Field of the Invention

The present invention relates to polyamides derived from mixed acids (a

polymeric fatty acid and a mono-dibasic acid) and mixed amines (a polyoxyalkylene

diamine, a short-chain diamine, and a medium-chain diamine). These thermoplastic

resin compositions are excellent reinforcing adhesives for flexible substrates and are

particularly useful as box-toe construction resins.

Background of the Invention

It is customary for shoe manufacturers to reinforce the toe end of the upper to

obtain improved wear and retention of shape. It is accepted practice throughout the

shoe industry to obtain such reinforcement by the application of a thermoplastic

stiffening resin, sometimes referred to as a box-toe resin, to the toe portion of the upper.

The thermoplastic resin is applied as a melt and upon cooling forms a stiffly resilient reinforcing coating on the upper.

For a thermoplastic resin to be an acceptable stiffener in this application, the

resin must satisfy the following requirements: first of all, the resin should have some

adhesive character; it should have a low melt viscosity, preferably less than 150 poise

at 190°C; the resin should set rapidly to prevent "welding" of stacked assemblages of

the manufactured articles; and the resin must be stiff to impart and retain the desired

shape, but it must also have sufficient flexibility, even at low temperatures, to resist

cracking upon impact and to "snap back" to its original shape. This latter property, or

more correctly, balance of properties is sometimes referred to as "rigid flexibility" and

is perhaps the most troublesome and difficult property to develop in a thermoplastic

resin, particularly in polyamide resins.

Summary of the Invention

This invention relates to polyamide resins obtainable by the reaction of an acid

component comprised of a major concentration of a dimer acid and a minor

concentration of a monobasic acid and an amine component comprised of a major

concentration of a short-chain alkylenediamine, a first minor concentration of a medium-

chain alkylenediamine and second minor concentration of a polyoxyalkylene diamine

having a molecular weight greater than about 500. By "major concentration" is meant

that the acid or amine component is comprised of at least 50 equivalent % of

equivalents contributed by that acid or amine. By "minor concentration" is meant that

the acid or amine component is comprised of less than 50 equivalent % of equivalents

contributed by that acid or amine. A polymeric fatty acid obtained by the polymerization

of an olefinically unsaturated monocarboxylic acid containing 16 to 20 carbon atoms is

an essential component of the acid mixture. Dimer acids having 36 carbon atoms are

especially useful in this invention. The acid component is preferably essentially free of

short-chain saturated aliphatic dicarboxylic acids containing 7 to 12 carbon atoms, such

as azelaic acid and sebacic acid. The equivalent ratio of dimer acid to monocarboxylic

acid preferably ranges from 0.95:0.05 to 0.7:0.3. The mixed diamines are comprised

of a short-chain diamine, preferably, ethylenediamine, a medium-chain diamine,

preferably hexamethylenediamine, and a polyoxyalkylene diamine having a molecular

weight preferably from about 600 to 5000. The equivalent ratio of short-chain to

medium-chain diamine will typically range from about 2:1 to about 6:1 and the

equivalent ratio of the sum of equivalents of short-chain and medium-chain diamine to

equivalents of polyoxyalkylene diamine will typically range from about 0.9:0.1 and

0.995:0.005. The resulting reinforcing copolyamide resins typically have an acid value

and amine value less than 15, softening point of less than about 125°C (preferably in

the range 90°-110°C), and viscosity (140°C) less than 150 poise.

This invention also relates to a composition comprised of the polyamide of this

invention in a major amount by weight and a first minor amount by weight of a polar wax

and a second minor amount by weight of a polyolefin elastomer. By "major amount" is

meant that the component makes up at least 50 weight % of the combined weight of the

three components. By "minor amount" is meant that the component makes up less than

50 weight % of the combined weight of the three components. These compositions can

be applied to a variety of substrates including leather and synthetic materials, woven

and nonwoven fabrics, and a wide variety of polymeric materials and will readily adhere

thereto. A 1-50 mil film of the composition on the substrate provides a tough resilient

reinforcing coating on the substrate so that it can be shaped and otherwise molded to

the desired configuration and will retain this shape during use. The compositions are

particularly adaptable for use with leather, fabrics and vinyl polymers used in box-toe

construction and impart greater stiffness to the substrate while maintaining flexibility.

