Characterization of eva-based adhesives containing different amounts of rosin ester or polyterpene tackifier

Different amounts (50-170 php--parts per hundred parts of EVA, 33-63 wt%) of two tackifiers (hydrogenated rosin ester, polyterpene resin) were added to an ethylene vinyl acetate (EVA) copolymer containing 28 wt% vinyl acetate. The EVA and the tackifier were characterized using infrared (IR) spectroscopy, DSC measurements, and stress-controlled plate-plate rheology. The properties and compatibility of the EVA-tackifier mixtures were studied using DSC, DMTA, and stress-controlled plate-plate rheology. Immediate adhesion was measured as a quantification of tack, and the T-peel strength of roughened styrene-butadiene rubber/EVA-tackifier adhesive joints was also obtained. The increase in the amount of tackifier noticeably changed the crystallinity of polyethylene blocks in the EVA, and the temperature at the cross-over between the curves of the storage and loss moduli as a function of the temperature was displaced to a lower value. Whereas the hydrogenated rosin ester was compatible with the amorphous ethylene vinyl acetate copolymer regions of the EVA (Tg value increased) reducing its crystallinity, the polyterpene resin was compatible with the polyethylene blocks of the EVA (T g value was not modified), increasing its crystallinity. Immediate adhesion of the EVA-tackifier mixtures was improved by adding both hydrogenated rosin ester and polyterpene tackifiers. On the other hand, there was an optimum tackifier content at which the maximum T-peel strength value was obtained.     

CHARACTERIZATION OF EVA-BASED ADHESIVES CONTAINING DIFFERENT AMOUNTS OF ROSIN ESTER OR POLYTERPENE TACKIFIER

Different amounts (50-170 php--parts per hundred parts of EVA, 33-63 wt%) of two tackifiers (hydrogenated rosin ester, polyterpene resin) were added to an ethylene vinyl acetate (EVA) copolymer containing 28 wt% vinyl acetate. The EVA and the tackifier were characterized using infrared (IR) spectroscopy, DSC measurements, and stress-controlled plate-plate rheology. The properties and compatibility of the EVA-tackifier mixtures were studied using DSC, DMTA, and stress-controlled plate-plate rheology. Immediate adhesion was measured as a quantification of tack, and the T-peel strength of roughened styrene-butadiene rubber/EVA-tackifier adhesive joints was also obtained. The increase in the amount of tackifier noticeably changed the crystallinity of polyethylene blocks in the EVA, and the temperature at the cross-over between the curves of the storage and loss moduli as a function of the temperature was displaced to a lower value. Whereas the hydrogenated rosin ester was compatible with the amorphous ethylene vinyl acetate copolymer regions of the EVA (Tg value increased) reducing its crystallinity, the polyterpene resin was compatible with the polyethylene blocks of the EVA (T g value was not modified), increasing its crystallinity. Immediate adhesion of the EVA-tackifier mixtures was improved by adding both hydrogenated rosin ester and polyterpene tackifiers. On the other hand, there was an optimum tackifier content at which the maximum T-peel strength value was obtained.     

Viscoelastic and adhesion properties of EVA/tackifier/wax ternary blend systems as hot-melt adhesives

Two types of wax were added to a ethylene vinyl acetate (EVA) copolymer/aromatic hydrocarbon resin (tackifier) blend in the molten state and the miscibility, viscoelastic and adhesion properties of ternary blends as hot-melt adhesives (HMAs) were investigated. Miscibility and viscoelastic properties were studied using differential scanning calorimetry (DSC), Brookfield viscometry and dynamic mechanical thermal analysis (DMTA), and their adhesion strength was determined in terms of single lap shear strength. DSC thermograms of both types of waxes showed their melting peaks in a similar region to that of EVA/tackfier blend. It was difficult to evaluate the miscibility of ternary blends using DSC because the melting peaks of the waxes overlapped with those of the EVA/tackifier blend, although the glass transition temperature (T _g) of the ternary blend systems slightly increased with increasing wax concentration. However, their storage modulus (E′) increased slightly and loss tangent (tan δ) showed different peaks when two types of wax were added to the EVA/tackifier blend. Therefore, the miscibility of EVA/tackifier blend altered with addition of waxes. In addition, their melt viscosity decreased with increasing wax concentration. Furthermore, the adhesion strength of the ternary blends decreased with increasing wax concentration, despite the increment of storage modulus. These results suggested that the ternary blends of EVA/tackifier/wax were heterogeneous.     

