US00562475 8A

United States Patent [191 [11] Patent Number: 5,624,758

Maksymkiw et al. [45] Date of Patent: Apr. 29, 1997

[54] WATER-BASED ADHESIVE FORMULATION Derwent Abstract of: JP 6256749 (Sep. 1994).
HAVING ENHANCED CHARACTERISTICS “Product Information -Dispercoll KA-8464. Aqueous Poly
[75] Inventors: Mike Maksymkiw. White Bear Lake; urethane Dispersion” of Mobay Corporation. a Bayer USA
Gary Haider. Maplewood; Michael Inc. Go. Pittsburgh. PA Rev. Jan. 1989.
Dochniak. St. Paul; Leonard “New High Performance Urethane Dispersion for Adhe
Jannusch. White Bear Lake; Paul sives” Technical Information Sheet by Zeneca Resins.
Wade. Stillwater. all of Minn. Wilmington. MA. (Jan. 1983).
[73] Assignee: ILB. Fuller Licensing & Financing, “NEOTAC R-9320” Technical Information. ICI Resins US.
Inc.. Arden Hills. Minn. Wilmington. MA. Bulletin R-9320. Revised Apr. 1992.
“Air?eX 320 Base for Adhesives” by Air Products & Chemi
[21] Appl. No.: 617,099 cals. Inc. 1989 (month unknown).
[22] Filed: Mar. 18, 1996 “Unitex 108” by Unitex Chemical Corp.. Greensboro. NC.
27406 (undated).
Related US. Application Data
“Material Safety Data Sheet for Benzo?ex®50 Plasticizer”
[62] Division of Ser. No. 484,347, Jun. 7, 1995, Pat. No. 5,523, by Velsicol Chemical Corporation. Rosemount. H3. (Aug.
344. 1991).
[51] Int. Cl.6 ......................... .. B32B 27/00; B32B 27/40; Derwent abstract for: US 4644030 issued Feb. 1987.
A43B 9/12; A43B 13/32
Derwent abstract for: JP 63023972 published Feb. 1988.
[52] US. Cl. ................................... .. 428/4231; 428/4234;
428/4239; 428/4251; 36/83; 36/ 19.5; 36/DIG. 1 “Polyurethane dispersions and emulsi?able polyisocyantes
[58] Field of Search ................................... .. 524/155. 168. for water based adhesives.” Holmbach. Bayer AG (Jul.
524/169. 284. 292. 296. 297. 303. 311. 1990).
507; 523/415; 525/123. 127. 438. 454.
455. 457. 458; 428/4231 423.4. 423.9.
425.1; 36/83. 19.5. DIG. 1 Primary Examiner-Paul R. Michl
Assistant Examiner—Patrick Niland
[56] References Cited Attorney, Agent, or Firm—Vidas. Arrett & Steinkraus. PA.
U.S. PATENT DOCUMENTS [57] ABSTRACT
4,303,774 12/1981 Nachtkamp et a1. ................... .. 528/71 Adhesive formulations are blends of aqueous polymer dis
4,636,546 1/1987 Chao ................ .. 524/507 persions and a hydrophobic plasticizer. The blended dis
4,870,129 9/1989 Henning et al. 524/597 persed polymers include at least one hard sulfonated poly
5,334,690 8/1994 Scha?leutle et a1. .... .. 528/71
5,373,050 12/1994 Morikawa et a1. ................... .. 524/591
ester urethane. at least one soft non-sulfonated polyester
urethane. and at least one polar non-polyurethane water
FOREIGN PATENT DOCUMENTS based polymer or copolymer. A high molecular weight
9304018 of 0000 Germany .
elastomeric non-sulfonated polyurethane polymer and a
crossljnker are optional further components in the blend.
OTHER PUBLICATIONS The formulations are useful as non-heat activating. one
Derwent Abstract of: JP 57030776 (Feb. 1982). component adhesives which generate excellent green
“Dispercoll Trial Products KA 8464 and KA 8481 as raw strength. water and heat resistant bonds.
materials for water-based dispersion adhesives”. Gauster et
al. Bayer AG (Aug. 1989). 3 Claims, N0 Drawings
 5,624,758
1 2
WATER-BASED ADHESIVE FORMULATION The preferred formulations of the invention. when used
HAVING ENHANCED CHARACTERISTICS with a crosslinker. have very long pot-lives. in some cases
up to a month or more after addition of the crosslinker.
This application is a division of application Ser. No. Surprisingly. such formulations even after a month exhibit
08/484347. ?led Jun. 7. 1995 now US. Pat. No. 5.523.344. excellent green strength characteristics without heat activa
tion. This allows formulations containing crosslinking addi
BACKGROUND OF THE INVENTION tives to be shipped by the manufacturer as one-component
compositions. and provides a substantially improved con
1. Field of the Invention venience to the end user.
This invention relates to a new water-based adhesive
The applied adhesive ?lms have a useful life or “open
formulation. Speci?cally. a formulation having enhanced time” (time between the making of said films and the using
characteristics such as excellent adhesion without heat acti of said films to form the bonded structure) ranging from
vation. More speci?cally. it relates to a one-component about an hour to a few hours. depending on the composition
aqueous sulfonated polyurethane adhesive formulation hav of the dispersion and the crossliukers chosen.
ing enhanced properties for use in applications where use of 15
heat for activation is undesirable or unavailable.
The invention is also directed to the use of the inventive
formulations as adhesives and to an adhesively bonded
