Author Biography 1/10/2006 David W. Horwat Lead Engineer Air Products Polymers, LP.

7201 Hamilton Boulevard Allentown, PA 18195-1501 Phone (610) 481-5646 Fax (610) 481-4839 Internet Address: HORWATDW@APCI.COM Dave Horwat is currently a Lead Engineer with Air Products Polymers. He has worked in the adhesives industry for 33 years since receiving his Masters Degree in Chemical Engineering in 1973. Employed by Air Products Polymers, he provided formulations development and technical service to the adhesives industry for emulsion adhesive raw materials for the past 19 years. Markets served are the packaging market, the wood working market, automotive adhesives, the insulation industry and other industrial bonding markets. Dave has a BS and an MS in Chemical Engineering from New Jersey Institute of Technology in the USA. Prior to his experience with Air Products Polymers, Dave worked for 14 years as a solvent borne and water borne polymer adhesives formulator for a major international adhesives manufacturing company. Dave began with experience in solvent based adhesives in the construction markets with contact cement formulation development. Additional work experience included wood and panel bonding, synthetic and natural elastomer formulations development, pressure sensitive and acrylic adhesives formulations and polymer development. His latest major emphasis is in the conversion to vinyl acetate/ethylene water based alternatives from solvent, hot melt and other non aqueous systems. A frequent speaker on technology issues at the Adhesives and Sealants council meetings, he has been published in North American and European adhesives industry magazines. He is an author of the industry standard training manual Working with Vinyl Acetate Based Polymers Adhesives Manual published by Air Products Polymers. His focus has been the mathematical modeling of adhesives systems from a rheological viewpoint. Dave resides in Emmaus, PA with his wife, three children, three cats and three computers.

Poly (Vinyl Acetate)/ Ethylene Polymer Dispersions for Adhesives

Poly (Vinyl Acetate)/ Ethylene Polymer Dispersions for Adhesives By David W. Horwat Lead Engineer Air Products Polymers, LP. 7201 Hamilton Boulevard Allentown, PA 18195-1501 Phone (610) 481-5646 Fax (610) 481-4839 Internet Address: HORWATDW@APCI.COM

2 Introduction Vinyl Acetate based polymers and copolymers have captured a large share of the adhesives market since their inception over 40 years ago. They earned this large portion of the market because they offer the advantages of excellent adhesion, high performance, good production speeds, low cost economics, and an ease of handling and processing over many previously used natural and solvent systems. The relatively polar nature of a vinyl acetate polymer or copolymer makes it a natural choice for bonding any cellulosic surface like paper, wood or similar composite materials. If properly flexibilized, adhesion to metallic foils, plastics, films and many modern printed surfaces is obtained. Vinyl acetate based polymer dispersions are high molecular weight polymers dispersed in an aqueous media, making a final adhesive film that can be highly heat, water and humidity resistant. Because they are two phase systems, these polymer dispersions are higher in solids and faster setting than solution polymers dissolved in water at equivalent machining viscosities. The polymers are saturated chains with no chemical double bonds , which allows them to remain stable to heat, light, water, oxygen, and micro-organisms. The polymerization proceeds to nearly 100% percent completion in water, so there is little volatile organic content to the dispersion, resulting in an environmentally friendly system. The Advantages of Polyvinyl Acetate Ethylene Based Adhesives Adhesion to a wide variety of surfaces High Molecular Weight Polymers Highly Resistant to Heat Humidity and Water High Solids at Low Viscosity Rapid setting speeds High levels of Wet Tack Resistance to Water , Heat and Solvents can be adjusted easily Good Machining Properties Ease of Compounding Micro-organism resistant Oxidation Resistant Non-Flammable Low Volatile Organic Content Environmentally Friendly

3 An additional reason for their growth and popularity is the ease with which the vinyl acetate homopolymer and copolymer dispersions are transformed into useful, low cost adhesives. One can develop excellent adhesives by blending common ingredients in relatively simple mixing vessels. The dispersions can be modified to become slightly water sensitive adhesives allowing easy cleanup and good machining properties when applied by rollers, nozzles, or spray systems. Conversely, their properties can be modified for improved water resistance, heat resistance or structural strength also via simple blending. Adhesive properties that are not capable of being developed through blending are fundamental polymer dispersion characteristics and are developed by the raw material manufacturer. The selection of the proper polymer dispersion or blend of dispersions is the key to a successful adhesives development project. The choice of the proper raw material dispersion can best be accomplished by examining and understanding four basic aspects of the dispersion i.e., the bulk polymer properties, any functionality added to the polymer, the colloidal properties and the particle size distribution. Each aspect of these dispersion properties will be covered in detail for ethylene vinyl acetate copolymer dispersions in this chapter.

The Properties of Adhesion Polymer Dispersions Bulk Polymer Properties Chemical Functionality Colloidal Protection System Particle Size Distribution

1. The Properties of Adhesion Polymer Dispersions: Bulk Polymer Properties The bulk properties are the properties of the polymer within the dispersed polymer spheres. The chemical composition along with the molecular weight and molecular structure of the polymer are responsible for the tensile strength, the adhesion characteristics, the toughness, the flexibility, and the heat, oxygen, and water resistance of the bondline. The bulk properties include the chemical composition determined by the selection of the type of monomers used, the relative amounts or ratios of the monomers used and the molecular weight of the polymer as determined by the production process. A polymer is a chain of molecular links. In the case of vinyl acetate, the chemical schematic of a vinyl acetate molecule is below. Individually monomers are separate links waiting to be formed into a continuous chain. Vinyl Acetate monomer has a polar acetate end group and a vinyl or double bond in the body of the monomer.

4
Polymer Building: Monomers Determine Bulk Properties
VAc VAc

O C O CH3

O C O CH3

Vinyl Acetate Monomer Molecules

Figure 1 It is the vinyl double bond which can chemically open up and cause a monomer molecule to polymerize with its neighbor. The acetate group does not change in the process. Essentially, a polymer is a macromolecule consisting of a large number of these chemically combined units called monomers linked together as a chain By the careful use of a free radical initiator we can join the individual monomer molecules together in a particular order to form a high molecular weight polymer. Because of the similarity in their structure the vinyl acetate molecules line up to form a regular ordered chain. The order and consistency of the groups results in a closely aligned polymer chains which reinforce each other. As a result, poly (vinyl acetate) homopolymer is hard and cohesive.

Polymer Building: Monomers Determines Bulk Properties

PVAc PVAc PVAc PVAc

C OC O C O C O CH3 CH3 CH3 CH3

Poly(vinyl acetate)
Polymer: Very Orderly , Regular Hard

Figure 2 Glass Transition Temperature A simple way to measure the hardness of a copolymer is to measure the glass transition temperature of the polymer or Tg. The Tg is the temperature at which the polymer turns from an amorphous polymer to a polymer glass. Hard polymers have a high Tg; while a flexible polymer has a low Tg. Because of the closely ordered and aligned chains, pure vinyl acetate homopolymer has a Tg of about 32 C. The polymer is very glass like at temperatures below 32C. Because we are dealing with a very ordered system which has a high degree of attraction for each acetate group, poly (vinyl acetate) has a minimum spacing between the chains. This minimum spacing and an attraction between the groups produces a strong internal cohesive force which limits the rotation and flow of the polymer. Conversely, the Tg or glass transition temperature is also a measurement of the relative flexibility of the vinyl acetate polymer, a vinyl acetate/comonomer mixture or a vinyl acetate polymer /plasticizer mixture. The Tg of vinyl acetate homopolymer is approximately 32C, making it a quite hard, nearly brittle polymer and a marginal film former at room temperature. Hardness or brittleness may not be desirable in many instances. Flexibility is usually imparted in some way to a vinyl acetate homopolymer system. A comonomer or external plasticizer is usually added to lower the Tg and give flexibility to the adhesive. Most adhesion and film formation improvements can be made by flexibilizing the polymer and lowering the Tg. Anything we do to diminish the order or regularity of the chain, lowers the cohesive forces of the polymer simultaneously increasing the molecular flow, the flexibility and the adhesive ability of the polymer. We can disrupt this order within vinyl acetate homopolymer by two methods, increasing the spacing between the chains and by disrupting the attraction between the acetate groups.

6 External Plasticization Functionally, the polymer spacing can be altered by external plasticization by the adhesives manufacturer. A common way to increase the polymer spacing between the chains and flexibilize the polymer by reducing inter-chain attraction and allowing the chains to Figure over each other is the introduction of plasticizer during the compounding step. Plasticizer penetrates the polymer sphere and swells the polymer. Because of the chemical compatibility and similarity between the plasticizer and the polymer, the plasticizer molecule diffuses within the sphere and spreads the polymer chains apart, reducing the cohesion of the resulting mixture; lowering the Tg and improving the flexibility and film formation characteristics. This is one reason most vinyl acetate homopolymer adhesives are commonly formulated with plasticizer.
Polymer Spacing Determines Polymer Flexibility

C O C O C O C O CH 3 CH 3 CH 3 CH 3
Plasticizer Molecule

CH 3 CH 3 CH 3 CH 3 C O C O C O C O O O O O

Figure3 Where rigidity is valued, as in a structural adhesive market - like the wood working adhesives market, unplasticized homopolymer formulations can be desired to promote high fiber tear and strong cohesive strengths. Having too hard a film can be self-defeating since optimum film formation characteristics are needed for best performance. The polymer spheres must flow and coalesce to form a strong film. Too high a Tg can result in a poorly formed film with poor tensile strength.

For paper and most cellulosic composites, the need for ultimate tensile strength is not great; since the composite materials tear easily compared to wood. Film formation and the rate of film formation are now important because the film formation rate is related to how fast a fiber tearing bond is developed. Industrial processes, with high productivity demands and very fast machines , require fast film formation rates. Early in the development of vinyl acetate polymers and copolymers the need to flexibilize and build fast film formation rates was great. Internal Plasticization There is a second way of increasing the polymer spacing between the chains to flexibilize the film. An alternate monomer with a bulky side group was polymerized into a vinyl acetate polymer.
Polymer Composition Determines Polymer Flexibility

C OO

C O O CH 2 CH 2 CH 3

C O C O

CH 3 CH 2 CH 3 CH 3 CH 3 CH 2 CH 2 C O C

CH 3 CH 3 CH 2 CH 3 C O C O O O O C

Polyv inyl Acetate/Butyl Acrylate copolymer

Figure4 This diagram shows butyl acrylate as a comonomer, which effectively hangs a pendant butyl group from the side of the polymer. The chains spread apart to allow for the spacing necessary to make room for the butyl group. This extra space between the molecules breaks the attraction of each chain for each other. They are now capable of sliding over each other and flowing easily. The resulting copolymer is softer, more adhesive, lower in Tg and less cohesive. It can form films at room temperature easily since the film is forming above the glass transition temperature, rather than near or below the Tg. The polymer spheres coalesce easily since they are softer and flowable rather than hard and glass like.