Peel adhesion and viscoelasticity of poly(ethylene-co-vinyl acetate)-based hot melt adhesives. I. The effect of tackifier compatibility

A series of poly(ethylene-co-vinyl acetate) (EVA)-based hot melt adhesives containing either a rosin or a hydrocarbon (C5–C9) tackifier have been prepared to investigate viscoelastic properties and peel adhesion. Fracture energies were determined by the use of a T-Peel geometry (two polypropylene films bonded with model EVA adhesives). The rosin has only one glass transition temperature, but the C5–C9 resin has two glass transition temperatures, indicating phase separation. The rosin has better compatibility with EVA than does the C5–C9 resin. The bond strength of tackified EVA to polypropylene depends not only on compatibility, but also on viscoelastic properties. A higher storage modulus results in a higher T-Peel strength. Under certain test conditions, glassy C5–C9-rich domains act as reinforcing filler, resulting in a higher storage modulus. Here, a C5–C9-tackified EVA adhesive has higher T-Peel strength than does one containing rosin. © 1997 John Wiley & Sons, Inc.     

Adhesion and rheological properties of EVA-based hot-melt adhesives

Ethylene vinyl acetate (EVA) copolymers of various melt indexes were blended with aromatic hydrocarbon resin in the molten state, and the thermal and adhesion properties as hot-melt adhesives (HMAs) were investigated. The thermal properties for the EVA blends with aromatic hydrocarbon resin were studied using differential scanning calorimeter, Brookfield viscometer and dynamic mechanical thermal analyzer. Their adhesion strength was also obtained using single lap shear strength. The examination of thermal properties for the blend of EVA copolymers with aromatic hydrocarbon resin over a large temperature range showed that the glass transition temperature was independent of their melt index (MI), but that their heat of fusion decreased with increasing MI of EVA copolymers. Furthermore, the storage and loss moduli of the blends decreased with increasing temperature and MI of EVA copolymers, but the loss tangent (tan δ) of the blends increased. An increase in the MI of EVA copolymers decreased the adhesion strength of the blend at the same test condition.     

Effect of natural and synthetic tackifiers on viscosities,adhesion properties and thermal stability of SNR and DPNR solution adhesives

Styrene-grafted natural rubber (SNR) and deproteinized natural rubber (DPNR) latexes were formulated with coumarone-indene (CI), gum rosin and petro resin (PR) tackifiers into solution adhesives with toluene as a solvent. The solution viscosities were evaluated by a Brookfield viscometer DV-II Plus with spindle No. 3. Pressure sensitive adhesives (PSAs) films were made and the adhesion properties were evaluated with loop tack, peel strength and shear strength tests. Thermal stability of the film was evaluated via Perkin-Elmer Pyris 6^TM thermogravimetric analysis at temperatures ranging from 30 to 600?°C at a heating rate of 10?°C per minute in nitrogen environment. Results indicate that as the tackifiers content increased, the solution viscosities increased with SNR/PR and DPNR/PR formulations showing the highest viscosities. Adhesion test also indicates that loop tack and peel strength of the adhesive solution increased but their shear strength decreased; increase of CI tackifier loadings conferred the highest peel strength for both SNR- and DPNR-based PSAs. Thermal analyses show that the addition of 40 phr CI tackifiers improved thermal stability of SNR adhesives based on their higher T_max and integral procedural decomposition temperature properties.     

