Skin Development during the Film Formation of Waterborne Acrylic Pressure-Sensitive Adhesives Containing Tackifying Resin

Tackifying resins (TR) are often used to improve the adhesive properties of waterborne pressure-sensitive adhesives (PSAs) derived from latex dispersions. There is a large gap in the understanding of how, and to what extent, the film formation mechanism of PSAs is altered by the addition of TR. Herein, magnetic resonance profiling experiments show that the addition of TR to an acrylic latex creates a coalesced surface layer or “skin” that traps water beneath it. Atomic force microscopy of the PSA surfaces supports this conclusion. In the absence of the TR, particles at the surface do not coalesce but are separated by a second phase composed of surfactant and other species with low molecular weight. The function of the TR is complex. According to dynamic mechanical analysis, the TR increases the glass transition temperature of the polymer and decreases its molecular mobility at high frequencies. On the other hand, the TR increases the molecular mobility at lower frequencies and thereby promotes the interdiffusion of latex particles to create a skin layer. In turn, the skin layer is a barrier that prevents the exudation of surfactant to the surface. The TR probably enhances the coalescence of the latex particles by increasing the compatibility between the acrylic copolymer and the solids in the serum phase.     

Surfactant concentration and morphology at the surfaces of acrylic latex films

The final outcome of surfactants during latex film formation is a topic of ongoing concern and interest. In this study of an acrylic latex containing an anionic surfactant, two notable phenomena are observed. (1) A higher surfactant concentration is present at the air surface of the latex films, regardless of the film-forming temperature and time. In some cases, surfactant is not visible in an atomic force microscope (AFM) image as a separate phase, but compositional profiles obtained with Rutherford backscattering spectrometry (RBS) reveal an enhanced concentration of surfactant over a depth from the surface that is comparable to the latex particle diameter. (2) The surfactant features that are imaged with the AFM evolve from a thin uniform layer, to a ‘finger-like' morphology, to small flat droplets, and finally to larger, hemispherical ‘blobs.' We suggest that surfactant is first deposited from the air/water interface onto the latex surface during the drying process. During this progression in the morphology of the surfactant, the ratio of the surface area-to-volume decreases. We speculate that this phenomenon is driven by a reduction in surface energy.     

Synthesis of high‐solid‐content,acrylic pressure‐sensitive adhesives by solvent polymerization

In this study, we prepared high solid content (SC), solvent‐based, acrylic pressure‐sensitive adhesives (PSAs) with n‐dodecyl mercaptan as a chain‐transfer agent (CTA) and studied the crosslinking reactions between the crosslinker and the acrylic PSAs. Acrylic PSAs were prepared from 2‐ethyl hexyl acrylate, acrylic acid (AA), and 2‐azobisisobutyronitrile with a solution polymerization process. The results show AA resulted in an effective molecular weight in the acrylic PSAs, as it improved the hydrophilicity with increasing peel strength of the acrylic PSAs. As for the high SC, the molecular weight and system viscosity decreased through the addition of CTA. At a constant AA amount, the addition of CTA decreased the molecular weight and increased the hydrophobicity of the acrylic PSAs; this decreased the peel strength of the acrylic PSAs on the glass. Furthermore, the addition of CTA decreased the molecular weight and improved the acrylic PSAs' surface morphologies and optical properties. The acrylic PSAs produced in this study could meet production needs. © 2018 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 46257.     

The influence of substrate absorbency on coating surface chemistry

The composition of the top surface of a coating layer can influence its functional properties or subsequent processing steps. The effect of the substrate absorbency on the coating surface chemistry is reported. Different coating systems containing a kaolin clay pigment, fine or coarse precipitated calcium carbonates, and a common latex binder were examined. The influence of a soluble polymer added into the coating was characterized. The surface chemistry was measured with attenuated total internal reflectance (ATR) and X-ray photoelectron spectroscopy (XPS).

Absorbent substrates generate bulky coatings with high voids and low gloss. Rapid dewatering by the absorbent substrate pulls the small particles, like latex binder, away from the top layers causing a low latex concentration at the surface. On non-absorbent substrates, the addition of the soluble polymer generates coating layers with higher void volume, lower gloss, and lower latex concentrations at the coating surface. However, on absorbent substrates, polymer addition causes coatings with lower void volumes and higher gloss. In this case, the rapid dewatering and mobility of particles is reduced by the polymer, which helps to retain the small particles at the surface. As a result, latex concentration at the surface increases with polymer addition on absorbent substrates.     

