Pressure-sensitive adhesives tackifiers

Uses Butyl mbber in sealants, coatings, elec, encapsulating compds., and conformal coalings incl. moisture-impermeable coatings, marine and construction sealants, elec, encapsulants, pressure-sensitive adhesives tackifier for pressure-sensitive adhesives processing aid, adhesion promoter... 

Heteroatom functionalized terpene resins are also utilized in hot melt adhesive and ink appHcations. Diels-Alder reaction of terpenic dienes or trienes with acrylates, methacrylates, or other a, P-unsaturated esters of polyhydric alcohols has been shown to yield resins with superior pressure sensitive adhesive properties relative to petroleum and unmodified polyterpene resins (107). Limonene—phenol resins, produced by the BF etherate-catalyzed condensation of 1.4—2.0 moles of limonene with 1.0 mole of phenol have been shown to impart improved tack, elongation, and tensile strength to ethylene—vinyl acetate and ethylene—methyl acrylate-based hot melt adhesive systems (108). Terpene polyol ethers have been shown to be particularly effective tackifiers in pressure sensitive adhesive appHcations (109). 

Pressure sensitive adhesives typically employ a polymer, a tackifier, and an oil or solvent. Environmental concerns are moving the PSA industry toward aqueous systems. Polymers employed in PSA systems are butyl mbber, natural mbber (NR), random styrene—butadiene mbber (SBR), and block copolymers. Terpene and aUphatic resins are widely used in butyl mbber and NR-based systems, whereas PSAs based on SBR may require aromatic or aromatic modified aUphatic resins. 

Rosin ester resins are used extensively in pressure-sensitive adhesives as tackifiers. The adhesive is formulated by blending the resin with a polymer in solution or as aqueous emulsions. Typical compositions may contain about 50% resin. The glycerol or pentaerythritol esters of stabilized rosins are often used because they are stable on aging. 

While there are a large number of elastomers that can be formulated into pressure sensitive adhesives, the following list is intended to focus on commercially significant materials. Two subsets are differentiated in Table 1 those polymers that can be inherently tacky, and those that require modification with tackifiers to meet the Tg and modulus criteria to become pressure sensitive. 

In the earlier art, there was some consideration that partial incompatibility of the tackifier resin with the rubber was responsible for the appearance of tack, but this no longer is seriously held in light of continuing studies by many investigators. Aubrey [38] has addressed this in his review of the mechanism of tackification and the viscoelastic nature of pressure sensitive adhesives. Chu [39] uses the extent of modulus depression with added tackifier as a measure of compatibility. Thus in a plot of modulus vs. tackifier concentration, the resin that produces the deepest minimum is the most compatible. On this basis, Chu rates the following resins in order of compatibility for natural rubber rosin ester > C-5 resin > a-pinene resin > p-pinene resin > aromatic resin. 

Among the different pressure sensitive adhesives, acrylates are unique because they are one of the few materials that can be synthesized to be inherently tacky. Indeed, polyvinylethers, some amorphous polyolefins, and some ethylene-vinyl acetate copolymers are the only other polymers that share this unique property. Because of the access to a wide range of commercial monomers, their relatively low cost, and their ease of polymerization, acrylates have become the dominant single component pressure sensitive adhesive materials used in the industry. Other PSAs, such as those based on natural rubber or synthetic block copolymers with rubbery midblock require compounding of the elastomer with low molecular weight additives such as tackifiers, oils, and/or plasticizers. The absence of these low molecular weight additives can have some desirable advantages, such as ... 

Besides the higher volume pressure sensitive adhesives discussed above, the industry also uses other synthetic elastomers as the base component for PSA formulation. Most of these elastomers require some form of tackification to make the materials tacky. However, a few materials are low enough in Tg and sufficiently compliant to be useful without requiring compounding with tackifiers. 

Tackifying resins enhance the adhesion of non-polar elastomers by improving wettability, increasing polarity and altering the viscoelastic properties. Dahlquist [31 ] established the first evidence of the modification of the viscoelastic properties of an elastomer by adding resins, and demonstrated that the performance of pressure-sensitive adhesives was related to the creep compliance. Later, Aubrey and Sherriff [32] demonstrated that a relationship between peel strength and viscoelasticity in natural rubber-low molecular resins blends existed. Class and Chu [33] used the dynamic mechanical measurements to demonstrate that compatible resins with an elastomer produced a decrease in the elastic modulus at room temperature and an increase in the tan <5 peak (which indicated the glass transition temperature of the resin-elastomer blend). Resins which are incompatible with an elastomer caused an increase in the elastic modulus at room temperature and showed two distinct maxima in the tan <5 curve. 

NR pressure-sensitive adhesives with a high tackifier content can be used as commercial tapes and surgical plasters. These PSA require the elimination of the gel fraction and a reduction in molecular weight to facilitate solution. 

