Polyurethane Reactive Hot Melt Adhesives Comprising Hydroxy

Terminated Resin Ester Modifiers

Executive summary
A new polyol family for the manufacture of novel "open" time. This lack of process versatility makes the
polyurethane systems, preferably of polyurethane compositions handling characteristics poor and limits
reactive hot melt adhesives is disclosed. The polyol(s) the composition's utility in some assembly operations.
are reactive modifiers that enhance the properties of
In polyurethane reactive hot melt adhesives
polyurethane systems. The inventive polyols are the
(polyurethane Rhma), an isocyanate terminated
reaction product of a monocarboxylic acid, a
urethane polymer is produced through the
polycarboxylic acid and a polyhydric alcohol. The
polymerization of polyols and excess polyisocyanate
polyol of the present invention is used to produce
compounds.
urethane polymers, preferably polyurethane reactive
hot melt adhesives by reacting the polyol with Polyurethane Rhma(s) typically are cured in the
polyfunctional isocyanates. These adhesives provide presence of moisture. Moisture, which is present in
good green strength and longer open time. the ambient atmosphere, reacts with the isocyanate
end groups to cause chain extension and or
Background
crosslinking. As a result of this curing reaction,
In conventional hot melt adhesives, typically a
polyurethane Rhma develop temperature and
polymer, a tackifier, and a selection of other additives
chemical resistance. A typical cured polyurethane
such as antioxidants, are mixed together to produce
Rhma would generally exhibit a degree of stiffness as
an adhesive composition. These materials tend to
well as toughness. Toughness of polyurethane Rhma
form bonds through their rapid solidification from the
is attributed to long chain polyols called "soft
melt. These materials have the advantage of being
segments". Stiffness of the polyurethane Rhma is
relatively easy to apply. However hot melt adhesives
attributed to relatively short chain, high Tg, regions
are typically not reactive in nature and therefore do
called "hard segments".
not develop sufficient strength and sufficient heat and
chemical resistance for certain applications. Typically, polyurethane Rhma(s) do not exhibit
In order to impart sufficient structural, heat and sufficient combined green strength and open time for
chemical resistance to adhesive formulations, reactive many manufacturing processes. Also, while moisture
or curable compositions are conventionally used. cured polyurethane Rhma exhibit good temperature
These materials tend to form durable bonds through a resistance when compared to typical hot melt
chemical reaction and as such are the adhesives of adhesives, a need exists for a polyurethane Rhma
choice for various applications and substrates. that exhibit a desirable balance of processing, thermal
However, reactive or curable compositions are and mechanical attributes.
typically lacking in versatility on the combined
Those skilled in the art of formulating polyurethane
property characteristics of "green" strength and
Rhma(s) have used so-called "modifiers" in an
Eastman Chemical Company Confidential Information Page 1
 attempt to improve the balance of processing, thermal display a heretofore unattainable balance of
and mechanical attributes of polyurethane Rhma(s). processing, mechanical and thermal properties.
These conventional modifiers have included rosin Particularly surprising and beneficial is the ability of
glycerol ester, polycaprolactone diol and terpene the inventive polyurethane Rhma to attain Shear
phenolic resins. These modifiers have not provided a Adhesion Failure Temperatures in excess of 200
viable solution to the formulators' needs and hence a degrees Centigrade.
need still exists for a modifier that can provide a
Adhesives of the present invention are of use in many
useful balance of processing, thermal and mechanical
end uses, particularly in assembly operations. Among
attributes to polyurethane Rhma(s).
the assembly operations are transportation uses such
Eastman addresses a need as; carpet bonding, door panels, instrument panel

The polyester polyols made in accordance with the assembly, recreation vehicles, over the road trailers,

present invention have resin acids incorporated heavy-duty trucks and marine uses. Also among the

therein through an esterification reaction. It is believed assembly operations that adhesives of the present

that the rosin acid brings advantages to the polyol of invention are of use in construction uses such as;

the present invention. First, the rosin's window assembly, garage door assembly and

monocarboxylic acid controls the hydroxyl structural insulated panels. Also among the assembly

functionality of the polyol, which allows use of operations that adhesives of the present invention are

polyhydric alcohols such as pentaerythritol, and of use in other assembly applications such as; shoe

improves structural performance of the adhesive. soles, non-wovens, and profile wrapping including