Structured latex particles with improved mechanical properties

Structured polymer latex particles are prepared by a swelling emulsion polymerization process, in which the initial particles are first swollen by ethylenically unsaturated monomers and the polymerization of the latter is then carried out. This special polymerization process leads to multi-phase particle morphology. Instead of a thermodynamically more favorable large-scale phase-separation, we obtain multiple, near-spherical domains dispersed within the particles. TEM analysis after selective staining reveals the size and distribution of the microdomains. Dynamic mechanical analysis of the polymer films confirms the absence of a distinct, large second phase and indicates that such microdomains interfere at the molecular level with the segmental mobility of the dispersing phase. We present examples of soft polymers as the continuous phase and hard polymers as the dispersed phase. The inclusion of hard microdomains into soft continuous phase increases dramatically both the films tensile strength and elongation, which means improved cohesive strength of the polymer material. The increase in tensile strength of the polymer film correlates directly with the hardness of the dispersed phase. Improvement in tensile strength and elongation is important in a number of industrial applications of polymers, such as flexible coatings, coalescent-free paints and pressure sensitive adhesives (PSAs). Examples are presented which demonstrate the potential applications of the swelling emulsion polymerization process.     

Acrylic emulsion pressure-sensitive adhesives (PSAS) reinforced with layered silicate

Composite acrylic pressure-sensitive adhesives (PSAs) were synthesized by emulsion polymerization in the presence of montmorillonite (MMT). An examination with X-ray diffraction (XRD) and transmission electron microscopy (TEM) showed that both intercalated and exfoliated structures of MMT coexisted in the composites. It was demonstrated by X-ray photoelectron spectroscopy (XPS) that enrichment of the surface by the surfactant during drying of emulsion PSAs was depressed by the layered silicate. Significant improvements in storage modulus and cohesive strength were achieved by incorporation of MMT. The addition of only a small amount of MMT was enough to improve the adhesion properties of acrylic emulsion PSAs.     

Self‐assembly of pH‐responsive acrylate latex particles at emulsion droplets interface

The self‐assembly of pH‐responsive poly (methyl methacrylate‐co‐acrylic acid) latex particles at emulsion droplet interfaces was achieved. Raising pH increases the hydrophilicity of the latex particles in situ and the latex particle acts as an efficient particulate emulsifier self‐assembling at emulsion droplet interface at around pH 10–11 but exhibits no emulsifier activity at higher pH. This effect can be reversibly induced simply by varying the aqueous phase pH and thus the latex emulsifier can be reassembled. The effect factors, including the aqueous phase pH, the surface carboxyl content, ζ‐Potential of the latex particles and oil phase solvent have been investigated. Using monomer as oil phase, the latex particles could stabilize emulsion droplets during polymerization and cage‐like polymer microspheres with hollow core/porous shell structure were obtained after polymerization. The mechanism of the latex particles self‐assembly was discussed. The morphologies of emulsion and microspheres were characterized by optical microscopy, scanning electron microscopy, and transmission electron microscopy. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 2007     

Surface and interfacial fourier transform infrared spectroscopic studies of latexes. XV. Orientation of the sodium dioctyl sulfosuccinate surfactant molecules in core/shell-type styrene/butyl acrylate latex films at the film–air and film–substrate interfaces

This study addresses the effect of particle structure and composition on the mobility and orientation of sodium dioctyl sulfosuccinate (SDOSS) surfactant molecules in polybutyl acrylate/polystyrene core/shell-type latex films near the film-air (F-A) and film-substrate (F-S) interfaces. In an effort to determine how the surface tension of the substrate influences the migration and orientation of the SDOSS surfactant molecules, polytetrafluoroethylene (PTFE) and liquid Hg substrates were used. It appears that, as the concentration of styrene monomer in the latex increases, SDOSS migrates toward the F-A and F-S interfaces. As the surface tension of the substrate changes from 18 mN/m in PTFE to 400 mN/m for liquid Hg, the surfactant also migrates toward the two interfaces. For the latex particles composed of 50%/50% styrene/n-butyl acrylate (Sty/n-BA) latex copolymer, the hydrophilic SO⁻₃Na⁺ groups of SDOSS surfactant are present primarily near the F-A interface, and they appear to be mostly parallel to the surface for the films cast on the PTFE surface. For the latex films cast on the liquid Hg surface, the SDOSS hydrophilic surfactant groups are found to be preferentially parallel near the F-A interface and perpendicular near the F-S interface. These studies indicate that the surfactant concentration and its orientation throughout the latex film change as a function of the initial monomer composition and the surface tension of the substrate. Furthermore, the SDOSS concentration appears to vary with depth into the latex interfaces. © 1996 John Wiley & Sons, Inc.     