Synthesis and characterization of new thermoplastic polyurethane adhesives containing rosin resin as an internal tackifier

Three thermoplastic polyurethane elastomers (TPUs) were prepared using the prepolymer method. MDI (diphenylmethane-4,4′-diisocyanate) and the polyadipate of 1,4-butanediol (M_w = 2400) were reacted to produce a prepolymer containing unreacted isocyanate groups; chain extenders were different mixtures of 1,4-butanediol and a rosin resin (0-50%). The specific feature of this procedure was the introduction of a rosin resin as an internal tackifier to provide higher immediate adhesion to the TPUs. The new TPUs were characterized using gel permeation chromatography, wideangle X-ray diffraction, differential scanning calorimetry, stress-controlled rheology, and stress-strain measurements. The TPUs were used as raw materials to prepare solvent-based polyurethane adhesives, the adhesion properties of which were obtained from T-peel tests on PVC/polyurethane adhesive/PVC and leather/polyurethane adhesive/PVC joints. The addition of rosin resin as an internal tackifier contributed to the production of two types of hard segments, which affected the properties of the TPUs. Therefore, rosin resin as an internal tackifier produced an increase in the average molecular weight, an increase in the viscosity, and improved the rheological properties. The glass transtition temperature decreased if the TPUs contained rosin resin, due to a greater degree of incompatibility between the hard and soft segments. Consequently, slower kinetics of crystallization was obtained in the TPUs containing rosin resin. Depending on the amount of rosin resin in the TPU, different structures and properties were obtained. On the other hand, the immediate T-peel strength in all joints was improved if the TPU contained rosin resin.     

乙烯-醋酸乙烯基钢质管道防腐用热熔胶的研究

以EVA树脂为主体树脂制备钢质管道防腐用热熔胶,选用聚合松香为增粘剂,聚异丁烯为增韧剂,研究了不同VA含量、不同熔体指数的EVA树脂、聚合松香及聚异丁烯对热熔胶环球软化点、脆化温度和剥离强度等性能的影响。     

Miscibility Between Ethylene Vinyl Acetate Copolymers and Tackifier Resins

A series of ethylene vinyl acetate copolymer (EVA) were blended with various kinds of tackifiers and the miscibility between the components was investigated. The miscibility of the blend is illustrated as a phase diagram. The EVA and modified rosin systems tended to have a phase diagram with lower critical solution temperature (LCST), whereas the EVA and petroleum resin systems tended to have that with upper critical solution temperature (UCST). The phase diagrams of EVA/tackifier resins systematically changed as VAc content in the copolymer increased, which is accounted for by the classical Flory-Huggins theory.     

Miscibility Between Ethylene Vinyl Acetate Copolymers and Tackifier Resins

A series of ethylene vinyl acetate copolymer (EVA) were blended with various kinds of tackifiers and the miscibility between the components was investigated. The miscibility of the blend is illustrated as a phase diagram. The EVA and modified rosin systems tended to have a phase diagram with lower critical solution temperature (LCST), whereas the EVA and petroleum resin systems tended to have that with upper critical solution temperature (UCST). The phase diagrams of EVA/tackifier resins systematically changed as VAc content in the copolymer increased, which is accounted for by the classical Flory-Huggins theory.     

Miscibility and adhesive properties of EVA‐based hot‐melt adhesives. II. Peel strength

A series of ethylene vinyl acetate copolymers (EVA) were blended with some tackifier resins that were made from wood extracts, and possible relations between their miscibility and properties as hot‐melt adhesives (HMA) were investigated. From our previous report on miscibility of various EVA‐based HMAs, we chose some blends that represent some of the typical miscibility types and investigated their peel strengths. When the blends were miscible at testing temperatures, the temperature at which the maximum value of peel strength was recorded tended to move toward higher temperature as tackifier content of blends increased. This result corresponds to the storage modulus of the blends whose curves tended to move toward higher temperature as tackifier content of blends increased when blend components were miscible as well as their maximum values of tan δ, or glass transition temperatures. It was characteristic for peel strength that there existed second peaks on peel strengths curves at ～ 100°C, which adhesive tensile strengths for the blends did not have. In terms of relationship between miscibility and HMA performances, we suggest that there are several factors other than miscibility that affect absolute values of peel strength more directly than miscibility; this idea has to be investigated further in the a future study. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 83: 726–735, 2002     

