USOO7348378B2

(12) United States Patent (10) Patent No.: US 7,348,378 B2

MelancOn et al. (45) Date of Patent: Mar. 25, 2008

(54) ADHESIVE 4,162.238 A * 7, 1979 Bergna ....................... 524,442

4,471,082 A 9, 1984 Kwok et al. .................. 524/46
(75) Inventors: Kurt C. Melancon, White Bear Lake, 5,284,897 A 2f1994 Columbus et al.
MN (US); Mark E. Fagan, Woodbury 5,306,749 A 4, 1994 Columbus et al.
s s 5,322,880 A 6/1994 Columbus et al.
MNoodbury,
t s' P.William
; W IIIlam J.
J. Hunt
Hunt, 5,416,140
5,473,005 A
A 5/1995 Columbus et al.
12/1995 Columbus et al.
Afton, MN (US) RE35,144 E 1/1996 Columbus et al.
6.423,379 B1* 7/2002 Ewing ... ... 427,387
(73) Assignee: 3M Innovative Properties Company, 2003/0044535 A1* 3, 2003 Goobich ... 427/256
St. Paul, MN (US) 2003/0077429 A1 4/2003 Schulz ....................... 428,195
2003.0109620 A1 6/2003 Zecha et al.
(*) Notice: Subject to any disclaimer, the term of this 2003. O158324 A1 8, 2003 Maxim
patent is extended or adjusted under 35 2003/0163957 A1* 9, 2003 Chen ........................... 51.298
U.S.C. 154(b) by 78 days. 2004/OO11250 A1 1/2004 Calienni
2004/0039.095 A1 2/2004 Jiratumnukul
(21) Appl. No.: 10/884,302 2004f0072003 A1 4/2004 Choi et al.
(22) Filed: Jul.e 2,
a? 9
2004 FOREIGN PATENT DOCUMENTS
AU 8313818 10, 1983
(65) Prior Publication Data DE 3724331 2, 1989
EP 22550 1, 1981
US 2005/O13732O A1 Jun. 23, 2005 GB 2294 466 A 5, 1996
O O JP 56014558 2, 1981
Related U.S. Application Data WO WO 93,21279 10, 1993
(60) Provisional application No. 60/.530,591, filed on Dec.
18, 2003. * cited by examiner
Primary Examiner Ling-Sui Choi
(51) a'sA00 2006.O1 Assistant Examiner M. Bernshteyn
(52) U.S. Cl ( So 524/5O1: 442/174 (74) Attorney, Agent, or Firm Trisha D. Adamson
(58) Field of Classification Search .................. 524/46, (57) ABSTRACT
524/501, 36,563: 442/174
See application file for complete search history. An adhesive composition includes a polymer adhesive mate
(56) References Cited rial and a thickener. The adhesive composition has a string
ing length of 9 cm or less and a phase lag of 45 degrees or
U.S. PATENT DOCUMENTS less or a sag distance of 5 mm or less. The adhesive can be
3,011,985 A 12/1961 Breslouf et al.
formed by combining a vinyl acetate polymer, an alkali
3,072,482 A 1/1963 Beeber et al. Swellable thickener, an alkali material, and water.
3,309.328 A * 3/1967 Carroll et al. .............. 524/145
4,059,114. A 11/1977 Richards 37 Claims, 1 Drawing Sheet
U.S. Patent US 7,348,378 B2

<!- CN O

Fig. 1
 US 7,348,378 B2
1. 2
ADHESIVE FIG. 1 is a schematic view of an illustrative adhesive
dispenser.
CROSS-REFERENCE TO RELATED While the invention is amenable to various modifications
APPLICATIONS and alternative forms, specifics thereof have been shown by
way of example in the drawings and will be described in
This application claims priority from provisional U.S. detail. It should be understood, however, that the intention is
Application No. 60/530,591, filed Dec. 18, 2003 entitled not to limit the invention to the particular embodiments
CRAFT OBJECTS. described. On the contrary, the intention is to cover all
modifications, equivalents, and alternatives falling within
BACKGROUND 10 the spirit and scope of the invention.
