New Developments of Solvent-Based Polyurethane Resins for Printing Inks.
The market for lamination lamination
a laminar structure or arrangement. inks is a specialty area that can be quite lucrative for the ink manufacturer but is also one fraught with many liabilities as well. The formulator who can provide quality inks that can adhere to adhere to
verb 1. follow, keep, maintain, respect, observe, be true, fulfil, obey, heed, keep to, abide by, be loyal, mind, be constant, be faithful
2. a wide variety of substrates, provide good laminating lam·i·nate
v. lam·i·nat·ed, lam·i·nat·ing, lam·i·nates
1. To beat or compress into a thin plate or sheet.
2. To divide into thin layers.
3. bonds on those substrates, and still print and clean up well on the press will be the one that succeeds in this difficult market niche.
Solvent-based inks still dominate in this market. However, with the ever increasing variety of substrates, better and faster printing technology and the demands of the customer for more package performance and eye appeal require the formulator to search as well for advanced resin technologies that will help in meeting these demands.
This paper discusses the new generation of solvent-borne polyurethane polyurethane
Any of a class of very versatile polymers that are made into flexible and rigid foams, fibres, elastomers (elastic polymers), surface coatings, and adhesives. resins that the formulator can obtain to aid in solving the complexities of not just film lamination printing but those encountered in other printing and coating applications as well.
The flexible packaging industry today is very dynamic. Abroad variety of substrates are introduced into the market every day with different surface properties.
Better and faster printing techniques are available today which are designed to give superior print quality with less down time, allowing the converter to run more and differentiated jobs in a shorter period of time.
Package designs are not only meant to please the eye with its glossy photo-like finish but also to preserve its contents.
For example, potato chip bags, coffee pouches etc. are designed not only to advertise the products and attract the consumers but also to preserve the freshness of the food in the package by eliminating or limiting the passage of moisture, oxygen and flavors.
Similarly the food packages for microwave cooking not only need to protect the food during storage but also need to have good heat resistance. The beverage packages require resistance to the environment found in refrigerator storage and handling. And finally, bakery packaging requires not only good grease resistance but also must be able to release the product for ease of consumption.
To meet the demands of the packaging industry, the ink manufacture today needs to formulate inks that can be used for multiple applications. Some of the application requirements are shown in Table 1.
The various performance requirements of an ink often demand that the ink maker utilizes two or more resins in a formulation to be successful. Nitrocellulose/polyurethane, nitrocellulose/ acrylic, PVC PVC: see polyvinyl chloride.
in full polyvinyl chloride
Synthetic resin, an organic polymer made by treating vinyl chloride monomers with a peroxide. derivatives, PVB PVB Polyvinylbutyral
PVB Pressure Vacuum Breaker
PVB Portametric Voltmeter Bridge
PVB Potemkin Village Band (Potemkin Village, Canada) and polyamides are simple generic examples of the resin systems required to meet the demands of the converter.
However, it becomes highly inconvenient and confusing to both the ink maker as well as the converter to maintain the large inventory of various resins and inks to solve the myriad of customer demands.
Moreover, there exists the problem that due to incompatibilities between the different resins and ink systems significant press down time results between print jobs due to the need for thorough cleaning of press equipment to prevent contamination of one ink system by another.
In addition, PVC and PVB based inks, used in lamination, are being notoriously difficult to clean up. There exist other concerns such as the chlorine given off during the incineration incineration
the act of burning to ashes. of old packaging printed with PVC based inks.
For PVB inks, odor and print behavior on the press can be frustrating frus·trate
tr.v. frus·trat·ed, frus·trat·ing, frus·trates
a. To prevent from accomplishing a purpose or fulfilling a desire; thwart: to the converter.
Bearing these facts in mind, it is obvious that an ink system capable of covering most of these requirements, should be well received in the industry.
Background: Polyurethane Chemistry
In recent years, urethane urethane (yoor´ithān´),
n ethyl carbamate used as an anesthetic agent for laboratory animals, formerly used as a hypnotic in humans. polymers have received intense attention in the ink, coating and adhesives industries, resulting in the synthesis of many specialized forms.
We can now synthesize To create a whole or complete unit from parts or components. See synthesis. polymers containing not only the urethane linkages (Fig 1.) but many other functional groups as integral units in or on the polymer chains, which lead to the versatility of polyurethane products.