Adhesion and Failure Mechanisms of a Model Hot Melt Adhesive Bonded to Polypropylene

A model hot melt adhesive (HMA) based on an ethylene/vinyl acetate copolymer (EVA), an Escorez® hydrocarbon tackifier, and a wax has been used to bond together polypropylene (PP) films to give equilibrium bonding. Peel strengths were determined over a broad range of peel rates and test temperatures. Contrary to the peel behavior of joints with simple rubbery adhesives [1], peel strengths with this semi-crystalline adhesive are not rate-temperature superposable, and multiple transitions in failure locus occur. The semi-crystalline structure of the HMA also prevents rate-temperature superposition of its dynamic moduli.

At different test temperatures, the dependence of peel strength on peel rate shows some resemblance to the dependence of the loss tangent of the bulk adhesive on frequency. This is consistent with a previous result [2] that the HMA debonding term. D, varies with the loss tangent of a HMA at the T-peel debonding frequency.

This model HMA, similar to block copolymer/tackifier blends [3], consists of two phases: an EVA-rich and a tackifier-rich phase, in its amorphous region. At a low peel rate of 8.33 × 10^-5 m/s, the peel strength shows a maximum at a temperature that corresponds to the transition temperature of the tackifier-rich phase (T₁). At a higher peel rate of 8.33 × 10^-3 m/s, the peel strength rises with increasing test temperature, but becomes essentially constant at temperature T₁'. It is believed that, to optimize the peel strength of a HMA at ambient temperature, it is advantageous to formulate the EVA polymer (or other semi-crystalline polyolefins) with a compatible tackifier that yields a tackifier-rich phase with a transition temperature (T₁') in the vicinity of room temperature.     

Temperature dependence of tack and pulse NMR analysis of polystyrene block copolymer/tackifier system

The influence of tackifier structure on the temperature dependence of tack for a polystyrene block copolymer/tackifier system was investigated. A blend of polystyrene-block-polyisoprene-block- polystyrene triblock and polystyrene-block-polyisoprene diblock copolymers was used as the base polymer. Four different tackifiers were used: special rosin ester resin (RE), rosin phenolic resin (RP), hydrogenated cyclo-aliphatic resin (HC), and aliphatic petroleum resin (C5). Tack at 20?°C increased with the tackifier content for both RE and HC tackifier systems. Tack is affected by two factors: the work of adhesion at the adherend interface and the viscoelastic properties of the adhesive. The good balance of these two factors brought high tack. The adhesive with 10 wt.% tackifier exhibited the highest tack at 20?°C, whereas those with 30 and 50 wt.% tackifier were lower than those systems with 10 wt.% of the RP or C5 tackifiers. The adhesive with overly high hardness lowered the work of adhesion and the tack was not improved with more than 30 wt.%. A compatibility test in toluene solution and in solid state showed that tackifier RE has good compatibility with both polyisoprene and polystyrene, whereas tackifier RP has lower compatibility. Tackifiers HC and C5 had good compatibility with polyisoprene, but poor compatibility with polystyrene, and that of C5 was poorer. Pulse nuclear magnetic resonance (NMR) analyses indicated that tackifiers RE and HC effectively restrict the molecular mobility of polyisoprene phase.     

