Tackiness

The adherence of solids is more often studied with a tensile test machine at constant crosshead velocity than at constant load, but the kinetics of separation is less easier to interpret, due to the competition for increasing G with time between increasing 8 with time at constant a, and decreasing a at constant 8. If the machine has an infinite rigidity one has A = 8 and the variation of G with time is given by 

---

A typical example is total monomers. 100 sodium stearate, 5 potassium persulfate, 0.3 lauryl mercaptan, 0.4 to 0.7 and water, 200 parts. In this formula, 75 parts of 1,3-butadiene and 25 parts of 4-methyl-2-vinylthiazole give 86% conversion to a tacky rubber-like copolymer in 15 hr at 45°C. The polymer contains 62% benzene-insoluble gel. Sulfur analysis indicates that the polymer contains 21 parts of combined 4-methyl-2-vinylthiazole (312). Butadiene alone in the above reaction normally requires 25 hr to achieve the same conversion, thus illustrating the acceleration due to the presence of 4-methyl-2-vinylthiazole. 

Polymers of different tacticity have quite different properties, especially in the solid state. One of the requirements for polymer crystallinity is a high degree of microstructural regularity to enable the chains to pack in an orderly manner. Thus atactic polypropylene is a soft, tacky substance, whereas both isotactic and syndiotactic polypropylenes are highly crystalline. 

Below T polymers are stiff, hard, britde, and glass-like above if the molecular weight is high enough, they are relatively soft, limp, stretchable, and can be somewhat elastic. At even higher temperatures they flow and are tacky. Methods used to determine glass-transition temperatures and the reported values for a large number of polymers may be found in References 7—9. Values for the T of common acrylate homopolymers are found in Table 1. 

Mechanical and Thermal Properties. The first member of the acrylate series, poly(methyl acrylate), has fltde or no tack at room temperature it is a tough, mbbery, and moderately hard polymer. Poly(ethyl acrylate) is more mbberflke, considerably softer, and more extensible. Poly(butyl acrylate) is softer stiU, and much tackier. This information is quantitatively summarized in Table 2 (41). In the alkyl acrylate series, the softness increases through n-octy acrylate. As the chain length is increased beyond n-octy side-chain crystallization occurs and the materials become brittle (42) poly( -hexadecyl acrylate) is hard and waxlike at room temperature but is soft and tacky above its softening point. 

Pressure-Sensitive Adhesives. A pressure-sensitive adhesive, a material which adheres with no more than appHed finger pressure, is aggressively and permanently tacky. It requkes no activation other than the finger pressure, exerts a strong holding force, and should be removeable from a smooth surface without leaving a residue. 

Poly(vinyhdene chloride) (PVDC) film has exceUent barrier properties, among the best of the common films (see Barrier polymers). It is formulated and processed into a flexible film with cling and tacky properties that make it a useful wrap for leftovers and other household uses. As a component in coatings or laminates it provides barrier properties to other film stmctures. The vinyUdene chloride is copolymerized with vinyl chloride, alkyl acrylates, and acrylonitrile to get the optimum processibUity and end use properties (see Vinylidene chloride monomer and polymers). 

Ethylene vinyl acetate copolymer (EVA) forms a soft, tacky film with good water-vapor barrier but very poor gas-barrier properties. It is widely used as a low temperature initiation and broad-range, heat-sealing medium. The film also serves for lamination to other substrates for heat-sealing purposes. 

In the case of some types of polyesters, the dried treated sheet is very tacky, and must be interleaved with a plastic release film to prevent blocking in the roU prior to use. Certain polyesters and acryhcs can be converted to a gelled state by exposure to actinic radiation. 

In methacrylic ester polymers, the glass-transition temperature, is influenced primarily by the nature of the alcohol group as can be seen in Table 1. Below the the polymers are hard, brittle, and glass-like above the they are relatively soft, flexible, and mbbery. At even higher temperatures, depending on molecular weight, they flow and are tacky. Table 1 also contains typical values for the density, solubiHty parameter, and refractive index for various methacrylic homopolymers. 