This invention also relates to a method of manufacturing an upper for a shoe

comprising applying a melt of a composition comprised of the polyamide of this

invention in a major amount by weight and a first minor amount by weight of a polar wax

and a second minor amount by weight of a polyolefin elastomer to a portion of an upper

and allowing said melt to cool to form a solid coating on said portion of said upper. The

applying and cooling are typically integrated into the manufacture of the shoe and thus,

the applying and cooling are typically accomplished within the cycle time of said

manufacturing. By "footwear upper" is meant that portion of the footwear above the

sole. While this method is particularly useful in reinforcing the toe portion of the

footwear upper, it will be useful in reinforcing other portions of the footwear upper, e.g.

the heel portion, if desired.

Detailed Description

The improved copolyamides of this invention are derived from polymeric fatty

acids. The term "polymerized fatty acid" is intended to be generic in nature and to refer

to polymerized acids obtained from fatty acids. Dicarboxylic acids produced in this

manner, that is, when two moles of the monocarboxylic acid are combined, are referred

to as dimer acids. Processes for the production of dimer acids are well known to the

art and by way of illustration, reference may be had to U.S. Pat. Nos. 2,793,219 and

2,955,121. Thirty-six carbon (C36) dimer acids obtained by the dimerization of an

unsaturated C18 acid such as oleic acid, linoleic acid and mixtures thereof (e.g. tall oil

fatty acids) are especially useful and advantageously employed for the preparation of

the copolyamides. Such dimer acids have as their principal component a C36

dicarboxylic acid and typically have an acid value in the range 180-215, saponification

value in the range 190-205 and neutral equivalent from 265-310. Dimer acids

containing less than 30% by weight by-product acids including monobasic acids, trimer

acids or higher polymer acids are especially useful for this invention. The dimer acids

may also be hydrogenated prior to use and/or molecularly distilled or otherwise purified

to increase the C36 dimer content to 90% or more.

The term "fatty acids" refers to saturated, ethylenically unsaturated and

acetylenically unsaturated, naturally occurring and synthetic monobasic aliphatic

carboxylic acids which contain from about 8 to about 24 carbon atoms. While specific

references are made in this application to polymerized fatty acid polyamide resins which

are obtained from C18 fatty acids, it will be appreciated that the methods of this

invention can likewise be employed with other polymerized fatty acid polyamides.

The preferred starting acids for the preparation of the polymerized fatty acids

used in this invention are oleic and linoleic acids, due to their ready availability and

relative ease of polymerization. Mixtures of oleic and linoleic acids are found in tall oil

fatty acids, which are a convenient commercial source of these acids. Fatty acids can

be polymerized using various well known catalytic and noncatalytic polymerization

methods. A typical composition of the polymerized C18 tall oil fatty acids which are

used as the starting materials for the polyamide resins used in the present invention is:

C18 monobasic acids (monomer) 0-15% by wt.

C36 dibasic acids (dimer) 60-95% by wt.

C54 (or higher) trimer acid or polybasic acids 0.2-35% by wt.

In preparing polymerized fatty acid polyamide resins for use in the present

invention, it is preferable that the starting polymerized fatty acid contain as high a

percentage as possible of the dimer (C36 dibasic) acid, e.g. at least about 90% by wt.,

in order to obtain optimum physical properties in the final product.

Monocarboxylic acids may be added, in addition to the monobasic acids

remaining in the polymerized fatty acid, to control molecular weight. Preferred

monocarboxylic acids are linear and have 2 to 22 carbon atoms, more typically from

about 12 to about 20 carbon atoms. Most preferred are stearic, tall oil fatty and oleic

acids. The total amount of monocarboxylic acids in the acid component should be

sufficient to limit the molecular weight of the polyamide to a degree which will yield the

softening point and the melt viscosity desired of the polyamide. In general, the total

amount of monocarboxylic acids in the acid component will range from about 5 eq.%

to about 15 eq.%, more typically from about 8 eq.% to about 12 eq.%, based on the

total acid equivalents of the acid component.