Effects of hydrocarbon tackifiers on the adhesive properties of contact adhesives based on polychloroprene - III. The effect of the molecular weight of the tackifier

Aromatic hydrocarbon resins with different molecular weights (M_w = 1300-50400 daltons) were added to a solvent-based polychloroprene adhesive. The hydrocarbon resins were characterized using infra-red (IR) and differential scanning calorimetry (DSC) measurements. The properties and compatibility of the polychloroprene/resin blends were studied using mechanical tests, DSC measurements, scanning electron microscopy (SEM), and stress-controlled rheology. Tack measurements were also carried out and the adhesion strength was obtained from T-peel tests on roughened styrene-butadiene rubber/polychloroprene adhesive joints. The addition of low-molecular-weight tackifiers produced a compatible polychloroprene/tackifier system (only one T_g was found in DSC measurements), while the addition of a high-molecular-weight (and broad molecular weight distribution) tackifier produced a partially incompatible system (two Tg's were found in DSC measurements). The compatibility of polychloroprene/tackifier blends was also assessed with stress-controlled rheology and SEM. An increase in the T-peel strength and tack were produced when the molecular weight of the tackifier increased, although the addition of a hydrocarbon resin with a M_w higher than about 50 000 reduced the tack. A broad molecular weight distribution in the tackifier favoured incompatibility with the polychloroprene, resulting in a reduction in the tack and rheological properties.     

Synthesis and characterization of hydrogenated sorbic acid grafted dicyclopentadiene tackifier

Hydrocarbon resins, which are defined as low molecular weight, amorphous, and thermoplastic polymers, are widely used as tackifier for various types of adhesives, as processing aids in rubber compounds, and as modifiers for paint and ink products, and for plastics polymers such as isotactic polypropylene. Typically, hydrocarbon resins are non-polar, and thus highly compatible with non-polar rubbers and polymer. However, they are poorly compatible with polar system, such as acrylic copolymer, polyurethanes, and polyamides. Moreover, recently the raw materials of tackifier from naphtha cracking had been decreased because of light feed cracking such as gas cracking. To overcome this problem, in this study, novel hydrocarbon resins were designed to have a highly polar chemical structure. And, it was synthesized by Diels–Alder reaction of dicyclopentadiene monomer and sorbic acid from blueberry as renewable resources. Acrylic resins were formulated with various tackifiers solution including hydrogenated sorbic acid grafted dicyclopentadiene tackifier in acrylic adhesive and rolling ball tack, loop tack, 180° peel adhesion strength, and shear adhesion strength were measured. The properties depend on the softening point and polar content of tackifiers.     

Tack and Shear Strength of Adhesives Prepared from Styrene-Butadiene Rubber (SBR) Using Gum Rosin and Petro Resin as Tackifiers

Tack and shear strength of styrene-butadiene rubber (SBR)-based pressure-sensitive adhesive were studied using gum rosin and petro resin as the tackifiers. The concentration of the tackifying resin was varied from 0 to 100 parts per hundred parts of rubber (phr). Toluene was used as the solvent throughout the experiment. The rolling ball technique was used to measure the tack of the adhesive, whereas, shear strength was determined by a TA-HDi Texture Analyser. Results show that the tack of the adhesive increases with increasing tackifier loadings for both tackifier systems. However, shear strength indicates the reverse behavior with increasing resin content, an observation which is attributed to the decrease in cohesive strength as the tackifier concentration is increased. Both tack and shear strength of the adhesives increases with molecular weight of SBR. Adhesive containing petro resin consistently exhibits higher values than the gum rosin system due to better wettability and compatibility in the former system.     

增粘树脂对聚丙烯酸酯压敏胶粘合性能的影响

聚丙烯酸酯乳液和增粘树脂松香、Ｃ_５石油树脂乳液共混，用共混液涂布成压敏胶带。考察了不同增粘树脂用量对压敏胶带粘合性能的影响。结果表明，随松香树脂量增加，１８０℃剥离强度提高，并出现峰值；快粘力不变；持粘力下降。随Ｃ_５石油树脂量增加，１８０°剥离强度，快粘力，持粘力均大幅度下降。     