2. Description of the Prior Art structure comprising said formulation as the adhesive.
Aqueous polyurethane dispersions have received a great The inventive adhesive formulations comprise:
deal of attention recently. These dispersions are compatible
a) at least one hydrophobic plasticizer. for instance a
with many other water-based polymers. and adhesives made member of the group consisting of alkyl and aryl
from them usually exhibit improved performance. Examples sulfonamides. benzoate esters. phthalate esters.
of these activities can be found in JP 57030776 and JP
adipates. titrates. and mixtures thereof; and
83046277. These patents disclose heat curing. water
resistant and stable adhesive compositions comprising dis b) an aqueous polyurethane dispersion blend comprising:
persions of partially saponi?ed polyvinyl acetate. aqueous 25 1) at least one hard sulfonated polyester urethane;
solutions of polyurethanes and dispersable polyisocyanate 2) at least one soft non-sulfonated polyester urethane;
compounds. The adhesive properties of these compositions and
are generated with a heat curing cycle. 3) at least one polar non-polyurethane water-based
polymer or copolymer.
JP 6256749 discloses another adhesive composition pre A high molecular weight non-sulfonated polyurethane poly
pared by adding polyisocyanate crosslinking agents to a mer and/or a crosslinker. such as a dispersable polyisocy
blend of aqueous polyurethane resins and polyvinyl latex. anate crosslinker. are optional components employed in
This polyurethane based adhesive composition is reported to preferred embodiments of the invention.
exhibit high adhesion. and excellent heat and water resis The invention also relates to a polyurethane dispersion
tance.
35 based adhesive formulation containing an interpenetrating
German Utility Model patent no. 9304018 discloses an network having crosslinked matrixes for improved heat.
adhesive comprising at least a two component polyurethane moisture and solvent resistance. and to the process of
dispersion having a pot life of 12 hours. This water-based manufacture and use of the same.
formulation describes a polymer blend of polyurethane
dispersions. EVA’s or methacrylic derivatives. characterized DETAILED DESCRIPTION OF THE
in that it comprises one essentially non-hydrophobic plasti INVENTION
cizer. In the inventive adhesive formulations an aqueous poly
A draw back for these prior art compositions is the need urethane dispersion blend is employed which includes at
for heat activation. making them unsuitable for use where least one “hard” sulfonated polyester urethane. at least one
heat for activation is either unavailable or destructive to the 45 “soft” non-sulfonated polyester urethane; and at least one
substrates or parts being bonded together. polar non-polyurethane water-based polymer or copolymer.
The present inventors have now discovered a one The “hard” sulfonated polyester polyurethane is a rela
component sulfonated aqueous polyurethane dispersion tively high molecular weight anionic sulfonated polyester
based adhesive formulation having excellent adhesive urethane polymer which is characterized by a shear storage
properties. good green strength. solvent resistance. and modulus (G‘) having a value of from about 109 to about 1010
capable of forming moisture and heat resistant bonds with dynes/cm2 at 25° C. and a frequency of 10 radians/sec. The
out heat activation. relatively high molecular weight. polyurethane useful as the
hard polyurethane in the aqueous polyurethane dispersion
SUIVIMARY OF THE INVENTION blends of the present invention can be linear aliphatic. cyclic
The present invention is directed to a novel adhesive 55 aliphatic. or aromatic sulfonated polyester urethanes. pref
formulation comprising plasticized aqueous polyurethane erably formed from at least one sulfonated polyamine or
dispersion blends. The formulations of the invention provide polyol and one or more diisocyanates. A suitable example of
excellent adhesion properties upon pressurized joining of such a sulfonated polyester polyurethane dispersion is Dis
coated substrates. This adhesion property. without heat percollTM KA-8464. sold by Mobay Corporation. Pittsburgh.
activation. and the unexpected heat resistant properties of 60 Pa. The hard polyurethane dispersion solids may comprise
the resulting bonds on aging. are believed to be unique from about 15 parts to about 35 parts. preferably from about
properties for polyurethane dispersion adhesive formula 20 parts to about 30 parts. based on 100 parts total solids.
tions. The inventive adhesive formulations have properties The “so ” non-sulfonated polyurethane component of the
superior to polychloroprene (e.g. Neoprene®) based contact inventive blends is a relatively low molecular weight poly