This invention relates to improved adhesives. Specifi DETAILED DESCRIPTION
cally, the invention relates to improved adhesives that
exhibit improved dispensability properties. The present invention is believed to be applicable gener
Typical consumer adhesives or white glues are formulated 15 ally to adhesives and their manufacture, as well as apparatus
at 40 to 60 percent solids and have a viscosity ranging from for dispensing such improved adhesives. While the present
2,000 to 300,000 cp as measured by on a Brookfield invention is not so limited, an appreciation of various
viscometer. These adhesives or white glues have a variety of aspects of the invention will be gained through a discussion
shortcomings such as, for example, regardless of Viscosity, of the examples provided below.
the glues run or sag when applied to a vertical Surface. In For the following defined terms, these definitions shall be
addition, these glues suffer from imprecise dispensability. applied, unless a different definition is given in the claims or
Low viscosity glues are excessively runny and high viscos elsewhere in this specification.
ity glues are excessively stringy. The term “polymer will be understood to include poly
In general, the more viscous glues tend to be slow to “set” mers, copolymers (e.g., polymers formed using two or more
and are difficult to obtain in thin sections since they do not 25 different monomers), oligomers and combinations thereof,
spread easily under modest stress. Thick glue sections can be as well as polymers, oligomers, or copolymers that can be
undesirable since upon drying, they exacerbate curl and formed in a miscible blend by, for example, coextrusion or
cockle effects in paper substrates. Thus, there is a need for reaction, including transesterification. Both block and ran
an improved adhesive. dom copolymers are included, unless indicated otherwise.
30 Unless otherwise indicated, all numbers expressing quan
SUMMARY tities of ingredients, properties such as molecular weight,
reaction conditions, and so forth used in the specification
Generally, the present invention relates to improved adhe and claims are to be understood as being modified in all
sives, their manufacture, and apparatus for dispensing the instances by the term “about.” Accordingly, unless indicated
35 to the contrary, the numerical parameters set forth in the
improved adhesive. In an illustrative embodiment, an adhe foregoing specification and attached claims are approxima
sive composition includes a polymer adhesive material and tions that can vary depending upon the desired properties
a thickener. The adhesive composition has a stringing length sought to be obtained by those skilled in the art utilizing the
of 9 cm or less and a phase lag, Ö, (hereinafter referred to as teachings of the present invention. At the very least, and not
“phase lag) of 45 degrees or less, or a sag distance of 5 mm 40 as an attempt to limit the application of the doctrine of
or less. The adhesive can be formed by combining a vinyl equivalents to the scope of the claims, each numerical
acetate polymer, an alkali Swellable thickener, an alkali parameter should at least be construed in light of the number
material, and water. of reported significant digits and by applying ordinary
In another illustrative embodiment, an article includes a rounding techniques. Notwithstanding that the numerical
dispenser container having a dispensing opening and an 45 ranges and parameters setting forth the broad scope of the
adhesive composition disposed within the dispenser con invention are approximations, the numerical values set forth
tainer. The adhesive composition includes a polymer adhe in the specific examples are reported as precisely as possible.
sive material and a thickener. The adhesive composition has Any numerical value, however, inherently contains certain
a stringing length of 9 cm or less and a phase lag of 45 errors necessarily resulting from the standard deviations
degrees or less. 50 found in their respective testing measurements.
In another illustrative embodiment, an adhesive compo Weight percent, percent by weight, % by weight, and the
sition includes a vinyl acetate polymer, an alkali Swellable like are synonyms that refer to the concentration of a
thickener, and water. The vinyl acetate polymer is dispersed substance as the weight of that substance divided by the
within the water and the adhesive composition has a pH of weight of the composition and multiplied by 100.
4 to 10. 55 The recitation of numerical ranges by endpoints includes
The above summary of the present invention is not all numbers subsumed within that range (e.g. 1 to 5 includes
intended to describe each disclosed embodiment or every 1, 1.5, 2, 2.75, 3, 3.80, 4, and 5).
implementation of the present invention. The Figures, As used in this specification and the appended claims, the
Detailed Description and Examples which follow more singular forms “a”, “an', and “the include plural referents
particularly exemplify these embodiments. 60 unless the content clearly dictates otherwise. Thus, for
example, reference to a composition containing “a com
BRIEF DESCRIPTION OF THE DRAWINGS pound includes a mixture of two or more compounds. As
used in this specification and the appended claims, the term
The invention may be more completely understood in “or is generally employed in its sense including “and/or
consideration of the following detailed description of vari 65 unless the content clearly dictates otherwise.
ous embodiments of the invention in connection with the The present invention provides an improved adhesive.
accompanying drawings, in which: The improved adhesive includes a polymer adhesive mate
 US 7,348,378 B2
3 4
rial, and a thickener. The improved adhesive has two or more embodiments the adhesive composition can be considered as
of the following physical properties: a limited Stringing being “acid-free” and have a pH of 7 to 9. In some
length; a limited phase lag; a limited sag distance; a viscosity embodiments, an alkali or alkaline material can be added to
such that the adhesive is flowable; a limited set time; a range the adhesive composition in any useful amount.
of complex shear modulus; and the adhesive composition Vinyl acetate polymers include, for example, vinyl acetate
may not be thixotropic. Many of these properties can be homopolymers and vinyl acetate co-polymers such as, for
determined by the methods set in the Methods section below. example, vinyl acetate-ethylene (VAE). These vinyl acetate
The adhesive composition can have a limited Stringing polymers can be combined in water to form a polymer
length. Stringing length of an adhesive can be determined by dispersion. Vinyl acetate based polymers can be obtained by
the stringing length method defined in the Methods section 10 conventional emulsion polymerization and are commer
below. A limited Stringing length can aid in precise place cially available from a variety of sources.