Basically polyurethanes are addition reaction products of a (polyether pol·y·e·ther
A polymer in which the repeating unit contains two carbon atoms linked by an oxygen atom. or/and polyester) with a diisocyanate or polyfunctional isocyanate i·so·cy·a·nate
Any of a family of nitrogenous chemicals that are used in industry and can cause respiratory disorders, especially asthma, if inhaled. materials (Fig. 2).
Typically a polyurethane has three basic building blocks: a polyol, diisocyanate and the chain extender See Media Center Extender, bus extender and DOS extender. . The properties of the polyurethane are determined by these basic segments, like the segment flexibility, chain entanglement and inter-chain forces (Fig. 3).
Properties of Urethane Polymers
Urethanes can be synthesized to range from very hard to soft to tacky. Most of the mechanical properties change with changes in the molecular weight of the polyurethane.
Intermolecular forces intermolecular forces, forces that are exerted by molecules on each other and that, in general, affect the macroscopic properties of the material of which the molecules are a part. Such forces may be either attractive or repulsive in nature. also influence these properties. Intermolecular forces are the result of hydrogen bonding hydrogen bonding
Interaction involving a hydrogen atom located between a pair of other atoms having a high affinity for electrons; such a bond is weaker than an ionic bond or covalent bond but stronger than van der Waals forces. , dipole moments Dipole moment
A mathematical quantity characteristic of a dipole unit equal to the product of one of its charges times the vector distance separating the charges. and polarizability. These intermolecular Adj. 1. intermolecular - existing or acting between molecules; "intermolecular forces"; "intermolecular condensation" attractive forces tend to hold polymer chains together in a manner similar to that of primary chemical bonds, but are much weaker and more readily affected by increase in temperature or stress.
Besides the intermolecular forces, obviously also the nature of the basic building blocks are determining the final urethane polymer properties.
Polyesters provide good weathering, good abrasion abrasion /abra·sion/ (ah-bra´zhun)
1. a rubbing or scraping off through unusual or abnormal action; see also planing.
2. a rubbed or scraped area on skin or mucous membrane. resistance, chemical resistance and toughness. Polyethers on the other hand provide good flexibility, elasticity and in-can stability.
The type of isocyanate used is also important Aliphatic aliphatic /al·i·phat·ic/ (al?i-fat´ik) pertaining to any member of one of the two major groups of organic compounds, those with a straight or branched chain structure.
adj. isocyanates improves hydrolytic hy·drol·y·sis
Decomposition of a chemical compound by reaction with water, such as the dissociation of a dissolved salt or the catalytic conversion of starch to glucose. stability and resists UV degradation and do not yellow. Aromatic isocyanates on the other hand provide chemical resistance and toughness but yellow on exposure to UV light.
When formulating with polyurethanes it helps to have an understanding of the relationship between the properties we seek for our application and the corresponding polymer structure.
While solvent-borne reactive polyurethane chemistry enjoy wide use in the industrial coatings An industrial coating is a paint or coating defined by its protective, rather than its aesthetic properties, although it can provide both.
The most common use of industrial coatings is for corrosion control of steel or concrete. and/or adhesives markets the reactive sites, curing requirements and solvents often limit their usage in many applications of the graphic arts graphic arts: see aquatint; drawing; drypoint; engraving; etching; illustration; linoleum block printing; lithography; mezzotint; niello; pastel; poster; silk-screen printing; silhouette; silverpoint; sketch; stencil; woodcut and wood engraving. market.
However, these disadvantages are overcome by polyurethanes which can be considered as "non-reactive," "plasticizing" or "capped."
Plasticizing resins based on polyurethane chemistry have been introduced to the market as a whole during the early 1970s and are now well established in the global printing ink industry.
However, for the most part very little has ever been written about their use. Basically they are reaction products of a polyol (polyether or/and polyester)with a di-isocyanate typically MDI (1) (Multiple Document Interface) A Windows function that allows an application to display and lets the user work with more than one document at the same time. or TDI TDI - Transport Driver Interface , where the excess NCO NCO
NCO noncommissioned officer
NCO n abbr (Mil) (= noncommissioned officer) → Uffz. is optionally reacted with a reaction terminating agent which can typically be an alcohol.
This capping of the isocyanate group prevents the polymer from any additional cross linking and only extreme changes in conditions can remove this cap.