adhesives. have good green strength and moisture resistance 65 urethane polymer characterized by a shear storage modulus
and can be spray-coagulated with acids (eg by HYDRO (G') having a value of from about 106 dynes/cm2 to about
pHUSETM process). 108 dynes/cm2 at 25° C. and 10 radians/sec. It can be formed
 5 ,624.758
3 4
from linear aliphatic. cyclic aliphatic. or aromatic non component has elastomeric properties. It may comprise from
sulfonated polyester urethanes. preferably formed from about 10 parts to about 30 parts. preferably from about 15
diisocyanates such as isophorone diisocyanate (IPDI). hex parts to about 25 parts. based on 100 parts total solids.
amethylene diisocyanate (HDI). tetramethylxylylene diiso The adhesive compositions of the present invention may
cyanate (TMXDI). and mixtures thereof. Such polymers are include a water dispersable crosslinker. Conventional water
tacky and give the ?nal adhesive composition added tack dispersible polyfunctional chemically activatable crosslink
and improved initial green strength characteristics. The soft ing agents are useful for the present invention. These
polyurethane dispersion solids are present from about 15 crosslinking agents include dispersable formulations of
parts to about 35 parts and preferably from about 20 parts to polyfunctional aziridines. isocyanates. melamine resins.
about 30 parts. based on 100 parts total solids. epoxies. oxazolines. carbodiimides and other polyfunctional
crosslinkers. Typically. the crosslinking agents are added at
The blended dispersion also includes a polar. non
a level of about 1 to about 20 parts. preferably from about
polyurethane water-based polymer or copolymer compo
5 parts to about 15 parts based on 100 parts total solids. It
nent. Addition of at least one such polar. water-based poly
is surmised that when crosslinking agents are added to the
mer or copolymer can improve the sprayability of the
dispersion. Examples of these polymers or copolymers 15 polyurethane dispersion adhesive composition. an interpen
etrating or interconnected network having crosslinked
include vinyl acetate-ethylene copolymers. acrylic matrixes is formed which link the blended polymers with
polymers. vinyl acetate polymers and other vinyl polymers. covalent and/or non-covalent linkages. The crosslinked net
The polar. non-polyurethane water-based polymer or
copolymer solids comprise from about 5 parts to about 40 work gives the adhesive composition further improved heat.
moisture and solvent resistance. A surprising feature of
parts. and preferably from about 5 parts to about 15 parts.
preferred embodiments of the invention is that the
based on 100 parts total solids.
crosslinker can be added to the adhesives at least a month
The inventive formulations also include a hydrophobic before use without destabilizing (gelling or high
plasticizer. The hydrophobic plasticizers enhance the water sedimentation) the system. Therefore the crosslinked com
resistance properties of the adhesive. They can be selected positions can be prepared by the supplier before shipping to
25
from the group consisting of alkyl and aryl sulfonamides. the end user.
benzoate esters. phthalate esters. adipates. citrates. and mix The crosslinked or uncrosslinked adhesives of the
tures thereof. Particularly preferred are alkyl sulfonamides. invention. in some cases. can be applied to one or both
aryl sulfonamides. alkylene glycol benzoates. dialkylene substrates and subsequently successfully bonded. with pres
glycol benzoates. and mixtures thereof. The amount of sure but without heat. as long as several hours later and still
30
plasticizer present in the adhesive composition can vary give adhesive strength properties which are similar to those
from about 1 part to 40 parts. and preferably from about 20 obtained when the substrates are joined promptly after
parts to about 40 parts. based on 100 parts total solids. application and drying or coagulan'on of the adhesive. This
The sulfonated polyester urethanes contain ionomers is a further signi?cant advance in the art of aqueous disper
capable of strong hydrogen bonding and ionic dipole inter 35 sion adhesives since it allows for separation of the adhesive
actions. These strong intermolecular forces give the poly application and bonding steps so that the adhesive can be
mers improved heat and water resistance. as well as good preapplied. for instance in a batch process and then bonded
adhesive properties. These same high inter-molecular forces assemblies can be subsequently prepared on a batch basis.
also oppose plasticization. This is well known in the art. The An especially preferred embodiment of the invention is an
documentation can be found in the proceedings of the 40 adhesive composition which comprises:
Plasticization and Plasticizer Processes symposium spon a) at least one hydrophobic plasticizer selected from the
sored by the Division of Industrial and Engineering Chem group consisting of alkyl and aryl sulfonamides. ben
istry at the 147th meeting of the American Chemical Society. zoate esters. phthalate esters. adipates. citrates. and
Philadelphia. Pa.. Apr. 6-7. 1964. The adhesive composi mixtures thereof; and
tions of the present invention surprisingly possess good 45 b) an aqueous polyurethane dispersion comprising
adhesive properties without heat activation. using hydro 1) at least one high molecular weight sulfonated poly
phobic plasticizers. ester urethane;
A preferred embodiment can comprise: 2) at least one high molecular weight non-sulfonated
a) at least one hydrophobic plasticizer selected from the polyester urethane;
group consisting of alkyl and aryl sulfonamides. ben 3) at least one tacky non-sulfonated polyester urethane;
zoate esters. phthalate esters. adipates. citrates. and and
mixtures thereof; and 4) at least one polar non-polyurethane water-based
b) an aqueous polyurethane dispersion comprising polymer or copolymer; and
1) at least one high molecular weight sulfonated poly c) at least one polyfunctional crosslinking agent selected
ester urethane; 55 from the group consisting of chemically activatable
2) at least one high molecular weight non-sulfonated crosslinkers.
polyester urethane; To prepare the adhesive formulations of the invention the
3) at least one tacky non-sulfonated polyester urethane; aqueous polymer dispersions are blended together with mild
and agitation and then the hydrophobic plasticizer is added.
4) at least one polar non-polyurethane water-based Crosslinkers are added last.
polymer or copolymer. Application of the adhesive formulations of the invention
In this embodiment the non-sulfonated high molecular can be accomplished in either one-side mode or two-side
weight polyester urethanes can be crystalline or semi mode. In the one-side mode the adhesive is applied to one
crystalline linear aliphatic. cyclic aliphatic. or aromatic of two substrates to be joined and dried. coagulated with
polyester urethanes. preferably also formed from diisocyan 65 acid or spray coagulated (acid added in spray droplet) for
ates such as isophorone diisocyanate (IPDI). hexamethyl instance by the HYDROpHUSETM process. The second
enediisocyanate (HDI). and mixtures thereof. Preferably this substrate is then brought into contact with the adhesive
 5,624,758
5 6
coated substrate with pressure. In the two-side mode the EXAMPLES 1-4
adhesive is applied to both substrates to be joined and then
the substrates are brought together with pressure. The fact Blended formulations were prepared as shown in Table 1
that heat activation is not required to accomplish bonding below. After formulation of the blended adhesive. the for
gives the formulations the characteristics of contact mulations were subjected to Peel Adhesion testing under the
adhesives. a unique characteristic for polyurethane disper conditions speci?ed above for Tests 1 and 2 above. Results
sion adhesives. are shown in Table 1 below.
It is especially surprising that even the crosslinked adhe
sive compositions possess good adhesive properties without TABLE 1
heat activation. 10
These adhesives can be used either in the aqueous dis
persion form. or in the form of a cast ?lm. to bond both Components 1 2 3 4
porous and non-porous substrates. for applications in the Hard Sulfonated Polyester 36.57 34.74 34.74
automotive. aerospace. and others where regular heat acti Polyurethane (Dispercoll K-8464,
vatable and/or heat curing polyurethane dispersion adhesive Miles Inc.)
formulations are being used. They are especially useful in High M01. Wt. Non-Sulfonated 12.29 11.67 12.29 11.67
applications where the use of heat for activation is either not Polyurethane (Neorez R-9630,
Zeneca Resins)
available or destructive to the substrates. Such applications Soft Tacky Non-Sulfonated 26.13 24.84 26.13 24.84
can include ?lm to ?lm lamination. Polyurethane (Neorez R-9320,
Although not necessary to obtain good bonding. sub Zeneca Resins)
strates coated with formulations of the invention can also be Hydrophobic Sulfonamide Plasticizer 15.49 14.71
(Uniplex 108, Unitex Chemical)
bonded with heat activation if desired. Hydrophobic Benzoate Plasticizer 14.71
The present invention is further illustrated by the follow (Benzo?ex 50)
ing nonlimiting examples. All parts are by weight unless Vinyl acetate ethylene copolymer 9.52 9.04
otherwise speci?ed. 25 emulsion (Air?ex 320, Air Products
Inc.)
Polyisocyanate crosslinker 5.00 5.00
EXAMPLES (Desmondur DA, Miles Inc.)
Test Results
In the following examples the following test methods
Test 1 (kg/cm) 3.24 2.93 2.40 2.69
were used 46 79 60 101
Test 2 (°c.)