ment of flowable adhesives. In some embodiments, the One or more co-monomers can be co-polymerized with
adhesive composition can have a stringing length of 0 to 9 vinyl acetate. In some embodiments, the vinyl acetate poly
cm, or 0 to 5 cm, 0 to 3 cm, or 0 to 2 cm. mer includes vinyl acetate, ethylene, and optionally one or
The adhesive composition can have a limited shear modu 15 more other ethylenically unsaturated monomers. Illustrative
lus phase lag. Shear modulus phase lag or “phase lag.” can examples of other ethylenically unsaturated monomers are
be determined by the phase lag method defined in the Cs-Co alkenoic acids, such as acrylic acid, methacrylic
Methods section below. In some embodiments, the adhesive acid, crotonic acid and isocrotonic acid and their esters with
composition can have a phase lag of 0 to 45 degrees, or 0 to C-Cls alkanols, such as methanol, ethanol, propanol,
30 degrees, or 0 to 20 degrees. butanol, and 2-ethylhexanol; vinyl halides, such as vinyl
The adhesive composition can have a limited sag distance chloride; alpha, beta-unsaturated C-C alkenedioic acids
when placed on a vertical Surface. Sag distance or sag Such as maleic acid, fumaric acid, and itaconic acid and their
resistance can be determined by the sag distance method monoesters and diesters with the same C-C alkanols; and
defined in the Methods section below. A limited sag distance nitrogen containing monoolefinically unsaturated mono
can aid in keeping adhesive on a surface where it is placed. 25 mers, such as nitriles; arnides; N-methylol amides; lower
In some embodiments, the adhesive composition can have a alkanoic acid ethers of N-methylol amides and allylcarbam
sag distance of 0 to 10 mm, or 0 to 5 mm, or 0 to 2 mm. ates, such as acrylonitrile, acrylanide, methacrylamide,
The adhesive composition can have a viscosity Such that N-methylol acrylamide, N-methylol methacrylamide,
the adhesive is flowable. Viscosity can be determined via a N-methylol allylcarbamate, and lower alkyl ethers or lower
Brookfield RVT with a #6 spindle at 20 rpm at ambient 30 alkanoic acid esters of N-methylol acrylamide, N-methylol
conditions. In some embodiments, the adhesive composition methacrylamide and N-methylol allylcarbamate. Illustrative
can have a viscosity of 3,000 to 50,000 cP, or 3,000 to vinyl acetate-ethylene (emulsion) polymers used in this
30,000 cP, or 10,000 to 30,000 cP. invention are commercially available products. Examples
The adhesive composition can have a limited set time. Set are AIRFLEXTM 320, AIRFLEXTM 323, AIRFLEXTM 400,
time of the adhesive can be determined by the set time 35 AIRFLEXTM 400H, AIRFLEXTM 401, AIRFLEXTM 405,
method defined in the Methods section below. In some AIRFLEXTM 410, AIRFLEXTM 420, AIRFLEXTM 423, AIR
embodiments, the adhesive composition can have a set time FLEXTM 426, AIRFLEXTM 460, AIRFLEXTM 465, AIR
of 0 to 180 seconds, or 0 to 60 seconds, or 0 to 45 seconds. FLEXTM 7200, AIRFLEXTM 920, AIRFLEXTM EN421,
The adhesive composition can have a range of complex AIRFLEXTM EP17, AIRFLEXTM 315, AIRFLEXTM 418,
shear modulus G*. Complex shear modulus G* can be 40 AIRFLEXTM EF350, and AIRFLEXTM EF940, all available
determined by the complex shear modulus method defined from Air Products Polymers, L.P., (Allentown, Pa.) and
in the Methods section below. In some embodiments, the ELVACETM 722, ELVACETM 725, ELVACETM 731,
adhesive composition can have a complex shear modulus G* ELVACETM 732, ELVACETM 733, ELVACETM 734,
of 50 to 1000 Pa, or 100 to 600 Pa. ELVACETM 735, ELVACE TM 736, ELVACETM 737,
In some embodiments, the adhesive composition includes 45 ELVACETM 739, ELVACETM 741, and ELVACETM 758
a polymer adhesive material and a thickener where the available from Forbo Adhesives, LLC (Durham, N.C.) and
adhesive composition has a stringing length of 9 cm or less DUR-O-SETTM E-200, DUR-O-SETTM E-200, DUR-O-
and a phase lag of 45 degrees or less. In another embodi SETTM E-230, DUR-O-SETTM E-130, DUR-O-SETTM
ment, the adhesive composition includes a polymer adhesive E-200HV, DUR-O-SETTM E-150, DUR-O-SETTM E-260,
material and a thickener where the adhesive composition has 50 DUR-O-SETTM E-100, DUR-O-SETTM E-220, DUR-O-
a stringing length of 9 cm or less and a sag distance of 10 SETTM E-171HS, DUR-O-SETTM C-325, DUR-O-SETTM
mm or less. In other embodiments, two or more of the above C-310, DUR-O-SETTM C-335, RESYNTM 1025, RESYNTM
identified physical properties can be combined, as desired. 1072, RESYNTM 1601, and RESYNTTM SB-321 available
The improved adhesive composition can be formed by from Vinamul Polymers, (Enoree, S.C.) and WB-3621,
combining an adhesive polymer, a thickener, and water. The 55 WB-3621 available from H.B. Fuller Co. (St Paul, Minn.).