These are some other examples of useful vinyl monomers which can be copolymerized with vinyl acetate. The length or size of the pendant group affects the chain distance and influences the Tg of the resulting polymer. The short pendant group monomers have high Tgs. The longer pendant lengths have lower Tgs

Polymer Composition: Vinyl Monomers OR

Cl O
Vinyl Chloride Acrylates

C2H5 C4H9CHCH2O2C

C2H5 CO2CH2CHC4H9

Dioctyl Maleate

O O CH3 CH2 CH2

Ethylene

Vinyl Acetate

Polymer:

Break up symmetry Add Properties

Figure 5

They are all polymerized through their double bonds to build the polymer chain. In addition to vinyl acetate, the other monomers shown are comonomers which can be polymerized with vinyl acetate. A large the pendant group in the acrylate family will drop the Tg greatly; a small pendant group will not drop the Tg of a copolymer appreciably. The Tg of the vinyl chloride polymer is higher than the Tg of vinyl acetate polymer. With the exception of vinyl chloride, all soften vinyl acetate polymers and produce improved flexibility and a lower Tg. We can numerically quantify the amount a comonomer will drop the Tg by comparing the Tg s of the pure polymer homopolymer

The Tg of the homopolymer can used as a guide of whether the comonomer is increasing the Tg of the final copolymer or decreasing it. A Tg higher than vinyl acetate will raise the overall Tg of the copolymer where a lower Tg will decrease the over polymer Tg Monomer Vinyl Chloride Vinyl Acetate n-Butyl Acrylate 2-Ethyl Hexyl Acrylate Ethylene Tg of Homopolymer 81 C 32 C -50 C -66 C -89 C

The relative Tg of each monomer homopolymer can give an idea of the effectiveness of the comonomer at lowering the Tg of a blend with vinyl acetate. 2-ethylhexyl acrylate introduces a large, bulky 2-ethylhexyl group when copolymerized on the polymer chain. Its homopolymer has a Tg of -66C which is very low. A low Tg is an indication of a highly efficient monomer capable of dropping the Tg significantly per mole percent added. Butyl acrylate introduces a slightly smaller butyl group to the side chain so it is not as flexible per unit mole of monomer as 2-ethylhexyl acrylate. Vinyl Chloride will raise the Tg of the copolymer because the homopolymer Tg is 81C, which is higher than the 32C Tg of Vinyl Acetate,. Ethylene introduces a space in the polymer chain and has the lowest Tg of the common comonomers. The Case for Ethylene: An alternate way to softening the polymer by spreading apart the polymer chains is to disrupt the order of the acetate groups. When we copolymerize ethylene into the polymer backbone there is no pendant side group. Ethylene leaves a space, a hole or a swivel point in the polymer backbone breaking the uniform pattern of the acetate groups.

Polymer Uniformity and Spacing Determines Polymer Flexibility

O C O CH 3 CH 3 CH 3 C O C O O O

C O C O CH 3 CH 3 CH 3 C O O

Polyv inyl Acetate/Ethylene Copolymer

Figure 6

The use of ethylene as a Comonomer to suppress the Tg of the vinyl acetate polymer backbone require the use of levels of ethylene less than 50 mole percent. Typical VAE emulsions can use 5 to 50 percent ethylene as an additive. Vinyl acetate is the dominant monomer in these systems. Hot Melt Ethylene Vinyl Acetate polymers are mostly ethylene in composition. Because ethylene exhibits crystallinity and short intramolecular chain distances when it is the dominant monomer, low levels of vinyl acetate are used in hot melt based polymers systems to break the crystallinity of ethylene based polymers. In hot melt, ethylene vinyl acetate systems the vinyl acetate levels needed to break the ethylene crystallinity are of the levels 18 to 40% Using ethylene to disrupt the regularity of a vinyl acetate based polymer does not spread the polymer chains apart since there is no bulky side group. It does break the regularity of the chain by inserting spaces or holes in the pattern. This reduces the attraction of the acetate groups for each other by disrupting the distance between them. Because the polymers can now rotate but the spacing between the chains is the same, the flexibility is improved but the heat resistance is not substantially impacted. This is the main chemical reason why the ethylene copolymers are widely commercialized in the marketplace. There is a minimal impact on the cohesive strength for the improvement in flexibility with ethylene as the flexibilizing comonomer. Copolymerization with ethylene is a way to internally flexibilize the spheres. The higher the ethylene level the greater the internal disruption of the attraction between the groups and the more flexible is the resulting polymer. The Tg drops as the amount of comonomer increases; flexibility improves, and adhesion improves. By improving the flexibility of the polymer, the ability to flow and wet out a surface is greatly improved, so the adhesion is improved. The film formation and the water resistance is improved if the spheres flow out and wet out to form a tight continuous film. Conversely, heat resistance, tensile strength and cohesiveness are all measurements of the internal attractive forces within the polymer. A higher Tg favors these properties

A Typical Tg Curve Versus Weight Percent Comonomer

35

Tg

30

25
Tg in Degrees Celsius

20

15

10

0 0 5 10 15 20 25

WT. PERCENT ETHYLENE

27

Figure 7 This graph approximately illustrates the drop in Tg and the increased flexibility of a combination of ethylene with vinyl acetate. Similar curves can be developed for acrylics and even for the post addition of plasticizers. The slope of the curve would change according to the effectiveness and compatibility of the plasticizing additive or comonomer. No slope would be as effective as ethylene.
The Effect of Ethylene as a Comonomer
Adhesion to Plastics

Decreasing

Cohesive Strength

Increasing

Water Resistance Hydrolysis Resistance Flexibility

Ethylene Content

Figure 8

The physical/ performance characteristics change according to the percent ethylene addition. In addition to the adhesion improvement, the water resistance of the polymer film increases due to the hydrophobic nature of ethylene. Ethylene doesnt hydrolyze under alkaline conditions so hydrolysis resistance is improved. Hydrolysis resistance also improves since the ethylene introduces a space or hole in the vinyl acetate segments. Under alkaline conditions, polyvinyl acetate will hydrolyze, exchanging the acetate group as an acetate salt while replacing it with a hydroxyl group. This is the basic reaction of the formation of polyvinyl alcohol. An adjacent acetate group will then continue in the hydrolysis reaction. The resultant process rapidly unzips the polymer; resulting in the conversion of the polyvinyl acetate to polyvinyl alcohol. This susceptibility to hydrolysis explains why polyvinyl acetate homopolymer is not recommended for performance under alkaline conditions. Copolymerization with ethylene, even more than with acrylic 14omonomers, effectively stops the hydrolysis reaction. The ethylene position will not promote the release of an adjacent acetate group easily. The energy to continue the hydrolysis reaction is higher in this form than in polyvinyl acetate homopolymer. This is why a common use for vinyl acetate ethylene copolymers is as a cement modifier or additive. They are resistant to hydrolysis compared with standard vinyl acetate or vinyl acrylic copolymers polymers. In fact, test films of vinyl acetate-ethylene copolymers have been exposed to weak alkalis and acids for more than a year without showing any signs of deterioration. A wide variety of commercial ethylene contents are available in the industrial dispersions marketplace. Aside from the chemical benefits of ethylene like hydrolysis resistance or water resistance, the general physical tradeoffs described below are cohesiveness versus adhesiveness.

Name

Tg C Poly(VinylAcetate) 35 Homopolymer Airflex 315 * 17 Airflex EP400 5 Airflex EP401 -15

Peel Adhesion to PVC foil N/cm Nil 2.5 9 10

Cohesive Strength N/mm2 25 13 8 4

Airflex is a Trade Mark of Air Products Polymers, LP Lowering the Tg by increasing the ethylene content increases the 180 angle peel adhesion value of a PVC foil wet bonded to plywood. The cohesion values, as measured by tensile strength, decrease in a similar fashion. The beneficial effect of increased ethylene upon adhesion reaches a point of diminishing returns. At a Tg below 0C, the amount of incremental adhesion improvement becomes limited. It is the molecular weight of these polymers that limits additional adhesion improvement.

Branching: In addition to the compositional aspects of the bulk properties, the molecular weight of the polymer is also a bulk characteristic. In the case of vinyl acetate polymerization, the chain length or molecular weight is extremely high. In addition to the normal linear chain growth, branching from the main chain as a side chain or a possible bridge between two chains can occur during polymerization. Branching or grafting can also link through the protective colloid. Internal branching can increase the molecular weight further by covalently linking the chains of the polymer within the sphere together. The molecular weight or percent grafting correlates well to the percent insolubles in a true solvent, like toluene. Highly crosslinked, insoluble vinyl acetate polymers and copolymers have very good heat resistance; but have reduced polymer cold flow properties at room temperature. They take longer to form perfect, continuous films. Lower molecular weight polymers have more ability to flow at room temperature so their film formation ability is faster along with their wetting/ flow and adhesion characteristics.

Structure of Grafted Poly(vinyl acetate)

C O C O C O C O CH3 CH3 CH2 CH3

C O C O CH3 CH3
Polymer Grafting Determines Polymer Cohesiveness

Figure 9 Branching increases the cohesive strength of the polymer and can raise the Tg of the polymer slightly by limiting the polymers flow.

The effect of increased polymer branching or grafting results in: The Effect of Increased Polymer Branching Increased Tensile Strength/ Toughness Increased Heat Resistance Reduced Tackiness of a Dried Film Increased Solvent Resistance Increased Acceptance of Polar and Water-Miscible Solvents

This internal grafting or crosslinking increases the tensile strength and the heat resistance of the polymer. It decreases the solubility of the polymer in polar solvents and reduces the surface tackiness of the polymer. Grafting can be promoted by the use of poly (vinyl alcohol) as a colloid and by altering various process variables. In the case of the polyvinyl alcohol stabilized vinyl acetate ethylene copolymers (VAE), the reduced polymer flexibility limits the polymer wetting and keeps adhesion from continually increasing with increasing ethylene content. 2. The Properties of Adhesion Polymer Dispersions: Chemical Functionality: Successfully developed adhesives balance the cohesive strength and the adhesive strength of the formulation to the strength and chemical characteristics of the substrates. Chemical functionality directly impacts the adhesion aspect of the bond. Since cohesion is related to composition, Tg and other bulk characteristics, it was previously discussed. Added chemical functionality generally improves the adhesion / cohesion balance, if desired. Prior to optimizing a formulation for a substrate; a discussion of bonding is necessary. The adhesives market hosts formulations based upon water-borne polymers, solvent solution polymers, hot melt polymer systems and 100% solids curable systems. The basic principles of adhesive bonding apply to all systems. Ideally, the combined forces of adhesion and cohesion should exceed the tearing strength of the substrate. Of the three modes of failure shown below, substrate failure is the most desired. Because bond failure could be adhesive or cohesive, proper bond performance is a formulation balancing act.

Adhesive Bond Failure Types

Substrate Failure
Adhesive Glue Line

Adhesion Failure
Adhesive Glue Line

Cohesion Failure

Adhesive Glue Line

Figure10 Anything that interferes with adhesion or substrate wetting reduces the ultimate bond strength. Because wetting is polymeric flow or wet-out on a substrate, it is highly dependant upon the liquid or viscous characteristics of thermoplastic polymers. The cohesive forces, often referred to as elastic forces, are the solid-like properties of the polymer. The cohesive properties are responsible for physical tensile strength characteristics and the durability under heat or water exposure. Unnecessary reductions of cohesive strength also reduce the ultimate bond strength. The optimum bond strength occurs when the proper combination of adhesive strength and cohesive strength exists in a bonded system. The interaction of the adhesive polymer and the strength of the substrates determine the optimum point.