The amine component will be a mixture of amines comprised of a short-chain

diamine, a medium-chain diamine, and a polyoxyalkylene diamine is reacted with the

above-defined acid mixture to obtain the improved copolyamide resin compositions.

The short-chain and medium-chain diamines preferably correspond to the formula:

H ₂ N-(CHR) _n -NH ₂

where "n" is 2 or 3 for the short-chain diamines and "n" is 4-8 for the medium-chain

diamine, and R is hydrogen for a straight chain diamine and R is lower (e.g. C1-C4)

alkyl for a branched chain diamine. Thus, examples of the useful short-chain diamines

are ethylenediamine, 1 ,2-propylenediamine, and 1,3-propylenediamine. Examples of

the medium-chain diamines include tetramethylenediamine, pentamethylenediamine,

hexamethylenediamine, octamethylenediamine, 2-methyl-1 ,5-pentanediamine,

5-methyl-1 ,9-nonanediamine, and trimethylhexamethylenediamine. Especially useful

copolyamides are obtained in accordance with this invention when the short-chain

diamine is ethylenediamine and the medium-chain diamine is hexamethylenediamine.

The equivalent ratio of short-chain to medium chain diamine will typically range from

about 2:1 to about 6:1 , more typically from about 3:1 to about 5:1 , and most typically

from about 3.8:1 to about 4.2:1.

The amine component is further comprised of a polyoxyalkylenediamine. The

polyoxyalkylenediamine reactant comprises one or more amino-compounds where the

amino-compound comprises both amine groups and a polyether chain.

Examples of useful polyoxyalkylenediamines have the structural formula:

H ₂ N-CH ₂ CH(R ² )-R ¹ -0-CH ₂ CH(R ² )-NH ₂

wherein:

R ¹ represents a polyoxyalkylene chain having the structural formula:

(0-CH ₂ -CH ₂ -) _a -(0-CH ₂ -CH(R ³ )) _b

wherein:

R ³ is a monovalent organic radical selected from the group consisting of C1 to

C4 aliphatic hydrocarbons, 'a' designates a number of ethoxy groups (0-CH ₂ -CH ₂ ),

'b' designates a number of monosubstituted ethoxy groups (0-CH ₂ -CH(R ³ )), the sum

of 'a' and 'b' is equal to or greater than 10 but less than or equal to 300, provided that

for any values of a and b the sequence of ethoxy and monosubstituted ethoxy groups

within a polyoxyalkylene chain may be completely random and/or there may be blocks

of ethoxy and/or monosubstituted ethoxy groups, and R ² designates hydrogen or a

monovalent organic radical selected from the group consisting of C1 to C4 aliphatic

hydrocarbons.

The techniques to prepare suitable polyoxyalkylenediamines are known in the

art, and include reacting an initiator containing two hydroxyl groups with ethylene oxide

and/or monosubstituted ethylene oxide followed by conversion of the resulting terminal

hydroxyl groups to amines. Illustrative of the polyoxyalkylenediamine reactants

employed in the invention are the Jeffamine™ brand of polyoxyalkyleneamines

available from Huntsman Corporation, Houston, Texas. These

polyoxyalkylenediamines are prepared from reactions of bifunctional initiators with

ethylene oxide and propylene oxide followed by conversion of terminal hydroxyl groups

to amines. The most preferred polyoxyalkyleneamines are the Jeffamine™ D-series

polyoxyalkyleneamines from Huntsman Chemical Company which have approximate

molecular weight between about 600 and about 6,000, more preferably having a

molecular weight from about 900 to about 5,000. The most preferred

polyoxyalkylenediamines contain only oxypropylene groups, i.e. those

polyoxyalkylenediamines of the above formula wherein "a" is zero and R ³ is methyl.