adhesive polymer can be a vinyl acetate polymer. The Commercially available vinyl acetate polymers, as provided,
thickener can be an alkali swellable thickener. In some typically can have a viscosity ranging from 500 to 3000 cp.
embodiments, the adhesive composition can have a glass Vinyl acetate polymers can be present in the adhesive
transition temperature in a range of -60 to 100 degrees compositions in any useful amount. In some embodiments,
Celsius; or, -50 to 50 degrees Celsius, -20 to 30 degrees 60 vinyl acetate polymers are present in the adhesive compo
Celsius. As used herein, glass transition temperatures of the sition from 5 to 75 wt %, or from 20 to 75 wt %, or 50 to
adhesive composition are taken from dried adhesive com 75 wt %, as desired.
positions. In illustrative embodiments, the adhesive compo Alkali swellable thickeners include alkali Swellable
sition can have a total solids content from 5 to 85 wt %, or acrylic thickeners. These acrylic thickeners can be termed an
30 to 85 wt %, or 60 to 80 wt %, as desired. 65 “associative thickener” and can be anionic alkali Swellable
In some illustrative embodiments, the adhesive composi acrylic aqueous emulsion copolymers containing carboxylic
tion can have a pH of 4 to 10, or 5 to 10, or 6 to 9. In other acid groups. These alkali swellable thickeners can be sub
 US 7,348,378 B2
5 6
stantially cross-linked. A partial listing of Suitable alkali (as described above): a limited Stringing length; a limited
swellable acrylic thickeners includes those commercially phase lag; a limited sag distance; a viscosity Such that the
available under the trade name RhoplexTM ASE-60, from adhesive is flowable; a limited set time; a range of complex
Rohm and Haas Co. (Philadelphia, Pa.) and RohagitTM SD shear modulus; and the adhesive composition may not be
15 available from Polymer Latex GmbH & Co. KG, (Marl, thixotropic.
Del.) and CarbopolTM and PemulenTM series thickeners from FIG. 1 shows an illustrative adhesive dispenser 100 that
Noveon, Inc (Cleveland, Ohio). can hold and dispense the improved adhesive described
Alkali swellable thickeners can be present in the adhesive herein. The dispenser 100 can include an adhesive contain
compositions in any useful amount. In some embodiments, ing portion 120 that contains the adhesive prior to being
Alkali swellable thickeners are present in the adhesive 10
dispensed. In some embodiments, the containing portion
composition from 0.1 to 10 wt %, or from 0.1 to 5 wt %, or
0.1 to 3 wt %, as desired. 120 is formed of a flexible material such as a polymeric
An alkali material or alkalinity source can be combined material. The dispenser can contain any useful amount of
with the alkali swellable thickener during the formation of adhesive such as, for example, 0.5 to 5000 ml, or 0.5 to 1000
the adhesive composition. The alkalinity source can be a 15 ml, or 50 to 500 ml. The dispenser 100 can include a
strong base material or a source of alkalinity which can be dispensing portion 130 disposed on the containing portion
an organic source or an inorganic source of alkalinity. For 120. The dispensing portion 130 can include a dispenser
the purposes of this invention, a source of alkalinity also opening 140. In one embodiment, adhesive can be dispensed
known as an alkali material is a composition that can be by a user by the user applying finger pressure to the flexible
added to an aqueous system and result in a pH greater than containing portion 120 which urges adhesive material
about 7. Organic sources of alkalinity are often strong toward and through the dispenser opening 140 to the appli
nitrogen bases including, for example, ammonia, monoet cation target. In some embodiments, the dispenser opening
hanol amine, monopropanol amine, diethanol amine, dipro 140 has an area in a range of 0.05 to 40 mm, 0.1 to 30 mm,
panol amine, triethanol amine, tripropanol amine, etc. The 0.1 to 10 mm, 0.2 to 1.8 mm, 0.5 to 1.5 mm, or 0.75 to
Source of alkalinity can also comprise an inorganic alkali. 25 1.25 mm, as desired.