Second, the rosin may serve to increase the glass edge banding.

transition temperature. Moreover, presence of the

Technology highlights
rosin in combination with the other components used
The present invention relates to new polyols,
to make the polyol enhances the peel strength of
urethane polymers made from these polyols and
adhesives made therefrom. For example,
reactive hot melt adhesive compositions which
incorporation of an effective amount of the polyols
include the urethane polymers.
made in accordance with the present invention into a
urethane adhesive enhances such physical properties The present invention particularly relates to polyols
as modulus, elongation, tensile strength and heat comprising the reaction products of a
resistance. polyesterification process employing monocarboxylic
acids, polyhydric alcohols and dicarboxylic acids as
The isocyanate functional urethane polymers of this
reactants.
invention and or their blends with conventional
isocyanate functional urethane polymers and or other The polyols of this invention have utility in
thermoplastic and or elastomeric polymers may be polyurethane compositions and confer upon such
used advantageously as moisture curable adhesives compositions a desirable balance of processing,
with excellent physical properties, including improved mechanical and thermal attributes, particularly when
heat resistance. The inventive polyurethane Rhma(s) such compositions are used as reactive hot melt
adhesives.

Eastman Chemical Company Confidential Information Page 2

 Technology details dicarboxylic acids include adipic acid and preferred

The present invention relates to new polyols, new aromatic dicarboxylic acids include phthalic and

urethane polymers made from these polyols and isophthalic acids. Phthalic acid is preferably used as

reactive hot melt adhesive compositions based on the its anhydride. Particularly preferred are aliphatic

new urethane polymers. In one embodiment, the dicarboxylic acids and especially adipic acid. When

present invention particularly relates to polyester the particularly preferred aliphatic dicarboxylic acid,

polyols which include the reaction products of a adipic acid, is utilized, aromatic dicarboxylic acids

polyesterification process employing monocarboxylic such as phthalic acid and isophthalic acids may be

acids, polyhydric alcohols and polycarboxylic acids as optionally and advantageously used as well in the

reactants. reactant mixture provided the moles of aromatic

dicarboxylic acid does not exceed about twice the
The preferred monocarboxylic acid reactants are rosin moles of aliphatic dicarboxylic acid.
acids including wood, gum and tall oil rosin acids.
Particularly preferred rosin acids are tall oil rosin Intellectual property portfolio
acids. The rosin acids may be a mixture of rosin acids US Patent No. 6,525,162: Polyols, polyurethane
obtained by a distillation process. Such distillates will systems and polyurethane reactive hot melt
comprise a mixture of various rosin acids including adhesives produced therefrom
abietic acid and its isomers.
Other technology and service offerings
The polyhydric alcohol reactants preferably have Eastman’s Technology Licensing and Alliances group
more than two hydroxyl functional groups per focuses on the licensing, sale, donation and disposition
molecule. Particularly preferred are polyhydric of intellectual capital for the enterprise. The scope of
alcohols having three or more hydroxyl functional our offerings can begin with the simplistic granting of
groups per molecule. Preferred polyhydric alcohols rights from the Eastman patent portfolio and progress
include pentaerythritol cyclohexane dimethanol, through the transfer of proprietary skills, design
trimethylol propane, dipropylene glycol, and specifications and knowledge captured in our
combinations thereof. confidential know-how.

The preferred polycarboxylic acid reactants have an

acid functionality of about two and may be aliphatic or
aromatic dicarboxylic acids. Preferred aliphatic

For more information:

Technology Licensing and Alliances Telephone:800-Eastman (800-327-8626),Ext. 6076

Eastman Chemical Company Fax: (423) 229-2811
P.O. Box 431 Bldg 280 Email: licensing@eastman.com
Kingsport, TN 37662 www.licensing.eastman.com

Eastman Chemical Company Confidential Information Page 3