Adhesion - Cohesion Balance

Bond Strength

35

30

25

Adhesion

Cohesion

20

15

10

0 0

Increased Crosslinking

Figure 11 There are two phases, which can be addressed by the crosslinking process, the bulk polymer, and the polymer sphere interface. Intra-particle crosslinking is impacted by the bulk properties of the polymer used. The polymerization process can be adjusted, along with the basic building block components to produce a wide variety of dispersed polymers, with many degrees of flexibility and strengths within the polymer bulk properties. The adjustments, which can be made during polymerization, include controlling the molecular weight, adjusting the Tg, adding an internal crosslinking monomer, and producing internal grafts between polymer chains. This is sometimes referred to as increasing the gel content or insolubles of a polymer. The polymerization process controls all these during manufacture. There is very little that a formulator can do to change the bulk properties of a polymer dispersion. He can only choose polymers based upon the information provided. Chemical Functionality and Crosslinking Building both cohesive strength and adhesion always results in a higher optimized tensile strength for a bond. Improvements in the overall balance of polarity vs Tg can be obtained by the incorporation of a third monomer into a vinyl acetate copolymer dispersion. The most common functional additive monomers would incorporate a carboxyl, amide and Comonomer or hydroxyl functionality into the polymer backbone.

Carboxyl Functionality A polymer can be chemically modified with a reactive acidic Comonomer to add carboxyl groups into the polymer backbone. The acidic nature of a Comonomer, like acrylic acid, yields substantial adhesion benefits, especially on metallic foils or other polar surfaces. It also adds a chemical site on the polymer backbone which can be used for crosslinking and changing the cohesive nature of the polymer through formulation.

Structure of Grafted Poly(vinyl acetate)

C O C O C O C O CH3 CH3 CH2 CH3

C O C O CH3 CH3
Polymer Grafting Determines Polymer Cohesiveness

Figure 12 The incorporation of carboxyl functionality in a vinyl acetate-ethylene dispersion offers three advantages over non-carboxylated products. They are: increased adhesion to metals and polymeric surfaces; reactive sites for cross-linking; and a means for thickening. Airflex 426 and Airflex 465 dispersions have similar glass transition temperatures with similar ratios of vinyl acetate to ethylene. They are both stabilized with the same colloidal systems and are manufactured with the same process. The essential difference between the two is that Airflex 426 dispersion contains a carboxyl functional comonomer and as a result adheres much better to metal substrates than Airflex 465 dispersion. Annealed and tempered aluminum foil may be bonded to natural kraft paper with Airflex 426 dispersion. The bonds are strong enough to resist 24-hour water immersion. Carboxyl functionality also increases the adhesion of vinyl acetate-ethylene to several metals.

Improving the Adhesion to metals via Carboxylation Airflex 426 Airflex 465 Aluminum 3.0 pli* 2.2 pli Brass 4.2 pli 2.6 pli Galvanized Steel 2.5 pli 1.4 pli Cloth to Metal T-Peel (lb/in) If sufficient carboxyl functionality is present the dispersion will be capable of self-thickening with a change in pH. Raising the pH of Airflex 426 dispersion will increase its viscosity. . The carboxylic acid on the polymer chain is neutralized by the alkali, producing similar ionic charges, which repel each other, causing the chain to uncoil. Additionally because of the presence of a neutralized salt on the polymer backbone, the polymer absorbs water and swells, resulting in a viscosity increase. Uncoiling of the polymer chain can also increase its adhesion to metal substrates because there are more carboxyl groups available for bonding. There is, therefore, a direct relationship between pH vs. adhesion peel value as well as pH vs. viscosity.

Effect of pH on the Viscosity of Carboxylated VAE Emulsion

3500 3000 2500

VISCOSITY (CPS)

2000 1500 1000

VISCOSITY
500 0 4.0 4.5 5.0 pH 5.5 6.0 6.5

14

Figure 13

It is necessary to properly buffer a VAE at a high pH to avoid the natural drift towards lower pH that occurs with the hydrolysis of residual vinyl acetate monomer to acetic acid at a high pH. The aging characteristics of alkaline VAE formulations need to be monitored for that reason. If available, functionalities like carboxyl groups can be crosslinked with post added crosslinkers. Crosslinking will increase the cohesive strength of an adhesive but it may reduce the polymers flow characteristics and thereby reduce the adhesion. Care must be taken to evaluate the change in both adhesion and cohesion when exploring crosslinkers. Crosslinkers may be used as 1 part (storage stable) or 2 part systems (mixed systems with a pot life)

Crosslinking Agents Functional Group Crosslinked Hydroxyl Glyoxal Yes Isocyanate Prepolymers Yes Zinc Oxide No Magnesium Oxide No Zirconium Ammonium No Salts Urea Formaldehyde Yes Melamine Yes Formaldehyde Aziridine No Agent

Functional Group Crosslinked Carboxyl No No Yes Yes Yes No No Yes

The phase which can be addressed by the formulator is the interface at the surface of the particles. When failure is at the interface between the particles, crosslinking can be very beneficial to developing higher performance systems. Since the polymer interfacial strength is usually weaker than the bulk polymer characteristics, crosslinking between the polymer spheres can address the weakest link of an adhesive and improve strength. If the polymer is modified with a chemically reactive functional carboxyl comonomer during the polymerization, the formulator can be left with a very significant spot to perform some crosslinking chemistry. A common method of crosslinking carboxylic acid functionality is with metal salts. Example metal salts can include salts of magnesium, calcium, aluminum, zinc and zirconium.

Crosslinking Carboxylic Acid Groups with Metal Salts

H+
Anion

Anion

CH2 ++ COOH + METAL

or Higher

CH2

CH2 ++

CH2

COOH

METAL COO -OOC

or Higher

CH2
Anion

CH2

CH2
Anion

CH2

H+

Figure 14

The inter-particle bonds are formed as the acid functionality at the sphere surface bonds with metal ions of opposite charges. There is a strong ionic attraction between a multi-valent metal ion and an acid group. This can serve to increase the inter-particle strength. The interfacial region between the spheres is usually the weakest link with water exposure. Since the colloid and surfactant still present at the spherical interface remain water sensitive, they are plasticized and solubilized heavily during water exposure. Crosslinking with di-valent and tri-valent metals can improve the water resistance performance of a dried adhesive polymer film. Tri-valent Aluminum ions seem to yield the highest performance improvement in water resistance testing or common metal ions tested. In heat resistance testing, Aluminum performs similarly to other metal ions like Calcium, Magnesium or Zinc. A test of various anions of aluminum salts show that all aluminum salts have better water resistance and heat resistance than the controls. The major performance enhancer seems to be the Aluminum ion itself.

Amide and Acrylamide Functionality

Self Crosslinking Functionality

VAc VAc NMA VAc

C O O C O C O C O NH C O O O CH3 CH OH
2

CH3 CH 3 CH3

Poly (vinyl acetate) Homopolymer with N-methylolacrylamide

Figure 15 Amide functionality can promote increased adhesion to polar surfaces. Amides and acrylamide functionality can also be crosslinked with external crosslinkers in a manner similar to carboxyl functionality. Where the carboxyl functionality crosslinked with metal salts is an ionic effect, impacting primarily heat resistance; crosslinking amide functionality is a covalent bond which will generally improve the water resistance of an adhesive. Common two part crosslinking systems which react to amide groups are melamine formaldehyde or urea formaldehyde technologies. If the reactive group on the polymer is a methylolated acrylamide, like N-methylol acrylamide (NMA), the polymer becomes capable of self crosslinking through self condensation with heat and/ or a mild acidic catalyst. This reaction commonly liberates formaldehyde as a byproduct of the self crosslinking reaction. Most of these crosslinking systems have a limited pot life and are designated as two part systems Hydroxyl Functionality Hydroxyl functionality can be incorporated into a polymer in two ways. A hydroxyl functional monomer can be copolymerized with the vinyl acetate and ethylene to place a pendant hydroxyl group on the polymer backbone. Hydroxyethylacrylate is a common comonomer capable of adding primary hydroxyls to a polymer. If the colloidal system is purely surfactant based, this is a good method to bring hydroxyl functionality into the polymer.

The protection system usually has some functionality associated with it because the hydrophilic portion of the surfactant / colloid molecule must be present to be attracted to the water phase. The second form of hydroxyl functionality can come from the colloidal protection system itself. It may be possible to perform some chemical reactions on the protective colloid present, depending upon its nature or chemistry. Polyvinyl alcohol is an extremely popular protective colloid, as it has many desirable rheological characteristics for the adhesives market and is very compatible with all vinyl acetate copolymer systems. Polyvinyl alcohol is a prime source of hydroxyl functionality.

The Emulsion Stabilizer as a Source of Functionality

PVOH Protected
PVAc
PVAc Increase mol. wt.

PVOH
PVOH grafted

Surfactant Protected
Increase mol. wt.

Figure 16 The protective colloid might be capable of being insolubilized or crosslinked, depending on functionality present on the molecule. During the polymerization process the polyvinyl alcohol is actually grafted to the polymer surface by hydrogen abstraction through the residual acetate groups. It is an integral part of the polymer, as if it were a hydroxyl containing comonomer.

Poly(vinyl acetate) With Grafted Poly(vinyl alcohol)

OH

OH

O C O CH2

OH

C O C O CH3 CH3

Figure 17 Surfactants usually exist prior to polymerization as small soap concentrations called micelles. The monomer can absorb into the micelles, swelling them. There may not be significant grafting of surfactants onto a polymer surface to consider them as sites for crosslinking. Their attachment is not chemical in nature, merely associative. A very effective two part crosslinker for crosslinking hydroxyl functionality is the use of isocyanate prepolymers. These are two part systems where 5 to 15 % of an isocyanate prepolymer is added to an adhesive prior to bonding. The mixed system can have a useful potlife of 1-4 hours. When formed within this useful potlife range, the resulting bonds demonstrate high water resistance. This is the basis for EPI systems (Emulsion Polymer Isocyanate). Wood or metal to wood bonds made with EPI adhesive systems resist boiling water and have a high degree of environmental exposure resistance. The use limitations on potlife make one part, storage stable crosslinking systems desirable. Frequently there is a tradeoff involving a lower level of performance vs two part systems.

A mild crosslinking system that is a stable one part crosslinker is boric acid. At a pH under 5.0, boric acid will crosslink adjacent hydroxyl groups on the same molecule reducing the water sensitivity and creating a tacky rheological flow. Frequently, adhesive compounders will take advantage of the boration reaction with poly (vinyl alcohol) stabilized dispersions to create quick-tacking adhesives. This tacky gel can hold substrates together while wet increasing green strength or wet tack

Crosslinking PVOH with Boric Acid

Borate Reaction pH > 5

CHOH CH HO 2 CH 2 OH B HO CHOH OH CH CH 2 O O B O CH O CH 2 O + 4H 2 CH

Borate Reaction pH < 5

CHOH CH HO CH 2 OH B HO CHOH CH CH 2 O O B OH

+ 2H O 2

Figure 18

The boration reaction is very pH sensitive. Below a pH 5, PVOH forms a monodiol with the boric acid group which provides a storage stable "tacky" structure. As the pH is raised above 5 the chemistry of the crosslinking changes dramatically. Above a pH of 5, the borated dispersion will begin to rise in viscosity. The boric acid ion turns into a borate ion and increases its attraction to two polyvinyl alcohol molecules. The result is a tight insoluble gel. This is a reversible reaction with pH. The table of organic crosslinking agents for the hydroxyl functionality also includes formaldehyde resins and glyoxal along with a variety of other agents. Most formaldehyde types of crosslinking agents are very effective in crosslinking hydroxyl functionality. They tend to be useful as a two-part system where the crosslinker is added directly before the adhesive is used. These can then crosslink slowly after the bond is made and wetting has occurred to greatly

enhance performance. As one-part systems, they tend to cause a rise in storage viscosity so their potential may be limited to two component packages.