As a result of elimination of the free isocyanate groups, the urethane is now compatible with the solvents and resins typically used in the flexo and gravure packaging industry. The ink formulator makes use of the urethane's physical properties rather than its reactivity to enhance the cohesive strength, flexibility and adhesion of ink formulations.
Non-reactive polyurethanes have been used primarily as co-resins for flexibility and to improve adhesion properties of nitrocellulose nitrocellulose, nitric acid ester of cellulose (a glucose polymer). It is usually formed by the action of a mixture of nitric and sulfuric acids on purified cotton or wood pulp. based flexo- and gravure inks for surface and reverse printing on polypropylene polypropylene (pŏl'ēprō`pəlēn), plastic noted for its light weight, being less dense than water; it is a polymer of propylene. It resists moisture, oils, and solvents. , polyethylene, foil and other film type substrates.
The range goes from very soft and flexible types with maximum plasticizing properties to less flexible types but with improved adhesion properties with a higher polyurethane content. The more flexible types of lower polyurethane content have generally a high alcohol tolerance Alcohol tolerance refers to a decreased response to the effects of ethanol in alcoholic beverages. This reduced sensitivity requires that higher quantities of alcohol be consumed in order to achieve the same effects as before tolerance began to occur. , while high urethane content grades are generally less alcohol tolerant.
For surface printing formulations Zeneca Resins offers a range of NeoRez products designed to fulfill each desired performance objective.
Typical examples of our range of polyurethane resins are can be found in Table 2.
Another important feature of polyurethanes is its low thermoplasticity, providing good release properties to inks that are printed in the heat sealing area of flexible packages and therefore unlike other plasticizers plasticizers
mostly triaryl phosphates, such as tricresyl, triphenyl phosphates, which are poisonous. See also triorthocresyl phosphate. impart good heat seal resistance.
Adhesion promoters, like titanium chelates, are often used in these ink systems to optimize adhesion properties by means of a complex cross linking mechanism involving the hydroxyl groups hydroxyl group (hīdrŏk`sĭl), in chemistry, functional group that consists of an oxygen atom joined by a single bond to a hydrogen atom. An alcohol is formed when a hydroxyl group is joined by a single bond to an alkyl group or aryl group. present in the binder system of the ink and the corona Corona, city, United States
Corona (kərō`nə), city (1990 pop. 76,095), Riverside co., S Calif.; inc. 1896. The city developed as a primary citrus fruit producer and shipping center. There is also light manufacturing. discharge treated surface of the substrate.
They also maximize heat seal resistance properties up to 180[degrees]C often required when packaging is done on high speed lines.
Inks based on these type of polyurethane resins are used successfully for flexo and gravure inks for surface and reverse printing on polypropylene and polyethylene substrates; heat resistant gravure inks for printing on aluminum foil Noun 1. aluminum foil - foil made of aluminum
aluminium foil, tin foil
foil - a piece of thin and flexible sheet metal; "the photographic film was wrapped in foil" and also to some extent in flexo-gravure inks for surface printing on polyester and polyamide polyamide
material used in the creation of nonabsorbable, synthetic, nylon sutures. substrates.
The disadvantages using these conventional types of solvent-borne polyurethane resins are that they do not form films and therefore need to be combined with other resins like nitrocellulose for heat resistance, and anti-blocking.
That is to say, these urethane polymers have to be used as modifiers in formulations containing much harder co-resins.
New Generation Elastomeric Polyurethanes
Unlike the conventional polyurethane binders described above, Zeneca Resins developed a new generation polyurethane binders having an optimized molecular weight balance giving a block free film with elastomeric properties.
This new generation of polyurethane binders are specifically suitable for adhesive and extrusion lamination enabling the ink formulator to achieve a close to an universal ink system; some of these new products can be used as sole binders or, as with conventional urethanes, can be used in combination with another resin like nitrocellulose. These resins when formulated into an ink system provide properties like excellent adhesion to a wide variety of films, excellent bond strengths in laminates, no blocking and good heat seal jaw release.
Table 3 exposes the most important differences between conventional and new generation film forming elastomeric polyurethanes. Zeneca Resins has developed two elastomeric polyurethane binders that meet the needs of the global graphic arts market.
These urethanes (NeoRez D and E) are designed for adhesives and extrusion lamination printing and differ in solvent tolerance. NeoRez E can be formulated into a mono-solvent system, that is ideal for gravure applications with solvent recovery. NeoRez D has broader solvent compatibility and as such can be used in both gravure and flexo applications.
