyamine condensation resin is explained in a second Westvaco patent - Modified Rosin Resins for Waterbased Inks. The condensation reaction product of polyamines with certain rosin-based polycarboxyhc acids results in an efficient pigment dispersion resin and gives a stable viscosity over a wide range in pH, between 8.5 to 10.5 [5]. These resins and others not discussed provide alternatives for dispersing pigments. 

The key solution polymers (resins) used in printing ink are styrene or rosin based. Styrene-a-methylstyrene monomer and acid functional co-monomers (i.e. acrylic or methacrylic acid) comprise the bulk of styrene acrylic solution vehides used in printing ink. Rosin acid reacted with fumaric add gives a tri-functional adduct . The adduct is partially esterified with polyols such as pentaerythritol, glycerin, diethylene glycol, etc. to achieve a range of addity, viscosity, Tg and molecular weight. 

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