PVOH Commercial Crosslinkers

Glyoxal Crosslinks Two Hydroxyl containing polymers
O OH OH + H H n O O O + H O O

Figure 19

Glyoxal is potentially useful as a one-component system. The crosslinking chemistry proceeds in accordance with this reaction. It is very powerful reaction and should be used at low levels to preserve storage stability. Again an exploration of the performance benefit of glyoxal as a crosslinking additive reveals the cohesion/ adhesion balance trade off.

The Adhesion / Cohesion Balance

Glyoxal with a VAE Emulsion
18
Creep Resistance at 77C, mm/min

16 14 12 10 8 6 4 2 0 0 1% 2% 4% 77C Heat Resistance x 100 (mm/min) PVC Adhesion

Wt.% Glyoxal

Figure 20 The same theme seems to run through these evaluations, i.e. cohesion and adhesion are antagonistic trade offs. Increasing one usually reflects a decrease in the other. Fortunately, compromise is usually achievable. 3. The Properties of Adhesion Polymer Dispersions: Colloidal Protection System The dispersion polymer is a bit more complex than a solution or 100% solids systems because of the multiple phases present, namely a polymer solids phase dispersed in an aqueous liquid phase. To promote stability the particle protection system is present at the interface of the two phases.

Polymer Spheres Dispersed in An Aqueous Media

A Two Phase System
Liquid Phase

Polymer Phase

Protective Colloid

Figure 21 Its presence is needed to keep the spheres apart and separated during manufacture, compounding, and during storage / handling. If the spheres were to collide and aggregate they would form grit or lumps. They would not be stable towards pumping, application, or materials handling. The surfactant or protective colloid can use ionic charges or non ionic steric hindrance to keep the spheres from colliding. There are two general types of protection systems i.e., colloidal polymers and actual surfactants. Mixtures of both systems are also used to generate combined properties Properties of Various Protection Systems Surfactants Colloids Possess a CMC Yes No Graft to the Particle Possible Yes Ionic Character Possible No Molecular Weight Low High Solution Viscosity Low High Surfactant Protection/ Stabilization Surfactants are members of the soap family. They have a hydrophilic end which orients itself toward the water phase and a hydrophobic end which orients itself toward the polymer phase. Because of their limited solubility in either phase they congregate at the interface of the phases. They may exhibit a property called micelle formation. This property can create tiny aggregates of the surfactant in the water phase once a certain concentration is reached. This is the critical micelle concentration or CMC of a surfactant. These micelles can act as seeding points for the formation of polymer particles during the polymerization process. Micelles are small so polymers created within the micelles tend to be of a small particle size. They may anchor to the particle by grafting into the polymer as it grows.

Surfactants may be nonionic or ionic. The characterization depends upon the method of solubilization that is used in the molecule. A nonionic surfactant will orient itself due to the polarity of the various functional natures built into the surfactant but it will not actually possess an ionic charge. Nonionic surfactants can be based upon polyethylene oxide or poly propylene oxide If an ionic surfactant possesses a negative charge on the hydrophobic group to help stabilize the polymer particle it is called an anionic surfactant. The ionic charge will always orient toward the water phase and possess very good solubility in that phase. If the hydrophobic side possesses a positive charge the surfactant is designated cationic. If a molecule has both charges associated with it, it is called amphoteric. Each type of surfactant has different emulsification capabilities, different attractions toward substrate surfaces, and different stabilities toward chemical additives. Higher molecular weight polymers that are water soluble but have no micelle formation capability are usually designated by the term colloids. Because of differences in polarity or solubility within the polymeric molecule they orient themselves at the particle surface between the polymer and aqueous phase. Water soluble, colloidal polymers that may be used are polyvinyl alcohol, cellulosic polymers, starches, dextrins and natural gums. Depending upon the emulsification ability of each polymer; a costabilized system with a surfactant may be required. Each is a high molecular weight polymer which adds viscosity to the dispersion. The particle sizes are generally larger than pure surfactant stabilized dispersions. They generally have higher surface tensions. . Colloidal Polymer Protection Systems Polyvinyl alcohol Partially Hydrolyzed Polyvinyl alcohol Fully Hydrolyzed HydroxyEthyl Cellulose Dextrin, Starches Natural Gums

Protective Colloids Hydroxyethyl cellulose, dextrin, starch, gum arabic are used to create specialized dispersions with unique properties. Each has a unique contribution to the rheological and adhesive properties of the resulting dispersion. As an example, HEC imparts a thixotropic rheology with added water resistance and chemical stability. Dextrins and starches impart extra water sensitivity for remoistenable gums, envelopes or tapes. These protection systems usually form the basis for the family of specialty vinyl acetate homopolymers and copolymers because of the different properties imparted by the colloidal system to the dispersion. Polyvinyl alcohol, because of the similar nature to poly(vinyl acetate) is the most common colloid in the vinyl acetate adhesives market. It comes in a number of degrees of hydrolysis which affects the emulsification capability of the polymer. The partially hydrolyzed variety has the best emulsification tendencies and the lowest surface tension of the poly(vinyl alcohol) family. It is the most commonly used colloid. If a high hydrolysis variety is used for water resistance, a low level of surfactant is sometimes added to enhance the emulsification capabilities of the overall colloidal protection system. The chart describes the nature of the emulsifying systems effect on various application properties. The range of properties affected is broad because there can be radical variations in average particle size and particle size distribution among these types. The Effect of Emulsifier on Adhesive Properties Colloidal Protection Large Narrow to Large Strong Good Rapid Newtonian, High Viscosity Characteristic Particle Size Mean Particle Size Standard Deviation Wet Tack Machining Speed of Set Rheology Surfactant Protection Small Narrow Low Poor Slow Newtonian, Low Viscosity

The table above compares the dispersion properties of Colloidal protection systems vs. Surfactant Protection systems in six different aspects; Mean Particle Size, Particle Size Distribution, Wet Tack, Machining Properties, Speed of set, and Flow rheology. In general surfactant protection produces smaller particles with a high surface area. These generally set slower and have lower viscosity than an equivalent colloidally stabilized dispersion. Polyvinyl acetate can be protected with colloid systems, surfactant systems or a combination of both. The type and amount of protection used in the polymerization of polyvinyl acetate have a great bearing on the physical properties of the resin and on the working characteristics of the dispersion. Dispersion rheology properties are controlled by the protection system.

A dispersion which is protected solely with a surfactant (nonionic surfactants are generally used with polyvinyl acetate) has a fine particle size, a rather narrow particle size distribution and a low aqueous phase viscosity. Because the mean particle size of surfactant stabilized systems is small and the water phase viscosity is low, the wet tack and setting speed of these products is low. Their flow rheology may be thixotropic rather than Newtonian so they could shear thin when applied by rollers, extrusion, and spray systems. Depending upon the application system a slight amount of shear thinning could be an advantage. It must be balanced against the loss of setting speed and wet tack development. The most frequently used protective colloid polymer for vinyl acetate is polyvinyl alcohol. It is the classic colloid because of a number of advantages. Since partially hydrolyzed polyvinyl alcohol is a poor emulsifier compared with a surfactant, a polyvinyl acetate dispersion protected with this colloid would have large particles. The molecular weight of the colloid is large compared to surfactant systems. This large particle size in combination with a high viscosity aqueous phase viscosity yields a fast setting, tacky, dispersion that does not change its viscosity much as it experiences high shear conditions. Polyvinyl alcohol is a high molecular weight water-soluble molecule. It will therefore contribute a high degree of wet tack to a dispersion that is not possible with surfactant protection. Polyvinyl acetate dispersions protected with partially hydrolyzed polyvinyl alcohol have a combination of properties usually described as good machining, which include good flow, clean running, easy cleanup, and a non-slinging or spitting rheology. A high level of wet tack and good machining properties allow the commercial use of these copolymer adhesives in modern application equipment. They work at acceptable line speeds yielding highly productive systems. Dried films are more water sensitive than surfactant stabilized dispersions; so the clean up of application equipment is easily accomplished. The environmental impact is minimal since recycle adhesive bonds can be broken easily by any modern repulping processes. Part of the highly efficient nature of these systems is due to their rapid speed of set. Colloidally stabilized polyvinyl acetate copolymer dispersions set by losing water through evaporation into the air and also by water absorption into the porous substrates to which they are applied. The large polyvinyl acetate spheres in the dispersion pack together and form capillaries which drive the water out at a rapid rate. The fine particles in an all-surfactant system are colloidally more stable; they form smaller capillaries and release water out at a slower rate. Dispersions which combine surfactant and colloid protection will display properties that fall somewhere between Those properties exhibited by colloid systems or surfactant systems alone

The Advantages of Polyvinyl Alcohol Protection Systems Good Machining Easy Clean Up Strong Wet Tack Rapid Setting Speed High Thickening Response High Heat Resistance Improved Non Block Crosslinking Potential . Because the partially hydrolyzed poly(vinyl alcohol) molecule has portions which are poly(vinyl acetate) like, the acetate groups of the colloid can participate in grafting in a similar fashion to the acetate groups within the particle. Poly(vinyl alcohol) becomes chemically grafted to the particle surface in this process which increases the durability of the protection system to mechanical shear and compounding ingredients. The grafted colloid can impact the properties of a dispersion favorably. The lack of shear thinning gives a predictable response on coating machinery in terms of consistent glue line application.

RHEOLOGY OF PVOH Stabilized Emulsion vs. an Alternate Colloid

VISCOSITY VERSUS SHEAR RATE

VISCOSITY (CPS)

1000

500

PVOH Alternate Colloid

0 0 1000 2000 3000 4000 5000

SHEAR RATE (1/SEC)

Figure 22 This curve shows the viscosity response of a polyvinyl alcohol protected dispersion and a non poly(vinyl alcohol) protected dispersion to increasing levels of shear stress. The poly(vinyl alcohol) protected dispersion resists the shear and maintains a higher viscosity under stress than the alternate colloid.