Both resins offer improved adhesion and bond strength over conventional urethanes on multiple substrates (PET, OPP OPP Opposite
OPP Office of Pesticide Programs
OPP Ontario Provincial Police (Ontario, Canada)
OPP Office of Polar Programs (National Science Foundation) , PE, and Nylon). Moreover NeoRez D&E can be used as pigment grinding medium for white pigments. These urethane also offer good flexibility, nitrocellulose compatibility, ink stability and block resistance. These vehicles offer increase versatility as they can be used for both lamination and surface print.
This new generation of urethane polymer products for printing inks will offer advantages to the formulator that standard urethane chemistry could not accomplish. These higher molecular weight urethanes with elastomeric properties offer faster rate of drying, more cohesive strength for better lamination bonds and broader adhesion latitude.
The benefits offered over conventional systems extend beyond physical properties and include:
* Low solvent retention for reduced odor in final packaging
* Single ink system for both flexo and gravure applications
* Single ink system for multiple structures
* Good print properties with easy clean up
These elastomeric urethanes offer the ink formulator a versatile vehicle that can be formulated into a single resin and/or mono-solvent ink system to meet the flexible packaging converters ever changing needs.
Shaivalini Purohit has a Ph.D. in organic chemistry from J.N.V University, India. She started her career with Council for Scientific and Industrial Research The Council for Scientific and Industrial Research (CSIR) is South Africa's central and premier scientific research and development organisation. It was established by an act of parliament in 1945 and is situated on its own campus in the city of Pretoria. , India and later joined Color Converting Industries as an R&D chemist. She joined Zeneca in 1996 as applications chemist and is currently working with graphic arts group as industry technical manager.
Sjaak Griffioen (1962) graduated in 1988 from Vrije Universiteit The language of instruction for the bachelors courses is Dutch. However, many of the masters programmes are given entirely in English in order to attract students from outside The Netherlands. Amsterdam in organo-metallic chemistry. Sjaak started his career within Sigma Coatings in sealants and later as R&D manager decorative paints. He joined Zeneca Resins in 1995 as industry manager "adhesives and sealants" and is now, as senior industry manager, responsible for the global product development for film coatings and graphic arts.
The authors would like to thank Joan Tiana, Jim Gistis and Hennie Passier for useful discussions.
* Adhesion to a wide variety of substrates
* Good bond strengths with laminates of different compositions
* Resistance to boiling and retorting treatments
* Deep freeze deep freeze
see freezer. resistance
* Heat seal resistance
* Specific chemical or product resistance
* Low solvent retention in laminating inks
* Good print properties
NeoRez Range Urethane Adhesion Heatseal Alcohol Flexibility content resistance tolerance A High Best B Medium [up arrow] [down arrow] [down arrow] [down arrow] C Low Best Best Best NeoRez Range Grease resistance A Best B [up arrow] C Properties Conventional Polyurethane Film formation No, remains sticky Co-binder demand in formulation High, to avoid blocking and to optimize heat seal resistance Suitable in gravure and flexo ink Depends on grade systems Adhesion latitude Critical on PET substrates Suitability for different laminating Not suitable for PET and PA applications laminates Solvent release Fair Anti-blocking Needs modification with e.g. NC Heat seal resistance Needs modification with e.g. NC Flexibility Depends on grade Suitable for pasteurization and Critical, yellowing because of high sterilization NC content of the ink Deep freeze resistance Excellent Properties Elastomeric polyurethanes Film formation Forms elastomeric film Co-binder demand in formulation None or very small amounts Suitable in gravure and flexo ink Depends on grade systems Adhesion latitude Excellent Suitability for different laminating Suitable applications Solvent release Fast Anti-blocking Superior Heat seal resistance Superior Flexibility Excellent because of low NC demand Suitable for pasteurization and Suitable sterilization Deep freeze resistance Excellent Properties NeoRez [D.sup.*]) NeoRez [E.sup.*]) Suitable as sole binder Yes Yes Application Flexo Yes No Gravure Yes Yes Suitable for monosolvent ink No Yes systems Multi-Substrate Adhesion Excellent Excellent Lamination: Adhesive Excellent Excellent Extrusion Excellent Poor Ink Stability Excellent Excellent Block Resistance Very Good Excellent Flexibility Good Very Good Nitrocellulose Compatibility Excellent Excellent