Molecular weight and crosslinking on the adhesion performance and flexibility of acrylic PSAs

Acrylic pressure sensitive adhesives (PSAs) are used in the production of flexible displays. Acrylic PSAs must have high flexibility and recovery to meet the industry demands for flexible displays. For these reasons, acrylic PSAs were designed to determine the effects of molecular weight and cross-linking on acrylic PSAs. Stress relaxation and creep tests were measured with dynamic mechanical analysis to identify the flexibility and recovery of the acrylic PSAs. The molecular weight and glass transition temperature of the PSAs were measured by gel permeation chromatography and differential scanning calorimetry. A texture analyzer was used to measure the adhesion performance of the acrylic PSAs. With increasing molecular weight, the adhesion performance increased, especially from 86 to 108 K molecular weight PSAs. This is due to the entanglement of the polymer chains. The stress and recovery of cross-linked acrylic PSAs was much higher than that of neat acrylic PSAs. This result is attributed to interactions between the polymer chains due to cross-linking.     

Adhesion of latex films. Part II. Loci of failure

In order to continue our work on surfactant effects on the adhesion properties of latex films, we investigated a new system based on an acrylic copolymer, synthesized in the presence of a hydrophilic polyester. The surfactants were either sodium dodecyl sulfate (SDS) or an ethoxylated nonyl phenol containing 30 ethoxy groups (NP30). As substrates, either glass plates or poly(ethylene terephthalate) (PET) films were used. This article describes the analysis of the loci of failure after peeling of the films. The analytical techniques used were X-ray photoelectron spectroscopy (XPS) (or ESCA), static secondary ion mass spectrometry (SSIMS), and contact angle measurements. It was shown that the loci of failure were independent of the peel rate and of the nature of the substrate. The failure occurs in a thick surfactant layer for SDS, and in a thin one for NP30. The thickness of the layer increases with the concentration of surfactant in the latex film. The surfactant is located near the surface of the substrate, on top of a layer of hydrophilic polyester. The consequences of the structure of the film-substrate interface on the adhesion properties is presented in Part III in this series.     

Self‐Healing Latex Containing Polyelectrolyte Multilayers

Self‐healing paints would have the potential benefit of protecting the underlying substrate and extending the coating's service life. As a step toward those types of coatings, this work examines layer‐by‐layer films of branched poly(ethylene imine)/poly(acrylic acid) with the inclusion of various types of latex particles with different T_g and different compositions. Due to high mobility of the polyelectrolyte chains when plasticized with water, water enabled self‐healing of these films is demonstrated, as well as steam enabled self‐healing. The films with various latex particles show different swelling ratios, surface hydrophilicity, as well as varying ability to self‐heal scratches. This self‐healing property is studied as a function of temperature. Also, the mechanical properties such as hardness and modulus of the films are measured.     

超浓乳液聚合苯乙烯—甲基丙烯酸的乳胶粒径及羧基分布

以苯乙烯、甲基丙烯酸为主要原料进行超浓乳液聚合 ,制备了含功能基的单分散性复合物。考察了乳化剂浓度、内相比、聚合程度对乳胶粒大小及分布的影响。同时 ,用电导滴定法测定了乳胶粒表面羧基的含量 ,探讨了乳化剂浓度、羧酸含量及内相比对羧基分布的影响。结果表明 ,随乳化剂浓度减小、内相比增加、聚合时间延长、乳胶粒径增大 ,随乳化剂浓度减小、内相比增加、粒子表面羧基减少 ,而羧酸含量对羧基分布的影响不太明显     

High solids content emulsions. III. Synthesis of concentrated latices by classic emulsion polymerization