The number average molecular weight of the polyoxyalkylenediamine is typically

between about 600 and about 6000 and, more preferably, about 1 ,000 and about

2,500. The equivalent ratio of the sum of the equivalents of short-chain diamine and

medium-chain diamine to equivalents of polyoxyalkylenediamine will typically be greater

than about 0.9:0.1 , and will more typically range from about 0.92:0.08 to 0.999:0.001 ,

even more typically from about 0.95:0.05 to about 0.995:0.005 and most typically from

about 0.975:0.025 to about 0.99:0.01.

The number of free acid groups and/or free amine groups present in the

polymerized fatty acid polyamide resin are directly related to the relative amount of the

polymeric fatty acids, dicarboxylic acids and diamines involved in the polymerization

reaction and the degree of completion of the reaction. For the above reasons,

approximately stoichiometric amounts (typically with a slight excess of acid groups, e.g.

a ratio of total acid to total amine groups of from about 1.001 :1 to about 1.1 :1 , more

typically from about 1.005:1 to about 1.05:1 , and most typically from about 1.01:1 to

about 1.02:1) of the polymerized fatty acids (and added monocarboxylic acids) and the

diamines based on the total number of available acid and amine groups should be used

to prepare the polyamide resins for this invention and the reaction conditions should be

selected to ensure completion or substantial completion of the amidation reaction.

It is desirable that the polymerized fatty acid polyamide be the result of as

complete an amidation reaction as possible between the starting acid component and

the diamine component. Those skilled in the art will recognize that the degree of

completion of the amidation process can be determined by evaluating the acid number

and the amine number of the final polymer. The polyamide resin should have a

relatively low acid number, typically less than about 40, more typically each less than

about 15, and even more typically each less than about 10. Ideally, the amine number

of the polyamide resin employed should be zero (0). However, it is often difficult, if not

impossible, to reach complete reaction, and this value should be two or less.

The instant copolyamide resins are prepared using conventional procedures and

reaction conditions known to the art. It should be noted that while reference is made

to acid and amine components for purposes of determining the relative amounts of each

acid and amine used to prepare the polyamide, there is no need to form a separate

premix of acids and a separate premix of amines, nor is it required that all reactants be

charged together at the beginning of the reaction. In general, the acid and amine

components are reacted until the final product has an acid value and an amine value

less than 15 and even more preferably less than 10, with the reaction being generally

conducted at temperatures from about 100°C to about 300°C for from about 1 to about

8 hours. Most often the reactions will be heated from 140° to 240°C until the theoretical

amount of water is evolved. Generally several hours are required to complete the

reaction. The reaction is preferably conducted under an inert atmosphere, such as

nitrogen, and during the final stages of the reaction a vacuum is applied to the system

to facilitate removal of the final traces of water and any other volatile materials. The use

of acid catalysts, such as phosphoric acid, and vacuum can be used, especially in the

latter part of the reaction, to yield a more complete amidation reaction.

This invention also relates to a composition comprised of the polyamide of this

invention in a major amount by weight and a first minor amount by weight of a polar wax

and a second minor amount by weight of a polyolefin elastomer. The wax used in the

compositions of this invention is a polar wax, i.e. a wax having sufficient polar

functionality to form a homogeneous melt with the polyolefin elastomer and the

polyamide. Preferred examples of polar waxes are low molecular weight polyolefin (e.g.

polyethylene) waxes having polar functionality arising from copolymerization or grafting

with an acid functional monomer or from oxidation of the polyolefin. These preferred

waxes typically have an acid number of from about 1 to about 50.

The wax component of the adhesive compositions of the present invention is

preferably present in an amount of from 5 to 30% by weight, preferably from 10 to 20%

by weight. It is preferred for the waxes to have a melting point of from 90°C to 110°C

(i.e. similar to those of the preferred polyamides) although some suitable materials may

have lower melting points.