A substantial fraction of commercially prepared methacrylic polymers are copolymers. Monomeric acryUc or methacrylic esters are often copolymerized with one another and possibly several other monomers. Copolymerization greatiy increases the range of available polymer properties. The aH-acryhc polymers tend to be soft and tacky the aH-methacryhc polymers tend to be hard and brittie. By judicious adjustment of the amount of each type of monomer, polymers can be prepared at essentially any desired hardness or flexibiUty. Small amounts of specially functionalized monomers are often copolymerized with methacrylic monomers to modify or improve the properties of the polymer directiy or by providing sites for further reactions. Table 9 lists some of the more common functional monomers used for the preparation of methacrylic copolymers. 

Substituted heat-reactive resins are most widely used in contact-adhesive appHcations and, to a lesser extent, in coatings (77,78) -butylphenol, cresol, and nonylphenol are most frequendy used. The alkyl group increases compatibiHty with oleoresinous varnishes and alkyds. In combination with these resins, phenoHcs reduce water sensitivity. Common appHcations include baked-on and electrical insulation varnishes, and as modifiers for baking alkyds, rosin, and ester gum systems. Substituted heat-reactive resins are not used for air-dry coatings because of theh soft, tacky nature in the uncured state substituted nonheat-reactive phenoHcs are the modifying resin of choice in this case. 

Adhesives. High concentration (>10%) solutions of poly(ethylene oxide) exhibit wet tack properties that are used in several adhesive appHcations. The tackiness disappears when the polymer dries and this property can be successfully utilized in appHcations that require adhesion only in moist conditions. PEO is also known to form solution complexes with several phenoHc and phenoxy resins. Solution blends of PEO and phenoxy resins are known to exhibit synergistic effects, leading to high adhesion strength on aluminum surfaces. Adhesive formulations are available from the manufacturers. 

The dry-processed, peel-apart system (Fig. 8b) used for negative surprint apphcations (39,44) is analogous to the peel-apart system described for the oveday proofing apphcation (see Fig. 7) except that the photopolymer layer does not contain added colorant. The same steps ate requited to produce the image. The peel-apart system rehes on the adhesion balance that results after each exposure and coversheet removal of the sequentially laminated layer. Each peel step is followed by the apphcation of the appropriate process-colored toners on a tacky adhesive to produce the image from the negative separations. The mechanism of the peel-apart process has been described in a viscoelastic model (45—51) and is shown in Figure 8c. 

Another technique to reduce the problems caused by stickies is to use additives to reduce the tackiness of these particles. This prevents their later reagglomeration and attachment to paper machine surfaces. These additives are usually added to the pulper. The most common is talc (17) usually added to the pulper in repulpable bags. Emulsified talc is also sometimes added to the pulp just before the pulp encounters high shear. Organic polymers (18) such as a polyvinylpyrrohdinone (PVP) copolymer (19) have also been reported to reduce the tackiness of stickies. 

Tackifiers are used to increase the tackiness and the setting speed of adhesives. They increase tackiness by softening the poly(vinyl acetate) polymer in the wet and the dry adhesive film. Tackifiers are usually rosin or its derivatives or phenoHc resins. Other additives frequently needed for specific apphcation and service conditions are antifoams, biocides, wetting agents, and humectants. 

Speciali2ed copolymer latices, which are inherently and permanently tacky, are available as pressure-sensitive emulsions. They are mechanically stable and have excellent machinabiUty. They are compatible with many other PVAc latices and, therefore, can be easily blended with other resins for modification of surface tack, peel strength, and creep. 

Stereoregular Polymerization. Chemists at GAF Corporation were first to suggest that stereoregularity or the lack thereof is responsible for both nontacky and crystalline or tacky and amorphous polymers generated from IBVE with BF2 0(C2H )2, depending on the reaction conditions (22,23). In addition, it was shown that the crystalline polymer is actually isotactic (24). Subsequentiy, the reaction conditions necessary to form such polymers have not only been demonstrated, but the stereoregular polymerization has been extended to other monomers, such as methyl vinyl ether (25,26). 

---