The inorganic alkali can be derived from Sodium or potas Described herein are adhesive compositions exhibiting a
sium hydroxide which can be used in both liquid (about unique combination of rheology and fast set time, and when
10-60 wt % aqueous solution) or in solid (powder, flake or applied to paper Substrates, can reduce the amount of
pellet) form. Other inorganic alkalinity sources are soluble curl/cockle observed. These adhesive compositions are eas
silicate compositions such as sodium metasilicate or soluble 30
ily and precisely dispensed from a fine tipped applicator
phosphate compositions such as trisodium phosphate, or any using only hand pressure to apply. Such adhesive/dispenser
other buffer derived from phosphoric acid. Exemplary alka combinations are often used in performing craft projects,
linity Sources include ammonia, or triethanol amine. The household repairs, or scrapbooking activities.
alkalinity source can include an alkali metal carbonate. The combination of adhesive rheology and fine tipped
Alkali metal carbonates which may be used include sodium 35
dispensers provides excellent control during adhesive dis
carbonate, potassium carbonate, sodium or potassium bicar pensing and allows the user to effortlessly apply the adhesive
bonate or sesquicarbonate, among others. The alkalimaterial in any shape desired (fine or coarse dots, streaks, lines, etc).
can be provided in the adhesive composition in any useful The adhesive rheology can also assist in the creation of thin
amount.
The adhesive compositions of the invention can option 40 bond lines due to the ease with which the adhesive spreads
ally include fillers. Fillers can be organic or inorganic fillers when compressed lightly between adherents with modest
and can be present in the adhesive in any useful amount. lamination pressure, e.g., light hand pressure used to lami
Fillers can be any organic or inorganic additives such as, for nate paper card stock together. Such thin adhesive bond lines
example, antioxidants, stabilizers, antioZonants, plasticizers, can also contribute to fast adhesive drying since the thin
cross-sectional area of the adhesive increases the rate at
dyes, U.V. absorbers, HALS, and pigments. In one embodi 45
which moisture is removed from the adhesive. In addition
ment, the adhesive composition includes a "glitter” material the rheology provided by associative thickened adhesive
as a filler. The glitter material can add sparkle and/or color polymers described herein also minimizes/eliminates the
to the adhesive as desired. The adhesive compositions of the tendency of the adhesive to string or leg when applied in
invention can optionally include colorants, such as pigments Small drops or in a fine continuous bead, thus allowing more
or dyes, to provide a tint or color to the adhesive composi 50
precise application of the adhesive.
tion.
In Some embodiments, the adhesive composition can Advantages of the invention are illustrated by the follow
include 5 to 75 wt % vinyl acetate polymer, 0.1 to 10 wt % ing examples. However, the particular materials and
alkali swellable thickener, and a balance water. In other amounts thereof recited in these examples, as well as other
embodiments, the adhesive composition can include 20 to 55 conditions and details, are to be interpreted to apply broadly
75 wt % vinyl acetate polymer, 0.1 to 5 wt % alkali swellable in the art and should not be construed to unduly limit the
thickener, and a balance water. In other embodiments, the invention.
adhesive composition can include 50 to 75 wt % vinyl
acetate polymer, 0.1 to 3 wt % alkali swellable thickener, Methods
and a balance water. In some of these embodiments, the 60
formation of the adhesive composition can include the Set Time
addition of an alkali material that may activate or swell the
alkali swellable thickener material and provide a resulting This test involves the following steps:
adhesive composition that can have a pH of 7 to 9. In 1. Coat a stripe (5-10 cm wide) of adhesive (-3 grams) onto
illustrative embodiments, the alkali swellable thickener 65 a first sheet of test paper (6" wide IP Thilmany 50H
material is substantially cross-linked. These embodiments Bleached Andro Base Paper) to obtain a 0.23 mm thick
can possess two or more of the following physical properties wet adhesive coating:
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7 8
2. While adhesive is wet, laminate a second sheet of the test The polycarbonate sleeve is used as a draft eliminator to
paper, which has been pre-cut into 0.5" width strips, to the reduce the effect of any air motion on the falling strand of
first sheet of test paper; adhesive. The sleeve is placed on the jack such that it is
3. Laminate the two sheets together by rolling with a 4.5 lb concentric with the circumference of the needle barrel. Two
rubber roller; and longitudinal slots are required on the sleeve to allow the
4. Peel the 0.5" width paper strips from the laminate at sleeve to pass by the small clamp and the flexible tubing as
regular time intervals to determine how long it takes to the lab jack is raised or lowered.