Two different methods of producing bi‐ and trimodal latices of a mixture of methyl methacrylate, butyl acrylate, and small amounts of acrylic acid were tested. It is shown that a combination of concentrating blends of seed particles by semibatch reaction, followed by a nucleation of small particles plus a second semibatch phase allowed us to obtain stable latices with solids contents over 65% and viscosities of below 2500 mPa s^?1 with little coagulum formation. The key parameter in determining latex stability, coagulum formation, and viscosity appears to be the the particle size distribution, and especially its modification attributed to secondary nucleation. Because it is not possible to eliminate water‐soluble monomers from the polymerization recipe, secondary (homogeneous) nucleation must be minimized by careful addition of the free‐radical initiator and choice of monomer feed flow rates. The nucleation of the third population in the trimodal latices is best accomplished with a mixed surfactant system because renucleation by anionic surfactant alone leads to detrimental changes in the particle size distribution (PSD) resulting from excessive flocculation of particles. In addition, it was found that the viscosity of the final products was not sensitive to small changes in the ionic strength of the latex, although neutralization to a pH of 6 effectively doubles the final latex viscosity. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 84: 1916–1934, 2002; DOI 10.1002/app.10513     

Hydrogenated rosin ester latexes/waterborne polyacrylate blends for pressure‐sensitive adhesives

Diethylene glycol ester of hydrogenated rosin (DGE‐HR) emulsion was prepared via phase inversion method and then blended with waterborne (wb) polyacrylate for pressure‐sensitive adhesives (PSAs). The preparation conditions of DGE‐HR emulsion were studied. DGE‐HR emulsion with an average particle size of about 220 nm was obtained. Furthermore, the thermal, adhesive, and viscoelastic properties and the morphology of DGE‐HR/polyacrylate composite were investigated. Thermal analysis indicated that glass transition temperatures (T_g) of the DGE‐HR/polyacrylate blends became higher as the DGE‐HR content increased and DGE‐HR did not have a significant influence on thermal stability of the blend films. Atomic Force Microscopy (AFM) observation revealed that the DGE‐HR particles added had a good miscibility with acrylic particles. Additionally, for these tackified acrylic PSAs, positive correlations between mechanical performance and viscoelastic response at bonding and debonding frequencies were also found. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 42965.     

Surface and interfacial FTIR spectroscopic studies of latexes. III. The effects of substrate surface tension and elongation on exudation of surfactants

This paper focuses on the effect of the substrate surface tension and mechanical elongation of EA/MAA latex films on the ionic and nonionic surfactant mobility. Although the mobility of anionic surfactants is inherently sensitive to the substrate surface tension, nonionic surfactants appear to remain uniformly distributed across the latex film. This behavior is attributed to the enhanced compatibility with the copolymer latex. Mechanical elongation of the latex films enhances surfactant exudation to the surface due to the increased surface energy of the film forcing surfactants to the latex surface.     

Untersuchung über die agglomeration von polymerisatlatices

Different polymer latices are often incompatible, even when the emulsifying agent is the same in each. If one polymer has a proportion of hydrophilic groups (type ?A”? latex) and the other does not (type ?S”? latex), a mixture of the two latices may coagulate within seconds of mixing. Quite small proportions of type ?A”? will cause agglomeration of the particles of a type ?S”? latex. If 1% of a latex prepared from ethyl acrylate and acrylic acid (95:5) is added to a poly(butylacrylate) latex, D?_w, = 800 Å, and the pH is adjusted to 8–9, the resulting latex is characterized by D?_n, = 6300 Å, D?_w, = 7300 Å; addition of any given type ?S”? latex increases the average particle size still more. The mechanisms involved were studied by observing changes in particle size distribution, by the use of polymerizable dyes as markers, and by electron microscopy. The results of these investigations are : The latices are protected only in some respect by the emulsifier. The protective ionic doublelayer formed by the emulsifier around a type ?S”? particle repels other particles, but not type ?A”? particles. If a collision occours between particles of type ?A”? und type ?S”? they stick together; this process is repeated as often as a type ?S”? particle hits the surface of ?A”?. All the type ?S”? particles of the associate combine to one big particle in such a way that the ?A”? particle stays at the surface and remains active for further agglomeration.     