Preferred waxes for use in the present invention are natural and synthetic waxes

based on a hydrocarbon backbone, including polyolefin waxes and their derivatives.

Synthetic waxes of this type are made, for example the Fischer-Tropsch and Ziegler

processes. Especially suitable are those based on low molecular weight polyethylene

generally having a molecular weight of less than 6,000, usually from 1,000 to 5,000.

These waxes generally have softening points in the range of from 97°C to 106°C and

those having a molecular weight between 2,000 and 4,000 generally have softening

points between 100.5°C and 104°C. Amongst suitable commercially available materials

there may be mentioned the Epolene polyethylene waxes sold by Eastman Chemical

Company including Epolene C16, available from Eastman Chemical, which is a maleic

anhydride modified polyethylene. This material has been described as being

manufactured according to the method of Example 1 of U.S. Pat. No. 3,484,403, the

disclosure of which is incorporated herein by reference. Examples of other useful

waxes are Epolene C18, also from Eastman Chemical, and the oxidized ethylene

homopolymers available from Eastman Chemical as the Epolene E series and which

have acid numbers ranging from 15-47.

It has been found that the incorporation of a polyolefin elastomer leads to

improvements in the low temperature flexibility and brittleness of the adhesive

formulations while maintaining an acceptable viscosity so that the compositions can still

be applied at moderate melt temperatures, e.g. from about 120°C to about 140°C. The

polyolefin elastomer is generally included in amounts not exceeding about 20% by

weight, preferably about 1% to about 15%, and more especially 5%- 10%, by weight of

polyamide, polar wax, and polyolefin elastomer together.

Examples of polyolefin elastomers are described in "Synthetic Elastomers",

Encyclopedia of Polymer Science and Engineering, index vol., pp. 106-127 (John Wiley

& Sons, Inc., N.Y..N.Y., 1990), the disclosure of which is incorporated herein by

reference. Preferred polyolefin elastomers are polyethylene copolymers having

densities of less than about 0.92 g/cc and secant moduli of 2000 psi to 10,000 psi. One

especially advantageous group of polyolefin elastomers are copolymers of ethylene and

a C ₃ -C ₂₀ alpha-olefin that have been polymerized in the presence of a constrained

geometry catalyst. Examples of such polymers are described in U.S. Patent Nos.

5,272,236 and 5,278,272, the disclosures of which are incorporated herein by

reference. Examples of such polymers, which are copolymers of ethylene and 1-

octene, more than 20% by weight of the polymer being derived from 1-octene, are

commercially available from Dow Chemical under the "Engage" brand name, e.g.

Engage 8200 (having a density of 0.87 g/cc and a secant modulus of 2900). Also

useful are the copolymers of ethylene and 1-butylene available from Exxon under the

"Exact" brand name.

The compositions can be employed to reinforce a variety of natural and

synthetic, flexible substrates. They are particularly useful with leather, suede and

synthetic materials; open- and closed-cell materials derived from polyurethane, vinyl,

natural rubber, neoprene, styrene-butadiene copolymer, polybutadiene or the like;

woven and nonwoven fabrics obtained from natural fibers such as cotton, wool, silk,

sisal, hemp, jute, kenaf, sunn and ramie; woven and nonwoven fabrics derived from

rayon (viscose), cellulose esters such as cellulose acetate and cellulose triacetate,

proteinaceous fibers, such as those derived from casein, and synthetic fibers or

filaments including polyamides such as those obtained by the condensation of adipic

acid and hexamethylenediamine or the like, polyesters such as polyethylene

terephthalate, acrylic fibers containing a minimum of about 85 percent acrylonitrile with

vinyl chloride, vinyl acetate, methacrylonitrile or the like and the modacrylic fibers which

contain lesser amounts of acrylonitrile, copolymers of vinyl chloride with vinyl acetate

or vinylidene chloride, the formal derivatives of polyvinyl alcohol and olefin polymers

such as polyethylene and polypropylene; paper; cork; elastomeric materials; and the

like. The copolyamides are applied to the substrate as a hot melt and upon cooling