develop Sufficient strength to tear the test paper strip. The needle was shortened, using a die grinder fit with
Sag Resistance or Distance 10 cut-off wheel, to provide a square end on the barrel of the
Adhesive sag resistance is assessed by depositing a 0.1 ml needle and a length of 6.4 mm, i.e., 6.4 mm of needle
drop of adhesive near an end of a horizontally positioned 2 protruded from the hub. The shortened needle barrel was
mil clean thick strip of poly(ethylene terephthalate) (PET) deburred with 320 grit sandpaper. The square-ended needle
film measuring ~15 cmx25 cm. barrel allows uniform discharge of the adhesive from the
Immediately following adhesive deposition, the PET film 15 needle and minimizes any tendency for the extruded adhe
is positioned vertically, with the adhesive drop located at the sive to drag or distort upon exiting the needle.
top of sheet, which allows the adhesive to flow downward
along the length of the film strip. Testing Procedure
When adhesive flow has ceased, the distance, in millime The adhesive is free of bubbles prior to performing this
ters (mm), the adhesive has flowed is measured and test. The syringe is filled with adhesive by immersing the
recorded. The specific distance measured is that distance Syringe tip into the adhesive and gently withdrawing the
from the bottom edge of the original adhesive drop, prior to plunger to fill the Syringe. Care must be taken during this
orienting vertically, to the bottom most edge of the adhesive operation to avoid introducing air into the adhesive as this
flow once the adhesive flow has ceased.
deleteriously affects the test outcome, i.e., air bubbles in the
Stringing Length 25 discharged adhesive can cause flaws in the stream that result
This test method provides a means of assessing the extent in premature breakage of the falling stream. The filled
to which an adhesive strings when dispensed. In general the syringe is fit with the flexible connection tube and needle,
test method involves dispensing glue through a vertically and mounted in the Syringe pump. The pump is started to
oriented Syringe needle at fixed rate, and measuring the provide an adhesive flow of 1.75 milliliters/minute (ml/min).
length of the glue fiber/strand that forms as the glue extends 30
The syringe needle is initially held by hand and oriented to
from the needle and falls to a stage below. discharge straight upward in order to purge any air from the
The longer the strand the higher the extent of stringing, flexible line, connections, or needle.
the shorter the strand the lower the extent of stringing. This
test method is conducted in a constant temperature room When a bubble free adhesive stream is observed exiting
having temperature of 22°C. and a relative humidity of 50% 35 the needle the pump is stopped, the needle orientation
and employs the following equipment. reversed (to discharge straight down), the needle clamped in
1. Syringe pump, catalog # 55-2226, Harvard Apparatus. So position for testing, and the jack and cylindrical sleeve
Natick, Mass. 01760 placed as described above.
2. 16 gax38 mm PrecisionGlideTM Needle 16G 1/2 dispos To run the test the stage is positioned at a distance of 2.5
able syringe needle, 1.19 mm ID, Becton Dickinson & 40
cm from the needle tip, the pump started, and the adhesive
Co, Franklin Lakes, N.J. 07417-1884 stream observed. If the adhesive stream is stable and con
3. 10 ml Luer Norm-Ject disposable syringe, Henke Sass tinuous the stage is slowly lowered in 1 cm increments, with
Wolf GMBH, Tuttlingen, Germany a 5 second observation time required at each height, until the
4. Teflon tubing 3.2 mm IDX 152 mm length fit with male/ stream breaks. The stage is then raised until the flow
female Luer connections on opposite ends to provide a 45
reconnects to provide a continuous stream. The stage is
flexible connection between the syringe and the needle lowered in steps to the point at which the stream breaks-off,
. Laboratory jack and the distance at which a continuous flow occurred is
. Laboratory jack stand recorded (i.e., that distance from the needle tip to the stage).
. Small laboratory clamp
. Cylindrical sleeve constructed from 0.45 mm thick clear 50 This protocol is repeated 2 more times to obtain a total of
polycarbonate ~14 cm diax38 cm tall and slotted appro 3 separate measurements of the maximum distance at which
priately to allow clearance for clamp and Teflon tubing a continuous strand could be observed. If upon starting the
clearance. test the stream is discontinuous, the stage is raised to a point
at which the flow connects to provide a continuous stream
Equipment Preparation and Layout 55 and the protocol described above followed to complete the
The Syringe/tubing/needle assembly is arranged with the test. For certain adhesives, during the course of the test, the
Syringe mounted horizontally in the Syringe pump and dispensed adhesive collecting on the stage may tend to pile
needle oriented vertically, such that the extruded adhesive up, thus when recording the maximum distance at which a
discharges Straight downward from the needle tip. continuous flow occurred, any buildup on the stage must be
The small clamp is affixed to the vertical member of the 60 taken into account, i.e., the build-up distance (the height
jack stand and the needle is secured with the clamp to from the stage to the top of the adhesive pile) subtracted
maintain orientation during the test. The lab jack is placed on from the overall measured distance. The average of the three
the jack stand below the needle to provide a movable stage measurements is recorded as the “Continuous Fiber String
onto which the flowing adhesive impinges. The range of lab ing Length” and reported in centimeter units. If the test is not
jack motion is ~38 cm total, i.e., the jack can be elevated to 65 completed with a unitary syringe filling, the test can be
touch the tip of the needle and can be lowered 38 cm below restarted with another syringe filling at the preceding stage
the tip of the needle. height and run to completion.