4. The Properties of Adhesion Polymer Dispersions: Particle Size Distribution: The final element to understanding the characteristics of an adhesive dispersion is the particle size and particle size distribution. From the previous discussion it is evident the bonding performance of a dispersion is not just based upon its chemical composition. The colloidal protection system and the resulting particle size distribution can greatly influence the properties of an adhesive dispersion. The size and packing of these spheres influences the wet tack, green strength, the film formation, the machining characteristics and the wetting of an adhesive. Adhesive Properties Affected by the Particle Size Distribution The Solids/Viscosity Relationship Thickening Response Setting Speed Wet Tack Film Formation Integrity Mechanical Stability A simple comparison of the solids and viscosity relationship of several dispersions at different solids shows how the average size, the breadth of the particle size distribution, can affect the final properties. The wider the particle size distribution; the higher the solids must be at equivalent viscosities. Plasticizer thickening response, setting speed, wet tack, and film properties vary greatly with particle size distribution. Not all dispersions are alike; even though their bulk properties could be identical. There are a wide variety of performance characteristics available to the adhesive compounder through the selection of the appropriate raw materials. This translates to a wide variety of potential adhesives being available to perform their tasks. The Variety of Properties of Typical Vinyl Acetate Ethylene Copolymers for Adhesives Solids 50 to 72% Viscosity 1000 to 10000 mps pH 4.0 to 6.0 Protective Colloid PolyVinylAlcohol Tg -20C to 38C

This schematic is a representation of the packing from a rather unimodal polymeric dispersion.
A Uniform Particle Size Distribution

Hexagonal Closed Packing of Uniform Spheres

Figure 23

The tightest packing for uniform spheres is the hexagonal closed pack cell. This theoretically occurs at a volume solids content of about 62%. In a system of identically sized spheres this would be the % volume solids point at which the spheres touch each other. This can be referred to as the critical packing factor. Adjusting for the density differences between the polymer phase and the water phase in a VAE dispersion, this critical packing factor volume percentage would translate to a weight solids percentage approximating 64.6%. However, there are commercially available VAE dispersions available at 72% weight percent and 2000 cps. Obviously, one of our assumptions must be wrong for this to theoretically agree with the 64.6% weight percentage limitation just discussed. In order to raise the solids content above this limit; one must not have a unimodal distribution of particle sizes. The tightest packing for the spheres is dependent upon the standard deviation of the particle size distribution. One can pack more solids into a given volume by using the fact that the small spheres can fill the voids between the larger spheres making more efficient use of available space. Essentially, one can pack more volume per unit cell size.

A Broad Particle Size Distribution

Packing of Non Uniform Spheres

Figure 24 Most adhesive dispersions have rather large particle distributions. A mean of 1 micron is typical for most PVOH stabilized products. The particle size distribution directly impacts a number of key adhesive rheological and compounding characteristics. The solids/ viscosity curve is determined by particle size to a major extent. The thickening response to plasticizer depends upon polymer crowding. The setting speed and wet tack are influenced by particle size distribution and the proximity of volume solids to the critical packing factor.

The Solids/Viscosity Curves of Conventional and High Solids Vinyl Acetate Ethylene Copolymers
VISCOSITY
100,000

80,000

60,000

40,000

20,000

55%

72%

0 0.5 0.55 0.6 0.65 0.7 0.75 0.8

%Solids

Figure 25 The broader distribution has a lower viscosity at any given solids because of the more effective packing of the spheres. The dispersion at 72% solids in Figure has been shifted to the right to yield equivalent viscosities at higher solids due, in part, to the broader particle size distribution of the particles. Dispersions with a broad particle distribution also have a lower degree of plasticizer thickening response because they are further from the critical packing factor concentration at any given viscosity than a more uniform dispersion. The varied particle size distributions that are possible, along with all the possible combinations of colloids and their quantities can produce a wide variety of dispersions with a wide variation of rheological properties. The vast potential of polymer characteristics represents only half of the potential variety that can be used in the development of an adhesive. Because some characteristics are a function of the polymer, polymer selection in adhesive development is critical. Other performance properties may be based upon speed or wet tack properties which are particle distribution and aqueous phase viscosity related.

Additives, such as plasticizer, rheology modifiers, humectants, fillers, and others can also greatly influence the performance of an adhesive. The individual nature of a bonding process is so specific due to machine variations, substrate variations and climate variations that frequently adhesives are formulated specifically to meet the needs of an individual machine running certain combinations of substrates at variable speeds in a changing environment. This individuality of the bonding process is the reason there is no such thing as a universal adhesive.

5.

Bond Formation: How do dispersion based adhesives bond?

All adhesives follow a basic three step process to forming an adhesive bond. The Mechanics of Bond Formation for Adhesives 1. Application as a Liquid Wetting of Substrates 2. Gain in Viscosity Green Strength or Wet Tack 3. Setting of Adhesive Drying Diffusion of water into substrate The application as a liquid phase allows for intimate contact on a molecular level. Wetting of the surface involves attractive forces like Vander Waals or electrostatic forces. The gain in viscosity can involve a rise in viscosity or a phase change. This can involve green strength or early strength of the bond before it is fully formed. Ultimately a polymeric film is formed and the glueline is a solid. The most common bonding method for dispersions is the use of wet combining to form an adhesive bond. For this method, it is mandatory that a porous surface be involved in the construction. If a porous surface is not involved then a heat sealing bonding process must be used. The physical condition of the applied adhesive is a liquid. Most dispersion adhesives can be applied by rolls, spray, brush, extrusion or other industrial coating processes. When an adhesive is applied to a porous surface a number of events begin to occur which ultimately result in a solid adhesive layer bonding two substrates. Bonds of polymer spheres are formed when the dispersion is placed on an absorbent substrate. They are applied as a liquid and flow to wet out the bonding surfaces; they gain viscosity and build green strength; and finally set to their final state. As the water ultimately diffuses away, the polymer solids are left behind to bridge the space between the substrates and form a bond. The polymers are hydrophobic and permit the water to leave more rapidly. Viscosity and green strength are built as the spheres of dispersed polymer are left behind and begin to inter react with each other as the water diffuses away in channels. Ultimately, the spheres touch each other, form a film and lose their identities and individuality. Figures 26 to 29 illustrate this process

The Bond Formation Steps

Initial Contact

Adhesive must flow and intimately wet surfaces contacted

Figure 26 Intimate wetting involves an attractive force built on the similarity in polarity between the polymer and the substrate as well as a similarity of surface tension between the aqueous phase and the substrate As water is absorbed into the porous surface, the concentration of the solids rises in the adhesive layer. As the solids rises, the spheres become starved of liquid and they come into contact. The viscosity of the liquid adhesive rises dramatically. This is reflected in the green tack or wet tack of an adhesive. It is this force which can hold substrates together until the bond is further dried. Many industrial processes require a high level of green strength or wet tack to achieve modern line speeds. In many cases, the force that fixtures the substrates in place may be required to be present instantaneously. There is no waiting for drying to occur.

The Bond Formation Steps DeWatering via Diffusion and Wetting

Adhesive remains in contact through external compression or through internal wet tack

Figure 27 With continued loss of water, the spheres interact. They will begin to crowd each other into formation to begin film formation

The Bond Formation Steps

Channel Formation and Film Formation

Osmotic pressure forces the water out through channels

. Figure 28 The spheres will begin to deform creating channels through which the aqueous media will diffuse away. Osmotic pressure will continue to press the spheres together to form a film. This pressure forces the water out via the channels into the surface nearest the substrate. For diffusion into the substrate and water absorption to occur; at least one substrate needs to be porous.

The Bond Formation Steps

Loss of Identity and Coalescence

The spheres lose their individual identity and merge into a single sheet

Figure 29 Ultimately, film formation occurs as a result of the drying step. The spheres lose their individual identity and merge into a single sheet We have visual proof of this sequence of events in the bonding process. Through the use of an atomic force electron microscope we can profile the surface condition of the film at any stage in the film formation process.

The Bond Formation Steps Film Formation under the Atomic Force Microscope
Initial Film Final Film

Figure 30 A comparison of a dry film that is 24 hours old (initial film) and the same dried film that is 28 days old (final film) is revealing. The film at the end of the 24-hour period still shows spheres with individual identities. The 28-day-old film shows how the polymers have flowed out and coalesced into a more continuous film. The amount and rate of polymer flow and film formation depend upon the inherent flow of the polymer itself and the temperature of exposure. A good bond develops where the adhesive bridges the gaps between the substrate and provides good wetting or mechanical interlocking between the adhesive and substrate surface. This process is referred to as the wet bonding method. Crosslinking, if desired, should ideally occur after the bond has been formed and the polymer has wet out the substrate. If crosslinking occurs prematurely; it limits the polymer wet out and flow which could interfere with adhesion. Limiting the adhesion can weaken a bond, although the final polymer film is tougher. If there is cohesive failure within the film, two possibilities exist; failure within the bulk polymer or failure at the surfaces between the spheres. The proper amount and type of crosslinking may resolve those difficulties. A dry bonding method also exists and is similar but adds an extra step. Dry bonding can be accomplished via the use of pressure sensitive adhesives, heat sealing adhesives, contact cement adhesives, or solvent reactivated adhesives. Remoistenable tapes, labels or stickers are included here because they actually use water as a reactivation solvent. A dried adhesive film is formed and then the three bonding steps are applied. Under time, temperature and pressure the adhesive flows and wets out the opposite substrate. This corresponds to the application as a liquid step. The adhesive is then allowed to cool, crystallize or solidify. Ultimately, the two substrates are bridged by a polymer that uniformly wets out both sides of the surfaces.

If the process goes well the bond should appear to look like the schematic drawing at the top of figure 31(GOOD WETTING). The adhesive has wet and flowed out into the pores of the substrate. It has subsequently developed its full set of properties with a large amount of physical interlock into the surface.

The Wetting of Substrates

Good Wetting
Substrate Not Wet

Poor Open Time Poor Wetting

Substrate Not Wet

Substrate Not Wet

Poor Wetting

Figure 31 The second schematic (POOR OPEN TIME) shows what happens if the open time of an adhesive is exceeded. Because the film has dried extensively, the film formation has failed to wet out the opposite side of the substrates. It fails to interlock and penetrate on that side. As a result the bond fails because of an improper match of the drying characteristics and the production process. The addition of humectants or hydrophilic additives to slow the water release is the common way to match the drying rate to a slower process. Lower solids can also help by having a higher concentration of water present. It is important that the machining, wetting, and other rheological factors match the production process. Most adhesive failure can be traced to improper inter relationships between machining and wetting.

The third schematic (POOR WETTING) shows what happens if the surface tension of the adhesive is too high. In poor cases, the substrate physically repels the water based adhesive. This can occur due to grease, or other low surface tension, hard to wet materials being at the surface to be bonded. Because the film has dried but not wet out either surface extensively, the film fails to interlock and penetrate on any side. Surfactants, which help drop the surface tension of an adhesive, may help alleviate a wetting problem The adhesion, cohesion and processing variables have now been covered. Lets try to fit all the pieces together with some suggestions on how to proceed in developing a number of adhesives with a wide variety of application and processing requirements. 6.0 Formulating Vinyl Acetate Ethylene based Adhesives

6.1 Formulating Ingredients Here is a list of typical ingredients which could be used but are not all necessary; unmodified VAE dispersions can make satisfactory adhesives. Any ingredient can be a possible additive for dispersion adhesives. Sometimes cost, an external requirement or a specification can trim down the number of allowable ingredients Typical Adhesive Ingredient Levels Main Emulsion 100 to 50% Blending Emulsion 0% to 50% Plasticizer 0% to 25% Polyvinyl Alcohol 0% to 10% Diluent 0% to 30% Humectant 0% to 30% Filler 0% to 30% A useful way to sort through the effects of additives is to sort them according to which phase they modify i.e., the solid polymer particles or the water soluble phase. An additive like an alternate dispersion will modify both the liquid and the solid phase. Humectant or water miscible additives will modify the aqueous phase and its viscosity. An additive like plasticizer will modify the solid phase. Modifying the solid phase could involve a bulk property change, like a Tg suppression. It could also involve changing the solids content and the particle size distribution. This would alter the relative position of the volume solids of the formulation to the critical packing factor. Typical Adhesive Ingredients Affect Differing Phases Main Emulsion Water Phase Polymer Phase Blending Emulsion Water Phase Polymer Phase Plasticizer Polymer Phase Polyvinyl Alcohol Water Phase Diluent Water Phase Humectant Water Phase Filler Polymer Phase