Test 1. Peel Adhesion (Non-porous Substrates)

The samples for testing were prepared in the following EXAMPLES 5-7
manner. The adhesive formulations were coated on two 15.2 35
cm by 17.8 cm sheets of polyvinyl chloride (PVC) using a Formulations were prepared as shown in Table 2 below in
#40 Meyer rod. The substrates were then dried at room the same manner as described for Examples 1-4. Testing
temperature and pressed together using a Sentinal Heat was the same as for Examples 1-4 except that the Example
sealer at room temperature for 30 sec. at 206.8 kPa (30 psi) 7 formulation was also subjected to Test 3. described above.
nip pressure. After aging at ambient conditions for 72 hours. Test results are also given in Table 2. Example 5 is a
the sheets were cut into 2.5 cm by 17.8 cm strips and tested comparative formulation which does not include the hydro
for peel adhesion on the Wing Albert 500. phobic plasticizer component of the inventive formulations.

Test 2. Peel Adhesion Failure Temperatures (Porous TABLE 2

Substrates) 45 Example
The samples for testing were prepared and tested in the Comparative Invention
same manner as Test 1. except that the substrates used were
5 6 7
2.5 cm by 2.5 cm samples of canvas which were bonded in
a T-peel con?guration and placed in the Tenney oven. The 50 Hard Sulfonated Polyester 43.27 36.57 34.82
T-peels were subjected to a 25° C. increase in temperature Polyurethane (Dispercoll K-8464)
each hour until bond failure. and the temperatures and the (High M01. Wt. N0n—SrLlfonated 30.91 26.13 24.88
times were recorded by the Tenney sensing unit. Polyurethane (Neorez R-9630)
Soft Tacky Non-Sulfonated 14.54 12.29 11.70
Polyurethane (Neorez R-9320)
Test 3. Peel Adhesion (Mixed Non-porous 55 Hydrophobic Plasticizer (N-ethyl- — 15.49 14.76
toluene sulfonamide mixture
Substrates) Hydrophilic Plasticizer (Triacetin) -— — ——
Vinyl acetate ethylene copolymer 11.28 9.52 9.07
The samples for testing were prepared and tested in the emulsion (Air-?ex 320)
same manner as Test 1. except that one substrate was ABS Polyisocyanate crosslinker — — 4.77
(acrylonitrile-butadiene-styrene block copolymer) and the 60 (Desmondur DA)
other substrate was PVC. Bonds were assembled with a Test Results
pressure of 206.8 kPa (30 psi) 30 sec. at room temperature Test 1 (kg/cm) 0.11 3.24 2.93
and at 82° C. (180° F.). Bonded assemblies were prepared as Test 2 (°C.) 61 46 79
in Test 1 and tested for green strength promptly after Test 3 (kgcm) - Immediately
bonding and then after aging the bond for 3 weeks. 65 Room Temp 2.50
In the formulations described below. component quanti [82° C.] 0.95
ties are given in parts by weight.
 5 ,624,758
7 8
Carpet laminations were made on both the gel coat and the
TABLE 2-continued rough side of marine ?berglass. The coated substrates were
immediately joined with a 2.3 kg (5 lb) hand roller. 180° peel
Example tests were completed after aging of the resulting bonded
Comparative Invention assembly for 7 days at ambient conditions. The test instru
ment was a 3M90 peel tester run at 30 cc/min. 30 sec. peel.
5 6 7
Bonded and aged assemblies prepared in the same manner
Test 3 (kg/cm) - Aged 3 weeks as described in the previous paragraph were placed in 22° C.
water for 24 hours after which peel strengths were measured
Room Temp 1.72 in the same manner.
[82° C.] 091
In addition to the formulation of Example 8 with citric
acid coagulation. a competitive water based adhesive 3M