 US 7,348,378 B2
9 10
Shear Modulus (Phase Lag “6” and Complex Shear Modulus LaponiteTM RD, synthetic layered silicate, Southern Clay
“G*) Products, Inc., Gonzales, Tex.
Dynamic mechanical properties of the samples were General Preparation Procedure
measured with a Bohlin CVO 120 HR NF rheometer. Bohlin
rheometers are available from Malvern Instruments Ltd., The inventive adhesive examples described herein typi
Enigma Business Park, Grovewood Road, Malvern, Worces cally consist of an adhesive polymer, associative thickener,
tershire, United Kingdom, WR14 1XZ. All measurements water, and base. Such samples are prepared by combining
were taken using the Bohlin C25 Mooney-Couette geometry the adhesive polymer, thickener, and water in a vessel and
at 25 degrees Celsius. A trap was placed over the top of the mixing well with a motor driven marine propeller to obtain
C25 cup to retard sample drying. Evaporation traps are 10 a uniform composition. With continued stirring the base is
available from Malvern Instruments. added in a single charge and agitation continued until the
The dynamic mechanical properties of interest are the adhesive composition is well mixed.
complex shear modulus, G, and the phase lag, which is also
Sometimes called phase shift. These two parameters are Examples 1, 2, 3, 5, 6, 7, 8
often used to describe the relationship between stress and 15
strain for materials, and in particular for Viscoelastic mate These Examples were prepared by the foregoing proce
rials. Materials with high moduli provide greater resistance dure and consisted of the materials and quantities (in grams)
to an applied stress, resulting in Smaller strains, than those shown in Table 1. The resulting adhesives were character
with low moduli. The phase lag is, by definition, bounded ized for Brookfield Viscosity, set time, Stringing, and rheol
between Zero and 90 degrees and represents the relative ogy according to the test methods set forth above. The
levels of elastic and Viscous response of the sample to the results are reported in Table 4.
applied stress. Purely elastic (i.e., Hookean) materials have
a Zero degree phase lag and purely viscous materials have a TABLE 1.
90 degree phase lag relative to the oscillatory stress. Adhe
25
G* and 8 were measured by loading 17 grams of each sive RhoplexTM NHOH
sample into the rheometer. The samples were equilibrated to Sample Adhesive Amount ASE-60 Water (ml)
25°C., sheared for 30 seconds at 50s", and then allowed Example 1 Airflex TM 7200 2OO 2.0 0.7
to rest for 30 seconds before each test was run. Sinusoidally Example 2 Airflex TM 465 2OO 2.5 0.7
oscillating stresses were applied to each sample at a fre Example
30 Example
3 Elvace TM 737 2OO 3.5 1.1
quency of 1 Hz. Ten stress amplitudes, increasing logarith 5 Airflex TM 7200 1OO O.S O3S
Example 6 Airflex TM 7200 1OO 4.63 45 O.S1
mically from 0.1 Pa to 100 Pa, were chosen as test condi Example 7 AirflexTM 7200 11.9 15 150 1.3
tions. The values of G* and 8 at 1.7 Pa recorded by the Example 8 Airflex TM 7200 61.2 15 150 1.3
instrument are used here.

EXAMPLES 35
Example 4
Materials
AirflexTM 7200, VAE copolymer emulsion provided at A sample of ElvaceTM 737 was neutralized as follows. To
175 parts ElvaceTM 737 being agitated with a mechanical
-72.5% solids, pH 4.5-5.5, Tg 0° C., Air Products Poly 40
stirrer was added 0.56 ml NHOH. The pH of the well mixed
mers, L.P., Allentown, Pa. solution was 7.63, as measured by a pH meter. To 100 parts
AirflexTM 465, VAE copolymer emulsion provided at -67% of neutralized ElvaceTM 737 being agitated with a mechani
solids, pH 4.5-5.5, Air Products Polymers, L.P., Allen cal stirrer was added 2.67 parts RhoplexTM ASE-60. After
town, Pa. mixing well an additional 0.25 parts NH-OH solution was
ElvaceTM 737, VAE copolymer emulsion provided at 45
added and mixed in well to complete the preparation of
67-70% solids, pH 4-5, Forbo Adhesives, LLC, Durham, Example 4 and provide an adhesive having pH of 7.12.