Two variables become important in understanding adhesives formulations, the aqueous phase viscosity and the packing factor. The aqueous phase viscosity is dependant upon the molecular weight and concentration of the aqueous phase colloids and ingredients. It can be affected by the inter-reaction between these ingredients. Conceptually, the packing factor of the solids phase is the ratio of the volumetric solids to the critical packing factor. This is a variable which is affected by concentration and the particle size distribution of the additives as well as any overall changes in the overall particle size of the blend which impacts the overall critical packing factor of the system. It is possible to add solids of a different particle size distribution and simultaneously raise the solids content and the critical packing factor. This can explain why blending of dispersions can produce a wide and varied effect on viscosity. 6.2 Polymer / Solid Phase Modifiers:

Blending with Other Dispersions Blending with other polymer dispersions is a common formulation technique. One can effectively create your own customized particle distributions by the proper mixing of neat dispersions. Care and experience should be used since the solids content, the water phase viscosity, the mean particle sizes and the standard deviation of the particle sizes are altered as dispersions are blended. On a bulk properties basis, you can simultaneously alter the adhesion vs cohesion balance with proper polymer choice. Plasticizer Plasticizer, the most common additive, penetrates the polymer sphere and swells the polymer spheres increasing their average particle size and volume solids. It has a modest affect changing their particle size distribution. Plasticizers are added to reduce the intermolecular attraction of the poly(vinyl acetate) polymers, causing the polymer chains to spread and the poly(vinyl acetate) particles to swell. This swelling raises the volume solids, which raises the viscosity, of the dispersion and destabilizes it for greater wet tack as well as faster breaking and setting speeds. In addition, the resin in the dispersion gains mobility. Increased mobility helps the resin to wet smooth, nonporous surfaces (e.g., plastics, foils and coated papers) and, consequently, to increase its adhesion to these surfaces. Moreover, softened polymer particles coalesce more rapidly and more completely at lower temperatures. Finally, plasticizers will increase the tackiness of the film, reduce its heat-sealing temperature, and improve its water resistance.

Fillers Fillers are added to dispersion adhesives to reduce cost by replacing resin solids without decreasing total solids, to reduce penetration into porous substrates, and to change the rheology of compounds. Depending on their individual properties, fillers can also add stiffness and strength or decrease tack and blocking. Uncooked starch fillers, in particular, reduce the cold flow in wood glues. Clays and other fillers impart stiffness to adhesive films. Clays reduce the penetration of adhesives into porous substrates. Large-particle clays are better able to control penetration and also impart more rapid setting speed. Calcium carbonates, clays, starch, wood flours, mica, talc feldspar and other minerals are general-purpose fillers that can be added to most adhesive dispersions.

6.3 Aqueous Phase Modifiers Water of Dilution Water performs two functions in diluting dispersions; it dilutes the viscosity of the aqueous phase dramatically. It separates the particles and lowers the volume solids concentration. Both factors contribute to the dramatic drop in viscosity that occurs as water is added to a formulation. It can act as a temporary plasticizer to the colloid and more modestly to the polymer on a bulk polymer basis. Polyvinyl Alcohol Poly (vinyl alcohol) is used as very important additives or modifiers in polyvinyl acetate / ethylene dispersion-based adhesives. Poly (vinyl alcohol) adheres particularly well to cellulosic substrates such as paper and wood. Adding it to polyvinyl acetate dispersions will increase the tensile strength of the resulting adhesive. Because it is a hydrophilic polymer, poly (vinyl alcohol) functions as a humectant to retard the loss of water from the formulation and prolongs the open time of the adhesive film. Wet tack is increased and can be enhanced further by adding a borated poly (vinyl alcohol). Poly (vinyl alcohol) is also used as a thickener to increase viscosity and control solids content. When a high-viscosity but low-solids formula is needed, high-viscosity poly (vinyl alcohol) should be added. When both a high-viscosity and high-solids formulation is needed, a mediumviscosity grade should be added. All grades demonstrate smooth flow from applicator reservoirs and Newtonian Flow at high speeds. Poly (vinyl alcohol) affords the best means of balancing the viscosity and solids content of a dispersion adhesive. Partially hydrolyzed poly (vinyl alcohol) increases the stability of dispersion adhesives by functioning as an emulsifier and a protective colloid. These alcohols increase the water sensitivity of adhesive films, making them very useful in remoistenable adhesives or those requiring easy cleanup. Low molecular weight poly (vinyl alcohol) is especially useful in remoistenable adhesives because their ultra-low viscosity permits the use of a large amount of PVOH, which results in a very tacky, fast grabbing front seal adhesive for envelopes.

Partially hydrolyzed poly (vinyl alcohol) wets surfaces better than fully or super hydrolyzed grades and works particularly well in wood adhesives. The addition of partially hydrolyzed poly (vinyl alcohol) to polyvinyl acetate wood glues permits the adhesive to wet the wood and penetrate the pores, thereby increasing the strength and fiber tear of these adhesives. Fully hydrolyzed poly (vinyl alcohol) increases the water resistance of adhesive films, particularly the medium and high molecular weight grades. Solutions of super hydrolyzed grades tend to increase in viscosity as they age and are not recommended as additives to polyvinyl acetate dispersion adhesives. Poly (vinyl alcohol) improves the machinability of dispersion adhesives by raising the high shear viscosity of the adhesive; i.e. spitting and throwing are reduced on high-speed equipment. All types have surface-active properties that promote thorough wetting of roller applicators and adherends. The lower surface tension of the partially hydrolyzed grades permits better wetting of hydrophobic surfaces. Since poly (vinyl alcohol) has a higher softening point (180-230C) than the dispersion to which it is added, it raises the heat sealing and blocking temperature of the film and increases its overall heat resistance. Humectants A humectant is a hydroscopic substance, one that absorbs and retains moisture from the atmosphere. In dispersion adhesives, humectants prevent the surface of the compound from skinning by keeping it wet. When poly(vinyl alcohol) or starch is present, the humectant holds water, which plasticizes these materials and keeps them flexible after drying. By retarding drying, humectants also slow setting speed and extend the open time of the adhesive. Humectants allow easier cleanup of a dried or semi-dried adhesive. Typical examples of common humectants are urea, glycerin, propylene glycol, sucrose, sorbitol and many inorganic salts. Viscosity/Rheology Modifiers Adhesives are most commonly industrially applied by machine. Each type of machine or applicator has its own viscosity/rheology requirements. Most roll applications use adhesives with a viscosity of 1500 to 3000 cPs and operate best with a slightly thixotropic flow. Spray equipment uses viscosities in the 200 to 800 cPs range. Construction adhesives are applied through a gun or trowel which needs thixotropic or pseudoplastic rheology. The proper choice of thickener will control viscosity as well as rheology. Thickeners added to an adhesive will raise viscosity and permit dilution with water. This reduces the total solids of the adhesive and also lowers its cost. Thickeners release water slowly, and when combined with lower solids, they slow the setting (prolong open time) of the adhesive. Thickeners, such as high molecular weight poly(vinyl alcohol), starch and clay, will improve adhesion to porous substrates by reducing penetration of an dispersion into substrates and decreasing the likelihood of a starved joint.

Some thickeners can prevent adhesives from spitting and throwing during high-speed applications. They permit them to transfer cleanly and break short rather than draw to fibers. Pseudoplastic adhesives can be prepared by adding polyacrylates such as sodium or ammonium polyacrylate. Starch and cellulosic thickeners will also confer pseudoplasticity. Thickeners that can be added to adhesive dispersions are: Polyvinyl alcohol, xanthan gum, hydroxyethyl cellulose, polyacrylic acid based thickeners, associative thickeners, inverse dispersion thickeners, most water soluble polymers Other Additives Wetting Agents and Dispersants Wetting agents aid the adhesive to wet the surface of the adherend by lowering the interfacial surface tension, thereby improving adhesion. When a VAE dispersion is used to bond PVC foils, the secondary plasticizers in the film exude to the surface, making the film very difficult to wet and bond. The addition of a good wetting agent corrects this situation. Wetting agents help water penetrate the surface of an adherend. This allows the polymer particles to coalesce and set rapidly. Dispersants are polyelectrolyte salts that are added to help disperse solids throughout the adhesive. They reduce agglomeration of the added fillers which reduces settling issues. Certain wetting agents cause foaming if used to excess, and may also increase the water sensitivity of the adhesive film. Therefore, these should be added in minimal amounts. Typical wetting agents and dispersants that can be used with most VAE dispersions are: Sodium Dioctylsulfosuccinate, Sodium alkyl benzene sulfonates, Acetylenic glycols, ethoxylated nonylphenols and many others . The Surfynol surfactant series of wetting agents from Air Products can also act as defoamers. Foam-Control Agents/Defoamers Foam-control agents include antifoam and defoamer compounds. Foam causes problems in both the manufacturing and the application of adhesives. Air in the formulation increases viscosity which can be misleading when adding ingredients. An inaccurate viscosity also prevents accurate metering during application of the adhesive, thereby preventing the deposit of sufficient solids on the glue line. Defoamers are typically used to destabilize or break down an existing foamy condition. Antifoams are added to the formulation to prevent foam from occurring. A small amount of foam-control agent, 0.10 to 0.30 percent of the adhesive, is usually sufficient to prevent or break foam. Caution: Too Much Foam-Control Agent Will Reduce the Wetting Ability of the Adhesive and Weaken the Bond. A foam-control agent should be retested in each new adhesive formulation and each time an ingredient is changed. Changing the amount of an ingredient can change foam-control requirements. The adhesive sample should age before analysis of foam-control efficiency. Some foam controllers may emulsify or separate upon aging and need to be stirred well before adding.