provide greater stiffness while maintaining flexibility of the substrate. The resin can be

applied using conventional hot melt application procedures, such as printing, dipping,

spreading, rolling, etc. and the film thickness can range from about 1 mil up to about 50

mils. While for most constructions the resin is applied to only one side of the substrate,

it may be applied to both sides and a fabric or the like applied to either side, or both, to

form a sandwich type construction. In a typical box-toe construction, the copolyamide

is printed onto one side of the substrate to a thickness of 2 to 10 mils. A fabric (nylon,

polyester, cotton, etc.) liner may be applied to the interior of the box-toe before the resin

has completely set.

Because the compositions of this invention typically have a softening point in the range of 90°-110°C, and viscosity (140°C) less than 150 poise, a melt of the

composition at a temperature of from about 120° to about 140°C can be easily applied

to a substrate by hot melt coating techniques. It is an advantage of the compositions

of this invention that such a melt can be applied at such temperatures because some

substrates can be degraded at higher temperatures. For example, water-proofed

leathers typically contain significant levels of organics that will volatilize from the leather

at temperatures used to apply conventional box toe coatings, e.g. temperatures of from

160°-175°C (or even higher). Such volatilization can cause the organics to evaporate

from the surface of the substrate and form bubbles in the composition. These bubbles

can thus roughen the surface of the composition and can lead to a degradation of the

properties of the resulting coating and/or substrate.

The following examples illustrate the invention more fully, however, they are not

intended to limit the scope of the invention and numerous variations will be evident to

those skilled in the art. In this specification, and the following examples, all parts, ratios

and percentages are on a weight basis unless otherwise indicated.

EXAMPLES

In these examples, the following general procedures were used.

Part 1 : (Polyamide base resin)

The polyamide acid and amine components were charged to a resin kettle

equipped with mechanical stirrer, thermocouple, nitrogen blanket and distillation

head. The dimer acid was a blend of predominantly C36 polymerized fatty acid

containing 2 wt. % monomeric acids, 96 wt. % dimeric acids and 2 wt. % trimeric acids

and a predominantly C36 polymerized fatty acid containing 12 wt. % monomeric acids,

77 wt. % dimeric acids and 11 wt. % trimeric acids in a weight ratio of about 2:1 of the

former to the latter (nominal equivalent weight of the blend being 282 g/equiv.). The

monocarboxylic acid had a nominal equivalent weight of 285 g/equiv. The

hexamethylenediamine (HMDA) was at 70% solids in solution. The

polyoxyalkylenediamine was a polyoxypropylenediamine having a molecular weight of

about 2000 g/mole and is available from Huntsman Chemical, Houston, Texas, as

Jeffamine D-2000. Then about 0.01 wt. % phosphoric acid as catalyst, 0.3 wt. %

antioxidant (high molecular weight hindered phenols available form Giba-Geigy as

Irganox 1010) and 0.05 wt. % defoamer were added and the reagents mixed. The

temperature of the reaction is raised to 227 °C. Water of reaction is removed overhead.

Once the reaction reaches temperature, it is held for a minimum of 90 minutes. At the

end of the 90-minute hold, vacuum is applied to the reaction for 45 - 60 minutes. The

vacuum is released with nitrogen. Part 1 is complete and may be dumped for use later,

or may be used directly for addition of Part 2. If the reaction is to be used directly, a

small sample can be removed for determination of Part 1 physical properties.

Part 2: (Blending of polyamide base resin with wax or wax/polyolefin elastomer)

The product from Part 1 is heated to 227°C. When the reaction is at

temperature, a second portion of antioxidant (0.24 wt. %) is added. The wax, Epolene

C16, Eastman Chemical, if added, is added in small steps in order to maintain the

reaction temperature above 204°C. The polyolefin elastomer, Engage EG 8200, Dow

Chemical, Midland, Michigan, if added, is charged to the reaction in small steps after

the wax has completely dissolved and is well mixed (typically 15 minutes after wax

addition is complete). When wax/elastomer addition is complete, the reaction is placed

under vacuum and held for 20-30 minutes. The vacuum is released with nitrogen and

the blend is dumped. Final properties are determined. The blend of Example 4

separated into distinct phases and was not further tested. The control resin is

commercially available as MACROROD 2600 from Henkel Corporation, LaGrange,

Illinois.