Schlademan, J., Tackifier resins. In Satas, D. (Ed.), Handbook of Pressure Sensitive Adhesive Technology, 2nd edn. Van Nostrand Reinhold, New York, 1989, p. 527. 

Tackifiers to produce pressure-sensitive adhesives were also prepared as a latex. Self-emulsifying resin or rosin composition, useful as tackifiers for ad-... 

NR, styrene-butadiene mbber (SBR), polybutadiene rubber, nitrile mbber, acrylic copolymer, ethylene-vinyl acetate (EVA) copolymer, and A-B-A type block copolymer with conjugated dienes have been used to prepare pressure-sensitive adhesives by EB radiation [116-126]. It is not necessary to heat up the sample to join the elastomeric joints. This has only been possible due to cross-linking procedure by EB irradiation [127]. Polyfunctional acrylates, tackifier resin, and other additives have also been used to improve adhesive properties. Sasaki et al. [128] have studied the EB radiation-curable pressure-sensitive adhesives from dimer acid-based polyester urethane diacrylate with various methacrylate monomers. Acrylamide has been polymerized in the intercalation space of montmorillonite using an EB. The polymerization condition has been studied using a statistical method. The product shows a good water adsorption and retention capacity [129]. 

Materials, such as acrylates with tackifiers, acrylate polyesters, and polyurethanes, that do not have properties as pressure-sensitive adhesives, but after cross-linking have desired pressure-sensitive properties... 

Applications and Formulation. Pressure-sensitive adhesives are most widely used in the form of adhesive tapes. The general formula for a pressure-sensitive adhesive includes ail elastomeric polymer, a tackifying resin, any necessary fillers, various antioxidants and stabilizers, if needed, and cross-linking agents. 

Styrene Copolymers. The so-called thermoplastic rubbers based on styrene-butadiene-styrene and styrene-isoprene-styrene block copolymers can be used for hot-melt adhesives, particularly when extended with tackifying resins and oils. They can be made into pressure-sensitive adhesives, as melts with low viscosity—being applied from fine spinnerets which are oscillated to make a... 

Resin as the Disperse Phase. Several kinds of resins (10) have been used to reinforce rubbers—e.g., phenolic or coumarone resins for natural rubber, styrene-butadiene resin for styrene-butadiene rubber, etc. One other important system, pressure-sensitive adhesive, also belongs to this class. These adhesives generally contain a low molecular weight resin functioning as a tackifier. In 1957, Wetzel (68) and Hock (19) found that these adhesives were actually two-phase systems (Figure 1). Under... 

Prior to this discovery, in 1954 Silberberg and Kuhn (62) were first to study the polymer-in-polymer emulsion containing ethylcellulose and polystyrene in a nonaqueous solvent, benzene. The mechanisms of polymer emulsification, demixing, and phase reversal were studied. Wetzel and Hocks discovery would then equate the pressure-sensitive adhesive to a polymer-polymer emulsion instead of a polymer-polymer suspension. Since the interface is liquid-liquid, the adhesion then becomes one type of R-R adhesion (35, 36). According to our previous discussion, diffusion is not operative unless both resin and rubber have an identical solubility parameter. The major interfacial interaction is physical adsorption, which, in turn, determines adhesion. Our previous work on the wettability of elastomers (37, 38) can help predict adhesion results. Detailed studies on the function of tackifiers have been made by Wetzel and Alexander (69), and by Hock (20, 21), and therefore the subject requires no further elaboration. 

If polymer A has a butadiene rubber block, it will not find application in pressure-sensitive adhesives. It is not readily tackified, it is not readily melt processable, and it will not close a box. However, if dissolved in solvent, compounded with filler and certain resins, it will make the world s best construction mastic, very capable of bonding drywall to wood, etc. If one wants to maximize the solids content in this mastic (use less solvent), and if one wants to design the SBS molecule to be soluble in more environmentally friendly solvents, then in what direction should one head If not A , then where in the region does one strike the balance for a highly extended but tough mastic that allows the solvents of choice while achieving maximum solids and a viscosity low enough to squeeze from a tube ... 

In general, they consist of a pressure sensitive adhesive layer which is composed of a so-called hydrocolloid dispersed with the aid of a tackifier in an elastomer and secondly a film coating composed of a gas permeable but water impermeable, flexible, elastomeric material. A currently available hydrocolloid dressing is a flexible mass with an adherent inner face and an outer semipermeable polyurethane foam. 

Furthermore, polymer layers applied to the respective substrates are known that show their own adhesiveness due to the addition of tackifying components (e.g., resins). With the application of adequate surface pressure, these systems known as pressure-sensitive adhesives (Section 5.6) result in a bonded joint. 

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