Surface tension of Nanofluid-type fuels containing suspended nanomaterials

ABSTRACT: The surface tension of ethanol and n-decane based nanofluid fuels containing suspended aluminum (Al), aluminum oxide (Al2O3), and boron (B) nanoparticles as well as dispersible multi-wall carbon nanotubes (MWCNTs) were measured using the pendant drop method by solving the Young-Laplace equation. The effects of nanoparticle concentration, size and the presence of a dispersing agent (surfactant) on surface tension were determined. The results show that surface tension increases both with particle concentration (above a critical concentration) and particle size for all cases. This is because the Van der Waals force between particles at the liquid/gas interface increases surface free energy and thus increases surface tension. At low particle concentrations, however, addition of particles has little influence on surface tension because of the large distance between particles. An exception is when a surfactant was used or when (MWCNTs) was involved. For such cases, the surface tension decreases compared to the pure base fluid. The hypothesis is the polymer groups attached to (MWCNTs) and the surfactant layer between a particle and the surround fluid increases the electrostatic force between particles and thus reduce surface energy and surface tension.     

The Segregation of Surfactant upon Film Formation of Latex Dispersions: an Investigation by Energy Filtering Transmission Electron Microscopy

We investigated the local distribution of emulsifier in dried films cast from latex dispersions. Energy filtering transmission electron microscopy (EFTEM) allowed the detection of heteroatom-containing domains in unstained samples by electron spectroscopic imaging and elemental mapping. If the samples were prepared at temperatures above the minimum film-forming temperature (MFT), separated domains of surfactant were observed in detachment replicas and ultrathin sections. If the preparation was carried out below MFT the emulsifier was retained at the particle surface and similar observations could not be made. It is suggested that the mobility of the emulsifier at the surface of the particles is increased upon deformation and coalescence in the process of film formation, and that this mobility is a prerequisite for its segregation. Both processes do not take place upon drying below MFT, owing to lower mobility. The correlation between the process of film formation and the segregation of surfactant is discussed for both a dispersion of poly(vinylacetate) and one of polyacrylate.     

Advances in emulsion polymerization for coatings applications: Latex blends and reactive surfactants

The utilization of latex blends to prepare zero-VOC coatings and the use of reactive surfactants in emulsion polymerization are two advances in waterborne technology that are of increasing interest to coatings formulators. The first part of this paper focuses on an investigation of the influence of the interface between high and low T_g latex particles on the gloss and surface morphologies offilms obtained from model latex blends. Gloss was influenced by the concentration of carboxyl groups present on the surface of the latex particles (optimal concentration for maximum gloss = 13% on the high T_g particles, the degree of neutralization of these groups (higher gloss with increased extent of neutralization), the type and concentration of the neutralizing base (higher gloss for stronger bases), and the presence of added surfactant (higher gloss with added surfactant). Gloss was found to be correlated with the surface smoothness of the film. The kinetics, partide size, molecular weight, and location of the reactive surfactant after polymerization, as well as the contact angle of films prepared from these latexes, are examined in the second part of this paper. The polymerization rate profiles were similar to those obtained using a conventional surfactant; however, the dependency of the rate on the number of particles was significantly lower. The amound bound increased and the molecular weight decreased with increasing surfactant concentration. Presented at the 78th Annual Meeting of the Federation of Societies for Coatings Technology, on October 16–20, 2000, in Chicago, IL. Emulsion Polymers Institute and Department of Chemical Engineering, 111 Research Dr., Bethlehem, PA, 18015-4791.     

Viscoelastic and adhesive properties of single‐component thermo‐resistant acrylic pressure sensitive adhesives

Poly(butyl acrylate‐vinyl acetate‐acrylic acid) based acrylic pressure sensitive adhesives (PSAs) were synthesized by solution polymerization for the fabrication of high performance pressure sensitive adhesive tapes. The synthesized PSAs have high shear strength and can be peeled off substrate without residues on the substrate at temperature up to 150°C. The PSAs synthesized in the present work are single‐component crosslinked and they can be used directly once synthesized, which is convenient for real applications compared to commercial multi‐component adhesives. The results demonstrated that the viscosity of the PSAs remained stable during prolonged storage. The effects of the preparation conditions such as initiator concentration, cross‐linker amount, organosiloxane monomer amount and tackifier resin on the polymer properties, such as glass transition temperature (T_g), molecular weight (M_w), surface energy and shear modulus, were studied, and the dependence of the adhesive properties on the polymer properties were also investigated. Crosslinking reactions showed a great improvement in the shear strength at high temperature. The addition of tackifier resin made peel strength increase compared to original PSAs because of the improvement of the adhesion strength. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 40086.