Toughening effects of ethylene–vinyl acetate copolymers with different vinyl acetate content and viscosity on nylon 1010 blends

Nylon 1010 blends with ethylene–vinyl acetate copolymer (EVA) and maleated ethylene–vinyl acetate (EVA‐g‐MAH) were prepared through melt blending. The vinyl acetate (VA) content and viscosity of EVA significantly affected the notched impact strength of nylon/EVA/EVA‐g‐MAH (80/15/5) blends. The nylon/EVA/EVA‐g‐MAH blends with high notched impact strength (over 60 kJ/m²) were obtained when the VA content in EVA ranged from 28 to 60 wt%. The effect of VA content on the notched impact strength of blends was related to the glass transition temperature for EVA with high VA content and crystallinity for EVA with low VA content. For nylon blends with EVA with the same VA content, low viscosity of EVA led to high notched impact strength. Fracture morphology of nylon/EVA/EVA‐g‐MAH (80/15/5) blends showed that blends with ductile fracture behavior usually had large matrix plastic deformation, which was the main energy dissipation mechanism. A relationship between the notched impact strength and the morphology of nylon/EVA/EVA‐g‐MAH (80/15/5) blends was well correlated by the interparticle distance model. POLYM. ENG. SCI., 2009. © 2009 Society of Plastics Engineers     

Rheological study on the adhesion properties of the blends of ethylene vinyl acetate/terpene phenol adhesives

Measurements of the shear, tensile, peel, and creep strength of ethylene vinyl acetate (EVA)/CaCO₃/terpene phenol adhesive system at three different ratios [100/60/0 (EVA-O), 80/48/20 (EVA-20), and 60/36/40 (EVA-40) by weight, using wood and aluminum as adherends] were conducted. Over a wide range of temperatures and rates of deformation, adhesion shear, tensile, and peel strength results, as well as the creep response over a broad range of temperature and stresses, were found to yield a single master curve by means of the reduced-variable technique. It was observed that the peak of E′ representing Tg, shifted toward higher temperatures as the amount of terpene phenol in the blend was increased. The most obvious effect of increasing the tackifier resin was the shifting of the adhesion strength master curves to the direction of lower rates. The shift was associated with the rise in Tg as the blend ratio was increased. The influence of the tackifier resin in modifying the viscoelastic properties of the adhesive was further described in a comparison of the adhesion strength master curves with corresponding dynamic viscoelastic curves of the adhesive films. The master curves for the creep response of the adhesives showed that the stress-breaking time relationship shifts toward longer time for EVA-40 with high Tg. Thus, it was found that the strength of adhesion is due mainly to dynamic effects in the adhesive of a viscous nature in the same way to the cohesive strength of the viscoelastic materials. © 1998 John Wiley & Sons, Inc. J. Appl. Polym. Sci. 70: 409–418, 1998     

The effect of tackifier on phase structure and peel adhesion of a triblock copolymer pressure-sensitive adhesive

The role of tackifier on the adhesive properties of pressure-sensitive adhesive tape was investigated. For this purpose, a model system consisting of polystyrene-b-polyisoprene-b-polystyrene triblock copolymer and a tackifier was prepared. The hydrogenated cyclo-aliphatic resin, such as tackifier, which has poor compatibility with polystyrene increased the peel adhesion significantly. The increase became stronger above 40 wt% tackifier. Nanometer-sized agglomerates of tackifier were found in the polyisoprene matrix and these agglomerates increased in number with an increase in the tackifier content. The higher peel adhesion was obtained in the system with the larger amount of agglomerates of tackifier in the polyisoprene matrix. It was estimated that the tackifier dissolved with initial mixing at the molecular level in the polyisoprene matrix, enhancing the wettability of the adhesive, and separated out in the form of agglomerates over time, developing the cohesive strength. On the other hand, the rosin phenolic resin tackifier had good compatibility with polystyrene, and the peel adhesion increased effectively at the lower tackifier content. However, no significant additional increase at higher tackifier content was observed.