Box Toe Testing

Box toe application: Box toe adhesives prepared above are tested for box toe

application performance by applying the adhesive to selected substrates. Flow

properties, stringing character, and flexibility are determined by printing onto vinyl

coated fabric pieces (vinyl side). Box toe thickness is adjusted to be approximately 1

mm at the center of the toe. The box toe application is carried out on a Sysco

Machinery Corp. Box Toe Application Machine. The melt pot temperature is set for the

desired application temperature and the melt temperature measured with a hand held

thermocouple. Once the adhesive has been applied and is cool, the print on box toe

can be removed from the face (vinyl side) of the material.

Box toe adhesive performance tests: The appearance, flow behavior, and stringing of

the box toe adhesive under evaluation are determined qualitatively by the operator.

Box toe flexibility/cracking tests: Box toes removed from the material are used to

determine flexibility. Samples are maintained for a minimum of 16 hours at the desired

test temperature. Low temperature samples were held in a freezer maintained between

-5 and -10 °C. Flexibility/cracking performance is determined by folding the box toe in

half twice, first along the short axis, then in half again along the long axis. The box toe

is considered to fail the cracking test if it breaks or cracks.

Tear Resistance: Box toes removed from material are torn by hand from top to bottom.

The relative amount of effort required to tear is used to judge the quality of tear

resistance and rated good or poor.

Softening point is determined after 18 hours in accordance with ASTM Test Method

I

E-28 and viscosity is determined in accordance with ASTM D3236 RVT, Spindle 27.

Formulations

Example number 1 2 3 4 5 6 7 8 9

PART 1 (Base Resin) wt. % of Part 1

Polymerized Fatty Acid 80.7 80.7 80.34 80.34 80.34 80.34 82.03 82 82

Monocarboxylic Fatty Acid 5 5 5 5 5 5 5.1 5.1 5.1

Ethylenediamine 7.1 7.1 7.1 7.1 7.1 7.1 7.25 7.25 7.25

HMDA (70%) 5.24 5.24 5 5 5 5 5.31 5.3 5.3

Polyoxypropylenediamine 1.6 1.6 2.25 2.25 2.25 2.25 0.00 0.00 0.00

CO

Catalyst 0.01 0.01 0.01 0.01 0.01 0.01 0.01 0.01 0.01

Antioxidant 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3

Defoamer 0.05 0.05 0.05 0.05 0.05 0.05 0.05 0.04 0.04

Part 2 (Added for Final Product) % added in Part 2, based on total Part 1 charge

Antioxidant 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3

Polar Wax 15 16.67 15 0.00 33.33 22.22 15 18.89 33.33

Polyolefin Elastomer 7.22 8.33 7.22 22.22 0.00 1 1.1 1 7.22 9.44 0.00

Physical Properties and Performance

Control 1 2 3 4 5 6 7 8 9

Softening Pt. Part 1 , °C — 106 101 99 -- 102 97 — 103 105

Softening Pt. Part 2, °C 137 102 103 100 -- 107 102 104 104 107

Viscosity at 140 °C, P — 143 171 133 — 163 190 158 185 265

Viscosity at 160 °C, P 235 61 68 56 — 71 81 64 76 110

Tensile Strength, 700 480 520 620 — 580 590 550 550 610

Ultimate, psi

SO

% Elongation at break 76 74 59 142 — 62 127 82 84 84

Box toe application, slight slight slight slight — slight slight very slight slight

Stringing

Tear resistance good good good good ~ poor good good good poor

Crack Test @ -5 °C 95 66 90 97 — 95 100 58 40 92

(% pass)

Bubbling on leather yes no —

155°C 130°C