FastbondTM 2000 NF. spray-coagulated with FastbondTM
EXAMPLE 8 Zinc sulfate. and a commercial SBR solvent cement. spray
15
A formulation was prepared as in Example 1 using the applied. were tested in the same manner. It was noted that
following components: the diisocyanate crosslinker employed in the formulation of
Dispercoll K-8464 35.4 Example 8 could not be satisfactorily added to the Fastbond
2000 NF formulation because the pot-life was too short in
Neorez R-9630 25.3 the high pH system of that adhesive. Results are given in
Neorez R-9320 11.9 20
Table 3 where all values are kg/cm.
Uniplex 108 15.0
TABLE 3
Desmondur DA 5.0 Dry Wet
The adhesive was applied with a paint brush to chrome 25
leather. SBR rubber sheet and suede leather samples and Rough Gel Coat Rough
Product Gel Coat Side Side Side Side
allowed to dry. Contact bonds were formed at room tem
perature with hand pressure between adhesive coated Example 8 2.1 1.4 2.1 1.0
samples of chrome leather and SBR sheet and between SBR solvent cement 0.8 1.0 0.7 0.1
adhesive coated SBR rubber sheet and suede leather. When 3M Fastbond 2000 0.9 0.5 0.9 0.2
NF
pulled apart. both samples failed by substrate failure of the
leather substrate indicating that the adhesive bond was
stronger than the substrate. and demonstrating the utility of What is claimed is:
the adhesive as a cold contact shoe adhesive. 1. A bonded assembly comprising a pair of substrates
The same adhesive was applied with a paint brush to 35 adhesively bonded wherein as is adhesive is a dried or
ponderosa pine blocks 7.5 cm ><7.5 cm square. allowed to coagulated disperson of an adhesive dispersion. said adhe
dry for 10~l5 minutes and then contact bonded with hand sive dispersion comprising a:
pressure at room temperature. The samples produced imme a) at least one hydrophobic plasticizer. and
diate strength which could not be broken by hand shear or b) a blended mixture of dispersed polymers. the mixture
torsion forces. When pried apart with a hammer and chisel 40 comprising:
the bond broke by wood failure. demonstrating the utility of 1) at least one hard sulfonated polyester urethane;
the adhesive as a cold contact wood adhesive. 2) at least one soft non-sulfonated polyester urethane;
and
EXAMPLE 9
3) at least one polar non-polyurethane water-based
An adhesive formulation as described in the previous 45 polymer or copolymer.
example was tested for carpet-to-?berglass (glass ?ber/ 2. An bonded assembly as in claim 1 wherein at least one
polyester laminate) wet and dry peel strength. The samples of said substrates is a member of the group consisting of
were prepared for testing by spray application to both leather. rubber. synthetic polymers and wood
surfaces at a dry spread rate of 54 g/m2 (5 g/ft2 ). The 3. Abonded assembly as in claim 1 wherein said assembly
adhesive were spray-coagulated (HYDROpHUSETM) with a 50 is a shoe.
Mattson Cross?rel"M spray gun using a dilute solution of
citric acid as the acid which is mixed in the spray process.
 UNITED STATES PATENT AND TRADEMARK OFFICE
CERTIFICATE OF CORRECTION
PATENT N0. : 5,624,758

DATED : APRIL 29, 1997

INVENTORiSi : Mike Maksymkiw, et al

It is certified that error appears in the above-identified patent and that said Letters Patent is
hereby corrected as shown below:

Col. 2, line 22, delete “titrates” and insert -- citrates -

Signed and Sealed this

Second Day of September, 1997

Anew: Zena W
BRUCE LEHMAN

Allt’Sflilig Officer Cmnmiminner nf'Pulvn/x 11ml Trudmnurkv