MIGRATION RESISTANCE

Raw Materials. PVC is inherently a hard and brittle material and very sensitive to heat it thus must be modified with a variety of plasticizers, stabilizers, and other processing aids to form heat-stable flexible or semiflexible products or with lesser amounts of these processing aids for the manufacture of rigid products (see Vinyl polymers, vinyl chloride polymers). Plasticizer levels used to produce the desired softness and flexibihty in a finished product vary between 25 parts per hundred (pph) parts of PVC for flooring products to about 80—100 pph for apparel products (245). Numerous plasticizers (qv) are commercially available for PVC, although dioctyl phthalate (DOP) is by far the most widely used in industrial appHcations due to its excellent properties and low cost. For example, phosphates provide improved flame resistance, adipate esters enhance low temperature flexibihty, polymeric plasticizers such as glycol adipates and azelates improve the migration resistance, and phthalate esters provide compatibiUty and flexibihty (245). 

Another important pigment in this class is Pigment Red 170 [6985-95-17, which provides medium shades of red, and when particle-grown produces an opaque modification which shows improved migration resistance and lightfastness. Like some other Naphthol AS pigments it shows the phenomenon of polymorphism. 

Tris(2-ethylhexyl) phosphate shows good compatibiUty with PVC and also imparts good low temperature performance in addition to good fire retardancy. 2-Ethyhexyl diphenyl phosphate has widespread use in dexible PVC appHcations due to its combination of properties of plasticizing efficiency, low temperature performance, migration resistance, and fire retardancy. 

Plasticizers. Plasticizers are materials that soften and flexibilize inherently rigid, and even britde polymers. Organic esters are widely used as plasticizers in polymers (97,98). These esters include the benzoats, phthalates, terephthalates, and trimeUitates, and aUphatic dibasic acid esters. Eor example, triethylene glycol bis(2-ethylbutyrate) [95-08-9] is a plasticizer for poly(vinyl butyral) [63148-65-2] which is used in laminated safety glass (see Vinyl POLYMERS, poly(vinyl acetals)). Di(2-ethyUiexyl)phthalate [117-81-7] (DOP) is a preeminent plasticizer. Variation of acid and/or alcohol component(s) modifies the efficacy of the resultant ester as a plasticizer. In phthalate plasticizers, molecular sizes of the alcohol moiety can be varied from methyl to tridecyl to control permanence, compatibiUty, and efficiency branched (eg, 2-ethylhexyl, isodecyl) for rapid absorption and fusion linear (C6—Cll) for low temperature flexibiUty and low volatility and aromatic (benzyl) for solvating. Terephthalates are recognized for their migration resistance, and trimeUitates for their low volatility in plasticizer appHcations. 

All members of this pigment family share good lightfastness, combined with poor solvent and migration resistance. These properties define and limit their application. Monoazo yellow pigments are used extensively in air-dried alkyd resin and in emulsion paints, and certain inks used in flexo and screen printing. Other applications are in letterpress and offset inks, as well as in office articles. 

These pigments are obtained by coupling substituted aryl diazonium salts with ary-lides of 2-hydroxy-3-naphthoic acid (2-hydroxy-3-naphthoic acid anilide = Naph-tol AS). They provide a broad range of colors from yellowish and medium red to bordeaux, carmine, brown, and violet their solvent fastness and migration resistance are only marginal. Naphthol AS pigments are used mainly in printing inks and paints. 

Although of comparatively good light- and weatherfastness, solvent and migration resistance, only a few members of the isoindolinone and isoindoline families are commercially available as pigments. Chemically classified as heterocyclic azome-... 

Flavanthrone Yellow, the only commercially used flavanthrone, is a moderately brilliant reddish yellow. Excellent lightfastness and weatherfastness, combined with good solvent and migration resistance, make this pigment an attractive supplement to Anthrapyrimidine Yellow, mainly in the automotive finish industry. 

The influence of the chemical constitution as related to solvent and migration resistance opens up a number of options to improve pigment performance ... 

Complexation of o,o -dihydroxyazo compounds or their corresponding azo-methine derivatives affords extremely solvent and migration resistant pigments (Sec. 2.10). 

In most cases the pigments used are also required to be migration-resistant. The suitability test is also carried out with 5 different pigment concentrations. To test the fastness to bleeding, the unvulcanized colorations are brought into defined contact with a white milled sheet of specific composition and vulcanized wet for 20 minutes in open steam at 140°C. During this process, half the coloration is often covered with a wet cotton cloth to determine whether the cloth, the rubber or both are stained by bleeding. 

Finishing not only improves the application properties of a pigment, such as hue, tinctorial strength, brilliance, transparency/hiding power, dispersibility, and flow behavior, but also considerably enhances its lightfastness and weatherfastness and its solvent and migration resistance. 

A more traditional approach consists of introducing sulfonic acid substituents into yellow monoazo compounds. These can simply be precipitated, i.e., converted to lakes by salt formation, especially with calcium, and thus afford the more solvent and migration resistant monoazo yellow pigment lakes. 

Introducing acidic substituents into the basic structure of a typical monoazo yellow pigment makes it possible to convert the material into a lake by salt formation. This improves the application properties of a pigment compared to its non-laked counterpart. Such pigments exhibit particularly good migration resistance and heat stability, making them useful colorants for plastics. 

Tables 11 and 12 list the currently available non-laked monoazo yellow and orange pigments. Most of them carry a nitro substituent in the diazonium component, usually in ortho position relative to the azo bridge. The more migration-resistant Pigment Yellow 97 lacks a nitro group in its molecule. Seven monoazo yellow pigments are based on 2-nitro-4-chloroaniline or derivatives as a diazo component.

Lightfastness in rubber, which meets almost all requirements, is accompanied by good curing properties and migration resistance. The resulting pigmented articles are very resistant to water and detergent solutions. 

Table 17 lists a number of commercially available pigments, along with their chemical structures, in order to illustrate the different structural types of Naphthol AS pigments. Fastness to solvents and migration resistance improve from top to bottom, i.e., with increasing number of CONH groups in the molecule. The first example, a simple (3-naphthol pigment, is the skeleton from which all other species are derived. 

P.R.95 is suitable for a variety of printing techniques. Poor migration resistance and insufficient fastness to plasticizers render the pigment unsuitable as a colorant in special gravure inks for plasticized PVC. 

Due to the disadvantage of comparatively poor migration resistance, P.R.5 is not used in plasticized PVC, but it can be applied in rigid PVC. Its lightfastness is excellent in this medium, transparent and opaque colorations (up to 0.01% pigment + 0.5% TiOz) equal step 7 and, respectively, step 6-7 on the Blue Scale. Dispersed pigment preparations are available for the mass coloration of viscose films as well as for spin dyeing of viscose rayon and viscose cellulose. 

The next step consisted of introducing groups to improve the hydrophilicity of the parent structure to a certain extent, but not enough to render it soluble in water. Best results were achieved by the carbonamide function. Additional introduction of several such groups, for instance into Naphthol AS pigments, resulted in very solvent fast and migration resistant pigments (Sec. 2.6.2). 

P.R.171 is used in plastics and in paints. Its lightfastness in PVC equals step 7 to step 8 on the Blue Scale, depending on the exact composition of the tested system, the pigment concentration, and the Ti02 content. Incorporated in plasticized PVC, P.O.171 is migration resistant and heat stable up to 180°C. It is used in conjunction with organic yellow pigments, frequently also with iron oxides, to produce shades of brown. Shades of bordeaux are accessible in deep transparent colorations. 

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