Biocides Biocides are always required when compounding dispersions, especially when animal or vegetable substances or their derivatives (starches, casein and other proteins, nut shell flours, sugar and cellulosic resins) are incorporated into VAE adhesives. Growing microorganisms feed on these substances and can generate foul odors, discolor the adhesive, lower its viscosity and weaken the bond. Typically, the inclusion of 0.05 to 0.10 percent of a biocide, based on the total wet weight of the formulation, prevents microbial growth. Nevertheless, microbes frequently adapt to a specific biocide and flourish. Biocides should be changed regularly to prevent this occurrence. The maximum allowable quantities of all biocides are regulated. The manufacturer should be contacted for the appropriate use level information. 6.4 Formulation Examples and Logic: There are five major requirements to specify or develop a specific adhesive for your process. Adhesive Requirements Requirements Bonding Method Substrates, and their Variability Performance, Specifications Economics Plant Conditions Adhesive Property Polymer flow and Substrate Wetting Adhesion Cohesion Failure Analysis Risk vs Reward Productivity / Statistical Quality Control

The first is to understand the bonding method. The bonding process and the application process such as roller, brush, spray, extrusion, etc., need to be considered in adhesive development and selection in great detail. The coating weight control is crucial to balancing the performance and economics of a process. Substrates vary or may need to be switched during a production run so sufficient adhesion is paramount. The final constructions performance characteristics need to be evaluated in terms of stress, heat, humidity or moisture resistance. Value is cost performance based. An evaluation of cost must consider the production costs associated with adhesive usage; this includes mileage and line speeds or productivity concerns. In all, there are always choices, selections and compromises to be made. Often compromises are exclusive; trade offs such as adhesion must be balanced versus cohesion. Heat resistance is the inverse of flexibility. The best solution generates a compromise that achieves acceptable values of both factors. Trade-offs in selecting an adhesive Adhesion Cohesion Machining Wet tack Cost Performance Water resistant Easy clean up Flexibility Heat resistant

A detailed review of the elements of adhesive selection reveals the bonding process needs to be described in terms of time, temperature and pressure. Because of the universal way adhesives bond and flow or wet out, time, temperature and pressure influence the success of adhesive development and polymer selection greatly. What you are bonding also places demands on the adhesive you select. A porous substrate can possibly use a homopolymer system where a metal foil or plastic film or even a hard to adhere paper surface may need a copolymer for adhesion. Value in the selection process balances the economic aspect versus the requirements for the end product. A proper evaluation of an adhesive needs to consider the strength requirements beyond room temperature exposure. At time, certain regulations may impact the adhesive through specifications. Over-engineering wastes money; but under-selection causes failures and rejects which wastes time and resources. The economics of adhesive selection is the basic risk/reward decision process. Economic factors that need to be considered are mileage or cost per unit produced as well as the reject rate and the line speeds. Every process needs to support a certain profitability requirement as judged by margin dollars per hour or return on investment. An adhesive that can not keep up with the variability of the production process may need to be modified to improve upon its window of operation. Being more fool proof is an apt adjective. Some formulating Examples are below: Formulation: General Purpose Packaging Adhesive Roller Based Economical, Safe, Good Machining for Paper and Corrugated Board Requirements Data Bonding Method Viscosity 2000 to 3500 mPa.s Substrates, and their Variability Corrugated or coated paperboard Performance, Specifications 140F to 160F during transportation Economics Competitive price with zero failures Plant Conditions 25C with varying humidity This typical packaging line would require an easy cleaning, relatively fast setting adhesive. The coated paperboard would require a VAE copolymer with a broad adhesive range. The heat resistance limits the plasticizer content and the Tg of the polymer. General Purpose Packaging Adhesive Roller Based Economical, Safe, Good Machining for Paper and Corrugated Board Vinyl Acetate/ Ethylene Copolymer 100 parts Airflex 400 Type Plasticizer 5 to 10 parts 0 to 10 Parts PVOH- HMW partially hydrolyzed 1 to 2 parts 0 to 2 Parts Water To: 50 to 52% solids 0 to 20 Parts 2000 to 3500 mPa.s

A typical economical packaging adhesive can be approached with a base dispersion like a vinyl acetate / ethylene copolymer with the appropriate regulatory clearances. To improve the tack and setting speed one may wish to swell the particles and increase the particle sizes of the dispersion. Plasticizer also improves the rate of film formation by raising the solids and lowering the Tg. To improve the machining a low level of poly(vinyl alcohol) can be added to increase the water sensitivity of the dispersion, thus allowing fresh adhesive to self clean older adhesive films on the machining rollers. Water is the typical diluent to reach the proper machining viscosity. PVOH stabilization allows for a consistent machining rheology under shear. If the paper is coated or hard to adhere due to a high recycle content the adhesion can be improved through blends with or a switch to a lower Tg VAE dispersion in the same general formulation. Packaging Adhesive Spray or Non Contact Extrusion Economical, Safe, Excellent Machining for Paper Board Requirements Data Bonding Method Viscosity 700 to 1000 mPa.s Substrates, and their Variability Coated paperboard Performance, Specifications 140F to 160F during transportation Economics Competitive price with zero failures Plant Conditions 25C with varying humidity Clean Extrusion No Down Time This typical spray or extrusion packaging line would require a very easy cleaning, relatively fast setting adhesive. The coated paperboard would require a VAE copolymer with a broad adhesive range. The heat resistance again limits the plasticizer content and the Tg of the polymer. The spray/extrusion aspect of the application method limits the degree of wet tack necessary in the packaging line. Improved machining is more highly valued than the wet tack to hold the substrates together since the application equipment requires more precise adhesive control and lower wet tack requirements. Packaging Adhesive Spray or Non Contact Extrusion Economical, Safe, Excellent Machining for Paper Board Vinyl Acetate/ Ethylene Copolymer 100 parts Airflex 401 Type @ Tg = -18C Plasticizer N/A 0 to 10 Parts PVOH- LMW partially hydrolyzed 1 to 2 parts 0 to 2 Parts Humectant - Urea 1 to 5 parts Water To: 52 to 55% solids 0 to 20 Parts 700 to 1000 mPa.s

Note of the Editor: For detailed information about packaging and paper adhesion, our reader should refer to the chapter Packaging Adhesives in volume 7 of this handbook

Water Resistant Packaging Adhesive Roller Based Economical, Safe, Good Machining for Paper and Corrugated Board Requirements Bonding Method Substrates, and their Variability Performance, Specifications Economics Plant Conditions Data Roller 2000 to 3500 mPa.s Corrugated or coated paperboard 140F to 160F during transportation Water Soak Resistance Competitive price with zero failures 25C with varying humidity

This typical packaging line would require a water resistant, relatively fast setting adhesive. The coated paperboard would require a VAE copolymer with a broad adhesive range. The heat resistance limits the plasticizer content and the Tg of the polymer. Water Resistant Packaging Adhesive Roller Based Economical, Safe, Good Machining for Paper and Corrugated Board Vinyl Acetate/ Ethylene Copolymer Airflex 400 Type Vinyl Acetate/ Ethylene Copolymer Airflex 7200 Type , High Solids Water Resistant Plasticizer- Benzoate Ester Type 0 to 10 Parts PVOH- HMW fully hydrolyzed 0 to 2 Parts Water 0 to 20 Parts 100 parts 25 to 50 parts

8 to 15 parts 2 to 4 parts To: 52 to 55% solids 2000 to 3500 mPa.s

In water resistant packaging, fast setting speed is needed along with water resistance. Start by blending a specialty copolymer for water resistance, tack, and speed is the best approach. Plasticizer improves the tack, speed, and water resistance; all desirable. Added water resistance can be developed with the addition of fully hydrolyzed PVOH if the dispersion is compatible with this material. Again water is the standard diluent.

Cigarette Tipping Adhesive High Speed Roller Based Economical, Safe, Extremely Good Machining for Non drying and High Wt Tack Requirements Bonding Method Substrates, and their Variability Performance, Specifications Economics Plant Conditions Data Roller 2000 to 3500 mPa.s Cigarette Papers High Wet Tack, Extremely good Machining Competitive price with zero failures 25C with varying humidity Elevated machine roller temperatures

A cigarette adhesive requires extremely high wet tack with great machining characteristics, combined with a relatively fast setting speed. The coated papers would require a VAE copolymer with a broad adhesive range. Cigarette Tipping Adhesive High Speed Roller Based Economical, Safe, Extremely Good Machining for Non drying and High Wt Tack Vinyl Acetate/ Ethylene Copolymer Airflex EP11 / or Airflex 400H Type PVOH- LMW partially hydrolyzed, Highly Borated Water 100 parts 2 to 8 parts To: 46 to 48% solids 2000 to 3500 mPa.s

In cigarette tipping, a fast setting speed/ high wet tack is needed along with excellent machining. Start by blending a specialty VAE copolymer for tack, and speed with a borated PVOH cook is the best approach. Again water is the standard diluent.

Vinyl or Plastic Films/Foils Adhesive Roller Based Economical, Safe, Good Machining for Paper Board or Wood Requirements Bonding Method Substrates, and their Variability Performance, Specifications Economics Plant Conditions Data Viscosity 2000 to 3500 mPa.s Wood or Board 160F to 180F during transportation Strong Peel adhesion Competitive price with zero failures 25C with varying humidity

For vinyl lamination, a plasticized homopolymer will not develop sufficient adhesion to PVC foils to be commercially useful. For a film like this a vinyl acetate/ethylene copolymer is needed for proper long term adhesion and durability. Plasticizer is a benefit for speed and tack improvement. A wetting agent is useful to promote wetting on a low surface tension film like vinyl. A defoamer is needed to avoid any foam generation during the application. Vinyl or Plastic Films/Foils Adhesive Roller Based Economical, Safe, Good Machining for Paper Board or Wood Vinyl Acetate/ Ethylene Copolymer Airflex 400 or Airflex EP 17 Type Vinyl Acetate/ Ethylene Copolymer Airflex 7200 Type , High Solids Water Resistant Plasticizer- Benzoate Ester Type 0 to 10 Parts Filler Water 0 to 20 Parts 100 parts 25 to 50 parts

8 to 15 parts 5 to 20 parts To: 62 to 65% solids 2000 to 3500 mPa.s

In foil and film laminating, fast setting speed is needed since laminations are frequently trimmed in-line. Start by blending a specialty copolymer for high solids, tack, and speed is the best approach. Plasticizer improves the tack, speed, and water resistance; all desirable. Added solids can be developed with the addition of fillers. Again water is the standard diluent.

Vinyl or Plastic Films/Foils Adhesive Roller Based Heat Reactivated Economical, Safe, Good Machining for Paper Board or Wood Requirements Bonding Method Substrates, and their Variability Performance, Specifications Economics Plant Conditions Data Roller Viscosity 1000 to 2000 mPa.s Wood or Board 160F to 180F during transportation Strong Peel adhesion Competitive price with zero failures 25C with varying humidity Heat sealed in-line

For heat sealed, vinyl lamination, even a plasticized copolymer may not develop sufficient adhesion to PVC foils at low reactivation temperatures below , about 80C, to be commercially useful. For a film like this a softer, flowable vinyl acetate/ethylene copolymer is needed for proper long term adhesion and durability. Plasticizer is again a benefit for speed and tack improvement. A wetting agent is useful to promote wetting on a low surface tension film like vinyl. A defoamer is needed to avoid any foam generation during the application. Vinyl or Plastic Films/Foils Adhesive Roller Based Economical, Safe, Good Machining for Paper Board or Wood Vinyl Acetate/ Ethylene Copolymer Airflex 7200 or Airflex EP 17 Type Plasticizer- Benzoate Ester Type 0 to 10 Parts Filler Water 0 to 20 Parts 100 parts 5 to 10 parts 5 to 20 parts To: 62 to 67% solids 1000 to 2000 mPa.s

In heat reactivated foil and film laminating, a low heat seal temperature with good polymer flow is needed since laminations are trimmed in-line. Start with a pure specialty copolymer for high solids, good polymeric flow and wetting is the best approach. Plasticizer improves the dry flow; Added solids can be developed with the addition of fillers. Again water is the standard diluent. The Tg is the critical variable in heat seal coatings. For industrial processes the Tg should be about 60C lower than the actual adhesive glue line temperature.

Vacuum forming/ Thermal Bonding: Vacuum bonding/ heat seal bonding is a growing market involves the dry bonding of a foil to a curved or shaped substrate. The bonding process involves spray coating of the curved part. Adhesive coated part could be allowed to dry at room temperature. In principal, the adhesive glueline needs to be heated significantly above its Tg to increase the flowable nature of the dry polymer film. This is accomplished by heating the vinyl or plastic foil above its softening point. When hot and pliable it is brought into contact with the curved adhesive coated surface with vacuum and possibly pressure being applied to pull the hot foil around the shaped part. As it cools the adhesive builds cohesive strength and adhesion. See diagram 1 Airflex EP17 or Airflex 7200 are high solids, flowable VAE polymers with an optimum balance of adhesion and cohesion with a low Tg and low heat reactivation temperature. A lower heat seal temperature can be accomplished with a minority blend of a polyurethane dispersion. This will maintain adhesion and promote flow at even a lower heat reactivation temperature than a pure VAE polymer. For heat resistance above 105C; a low level, circa 5%, addition of an aliphatic isocyanate crosslinker as a two part system can yield a long potlife, maintain a low heat seal temperature and yet build a cured network with the polyvinyl alcohol protective colloid. This is a way to overcome the seemingly contradictory requirements of heat sealing at 80C but developing good hot bond strength at 110C. General trends in most industries are the reduction improvements in worker safety and compliance to environmental laws on emissions and spillage. Productivity is an ever present trend in todays age. Faster adhesives can be economically justified over less productive, older formulations. The user and manufacturer of adhesives are both in a highly leveraged position and mutually dependant upon each other for global success. Pennies worth of adhesive can be responsible for bonding anything from the tiles on the space shuttle or the legs on an expensive piano, to the mundane production of millions of boxes of breakfast cereal. A recall in either case is an expensive proposition that can put the financial future of a company at risk. It is all about making choices and an informed decision is universally better than an uninformed decision.

AIR PRODUCTS POLYMERS Raw Material Dispersions: A HISTORY OF INNOVAT I O N For more than 40 years, Air Products Polymers has been a major producer and supplier of polymer emulsions for the adhesives industry. Over the years, as industry needs have evolved, Air Products Polymers has been the leader in providing state-of-the-art technology to meet such changes. A history of the companys contributions to adhesives included many firsts. For example, starting back in the 1960s, the company developed the first effective vinyl acetate-ethylene emulsion copolymer, Airflex 400, which provided a stronger, more economical base for laminating adhesives. The chemistry and technology of this product have since been expanded into a broad range of products to meet a host of specific adhesive applications. Then, in the 1970s, Air Products Polymers commercialized another breakthrough product, with its ethylenevinyl chlorides (EVCLs) which built flame retardance into adhesives. The 1980s saw the introduction of Airflex 300 and 320 emulsions, which redefined the use of vinyl acetate emulsions for packaging adhesives. Recent years have been marked by innovations in the area of high solids and high adhesion products, with the development of Airflex 426, 465, 7200 and 920 emulsions.

BUILDING FROM STRENGTH, POSITIONED FOR THE FUTURE

During the 1990s, Air Products Polymers became the worlds largest manufacturer of vinyl acetate ethylene (VAE) emulsions. The adhesives market is the single largest market we serve. To strengthen this position, Air Products Polymers has taken several steps to ensure that we and our customers ride the momentum into 2000 and beyond. First, we have expanded globally to bring consistently high quality and cost-effective production to customers around the world. Our 1998 joint venture with Wacker-Chemie improved our presence in Europe. That venture enabled us to combine technology, Experience and market position strengths of each partner to serve customers with the best product technology available. That same year, we purchased TaeYoung Chemicals in Korea to improve our ability to serve customers in Asia. These new operations complement our six United States plants making Air Products Polymers the only VAE manufacturer with manufacturing facilities on three continents. Secondly, our globalization will allow us to bring more technology to our domestic and international customers. We will be able to offer adhesive compounders the best adhesive emulsions from around the globe... leading edge technologies such as ultrahighsolids (72%) Airflex 7200 emulsion and high adhesion Airflex 920 emulsion. Thirdly, our focus on VAEs continues to meet environmental needs around the globe. We are dedicated to developing new products that meet high-performance applications and constantly changing enduser needs.

The tables and figures below describe the complete selection of VAE polymer dispersions for world adhesives market.

APP North American VAE Product Line Polyvinyl Alcohol Stabilized Emulsions for Adhesives
General Purpose Vinyl Acetate / Ethylene Grades
Highest heat resistance combined with fully hydrolyzed PVOH compatibility for improved water resistance. Highest wet tack and speed of set with excellent adhesion to coated paperboard, high heat resistance . Ultra low formaldehyde levels. Balance of high wet tack, fast speed of set, adhesion and heat resistance with fully hydrolyzed PVOH compatibility for improved water resistance. Highest adhesion properties while maintaining excellent speed of set and heat resistance. Excellent plasticizer thickening response and clean machining. Higher viscosity Airflex 400 for enhanced wet tack and thickening. Improves yields of formulated adhesives. Lower viscosity and solids emulsion offering easy clean-up and excellent machining properties for spray and extrusion equipment. Excellent balance of wet tack, speed of set, adhesion and heat resistance with greater flexibility and easier clean-up compared to Airflex 400. Highest adhesion to difficult-to-adhere polymeric and metalized films. Moderate heat resistance.

Airflex 323

Airflex 315

Airflex 320

Airflex 400

Airflex 400H

Airflex 418

Airflex 401

Airflex 920

Specialty High Solids Vinyl Acetate / Ethylene Grades

Low viscosity with good speed of set, adhesion and moderate thickening response, and ultra low formaldehyde levels. High adhesion and high heat resistance, superior wet tack, higher thickening response than other high solids products. Carboxyl functionality offering excellent film and metal adhesion, high wet tack,

Airflex 460

Airflex EP17

Airflex 426

good heat and water resistance.

Airflex 7200

Airflex 465

Ultra high solids, excellent wet tack and speed of set with excellent adhesion and good water resistance. Lower viscosity with rapid speed of set, excellent adhesion and moderate thickening response for maintaining high solids formulations.

General Purpose Vinyl Acetate / Ethylene Grades

Solids Airflex 323 Airflex 315 Airflex 320 Airflex 400 Airflex 400H Airflex 418 Airflex 401 Airflex 920 55 55 55 55 55 53 55 55 Viscosity 1800 2250 2250 2250 3750 400 1750 1500 pH 5.5 4.5 4.5 4.5 4.8 7.3 5.8 5.0 Tg, C 23 17 14 0 0 -12 -15 -20 Stabilization PVOH PVOH PVOH PVOH PVOH PVOH PVOH PVOH

Specialty High Solids Vinyl Acetate / Ethylene Grades

Airflex 460 Airflex EP17 Airflex 426 Airflex 7200 Airflex 465 63 60 63 72 67 500 3800 1400 1750 1050
2

6.8 4.5 4.8 5.0 5.0

5 0 0 0 -5

PVOH/nonionic PVOH/nonionic PVOH/nonionic PVOH/nonionic PVOH/nonionic

1. Brookfield Viscometer, Model RVF, @20 rpm 2. Brookfield Viscometer, Model LVF, @60 rpm

APP Europe VAE Product Line

Basic properties Flexible elastic polymers High cohesion and heat resistance Good adhesion to cellulose, mineral and plastic substrates Polyvinyl alcohol stabilisation Compliance with food contact regulations (BGVV; FDA) Main applications Paper and packaging adhesives Cigarette adhesives Furniture foil lamination adhesives

Main APP Dispersions: Airflex EP1, EP11, EP14, EP17, EP24, EP400
Airflex EP1 50 % paper/packaging, high performance adhesion, flexibility Airflex EP11 50 % paper/packaging, cigarette adhesive base, PVC Foil Lamination, good rheology, penetration, fast setting Airflex EP400 55 % paper/packaging, cigarette adhesive base fastest setting, cohesion Airflex EP14 55 % paper/packaging, PVC-Foil-Lamination good adhesion Airflex EP24 57 % like EP 14, high viscosity Airflex EP17 60 % paper/packaging good adhesion, fast setting, high solids

EP 1

EP 11

EP 14

EP 17

EP 24

EP 400

Solids

50

50

55

60

57

55

Viscosity

9000

5000

5500

3800

12000

2400

Tg C

Set Speed [s]

3,8

1,7

2,2

1,9

1,9

1,6

Cohesion [N/mm2]

0,7

3,7

2,5

1,8

2,5

3,0

Adhesion [rating]

18

22

21

18

19

20

Main Features

Versatile grade with good adhesion

Fast setting, good rheological properties, Tobacco

Recommende d for P&P, good adhesion/ cohesion balance

Fast setting, good adhesion, on fast running machines PVC foillamination

High viscosity, for manufacture of cost effective adhesives

Fastest setting, especially recommended on fast running machines

APP Asia VAE Product Line

Source Viscosity (cPs) Solids (%) Tg (C) Remarks

Airflex EP704 Airflex EP706 Airflex EP706K Airflex EP707K Airflex EP709 Airflex EP724 Airflex EP760

Korea Korea Korea Korea Korea Korea Korea

1,500 2,500 3,500 4,500 4,400 5,500 1,300 2,000 1,500 2,500 2,700 3,700 2,000 4,000

55 55 55 55 55 55 60

0 0 0 0 7 19 0

General purpose Lamination (PVC or OPP) Packaging adhesives Foam / Textile

Fast setting speed Cement Admixture High Tg applications High thickening

Airflex EP VAE Emulsions (Korea)

Viscosity 1,000 2,000
0oC)

3,000

4,000

5,000 cps

Characteristics & Applications

EP704 (1,500-2,500; Tg =

Standard Grade * High Viscosity Thickening * Excellent Adhesion Strength PVC lamination, OPP lamination Carton & Case Cigarette adhesives, Bottle label Envelop, Book Binding Packaging Adhesives Foam / Textile

EP706 (3,500-4,500; Tg =
0oC)

EP706K (4,400-5,400; Tg = 0oC)

Specialty Grade
707K (1,300-2,000; Tg = 0
oC)

* Excellent Water Resistance * Fast Setting Speed - Higher Speed Packaging Machine (707K) - Wood Lamination, Wood / PVC (706J)

724 (1,500-2,500; Tg = + 19 oC)

* EP724: High Tg (+19 C) - Wood Working Adhesives * EP709: Medium Tg (+7 C) - Cement Mortar Admixture - Good bonding to hard surface

709 (2,700-3,700; Tg = + 7 oC)

Standard Grades in Airflex EP (Korea)

High Viscosity Thickening Strong Wet Tack Designed for General-purpose Waterborne Adhesives

Solids Airflex EP704 Airflex EP706 Airflex EP706K 55% 55% 55%

Viscosity 1,500-2,500 cps 3,500-4,500 cps 4,400-5,400 cps

Tg 0 oC 0 oC 0 oC

Remarks Good flow behaviors High starting viscosity

Airflex EP (Korea)

Specialty Grades

Low Viscosity Thickening Protected by both Fully and Partially Hydrolyzed PVOH Has its own special features, respectively

Solids Airflex EP707K Airflex EP709 Airflex EP724 55% 55% 55%

Viscosity 1,300-2,000 cps 2,700-3,700 cps

Tg 0 oC 7 oC

Remarks Fast Setting Speed & Excellent flexibility Compatibility with inorganic fillers High Tg Grade

1,500-2,500 cps 19 oC

Airflex EP (Korea) Elongation

at Break (%)

704 705K 706 706K 706J 707K 709 724 0 200 325 400 600 690

810 780 810 790 850 890

800

1000

Airflex EP (Korea) Water Resistance

500 420 400 380 340

Seconds
300 230 200 240 230 240

100

704

705K

706

706K

706J

707K

709

Test Method: Measure the time interval required for an opaque white-color spots with water droplets to occur on the dried emulsion film