N.C. RhoplexTM ASE-60, alkali swellable associative Example 4 was characterized for Brookfield viscosity, set
thickener supplied at 28% solids, Rohm and Haas Co., time, stringing, and rheology. The results are reported in
Philadelphia, Pa. Table 4.
Ammonium hydroxide, 28-30% NH3, EM Science, Gibb 50
stown, N.J. Comparative Examples C4, C5, C6, C7
Aleene's Fast Grab Tacky GlueTM, Duncan Enterprises,
Fresno, Calif. This series of comparative examples consisted of com
Aleene's Original Tacky GlueTM, Duncan Enterprises, 55 mon commercially available consumer white glues listed in
Fresno, Calif. Table 2. These Examples were characterized for Brookfield
Aleene's Quick Dry Tacky GlueTM, Duncan Enterprises, Viscosity, set time, stringing, and rheology. The results are
Fresno, Calif. reported in Table 4.
Elmer's Glue-AllTM, Elmer's Products, Inc., Columbus,
Ohio. 60 TABLE 2
KelzanTMS, Xanthan gum, lot 40863A, CP Kelco U.S., Inc., Example Adhesive
San Diego, Calif.
Sodium carboxymethylcellulose (Na CMC), type 7H4XF, C4 Aleene's Fast Grab Tacky Glue TM
lot 83724, Aqualon Division of Hercules Inc., Wilming C5 Aleene's Original Tacky Glue TM
C6 Aleene's Quick Dry Tacky Glue TM
ton, Del. 65 C7 Elmer's Glue-AITM
KelginTMMDH, sodium alginate, lot 281211, ISP Technolo
gies Inc., San Diego, Calif.
 US 7,348,378 B2
11 12
Comparative Examples C8, C9, C10, C11 We claim:
1. An adhesive composition consisting of
This series of Comparative Examples employ as the a vinyl acetate-ethylene copolymer;
adhesive neutralized ElvaceTM 737 from Example 4. The an alkali Swellable thickener;
adhesive, thickeners, and amounts of each are provided in 5 water, and
Table 3. Samples were prepared by adding the thickener a source of alkalinity;
charge slowly to ElvaceTM 737 that was agitated with a wherein the vinyl acetate-ethylene copolymer is dispersed
mechanical stirrer and mixed for 15 minutes until the within the water and the adhesive composition has a pH
additive was well incorporated. After standing for 24 hr of 4 to 10; and wherein the adhesive composition has
Some of the samples appeared to contain Small gel particles 10 a stringing length of 9 cm or less, a set time of 180
that could possibly be attributed to thickener that was either seconds or less, and one or more of the following
Swollen or not completely dispersed initially. Each sample properties:
was mixed again for 15 minutes at which time all samples a phase lag of 45 degrees or less;
appeared very Smooth. Samples were additionally assessed a viscosity of 3,000 to 50,000 cF:
for uniformity on a fineness of grind gauge (Precision Gage 15
& Tool Co., Dayton, Ohio) which showed all to be smooth, a complex shear modulus of 50 to 1000 Pa; and
uniform, and free of particulate. At this time some of the a Sag distance of 10 mm or less.
samples had an additional charge of ElvaceTM 737 added to 2. Aadhesive composition according to claim 1, wherein
them and mixed in well as shown in Table 4. These the Vinyl acetate-ethylene copolymer is present in the adhe
Examples were characterized for Brookfield viscosity, set 20 sive composition at 5 to 75 Wt 90.
time, stringing, and rheology. The results are reported in 3. An adhesive composition according to claim 2, wherein
Table 4. the alkali swellable thickener is present in the adhesive
composition at 0.1 to 10 wt %.
TABLE 3 4. An adhesive composition according to claim 1, wherein
25 the vinyl acetate-ethylene copolymer is present in the adhe
Comparative Elvace TM Thickener Additional sive composition at 20 to 75 wt %.
Example 737 Type Thickener Elvace TM 737
5. An adhesive composition according to claim 4, wherein
C8 100 Kelzan TMS O.38 the alkali swellable thickener is present in the adhesive
C9
C10
100
100
Na CMC
Kelgin TM MDH
O.31
O.17
24
30.8
composition at 0.1 to 5 wt %.
C11 100 Laponite TM RD OSO 71.8 30 6. An adhesive composition according to claim 1, wherein
the vinyl acetate-ethylene copolymer is present in the adhe
sive composition at 50 to 75 wt %.
TABLE 4
Shear Modulus’
Brookfield Continuous Fiber Sag Distance G*, Pa. 8, deg
Example Viscosity', cP Set Time, S Stringing Length, cm l 1 Hz, 1.7 Pa. 1 Hz, 1.7 Pa
1 3OOOO 48 2 2 S42 13
2 23SOO 45 1 4 401 12
3 23SOO 48 2 9 264 18
C1 3500 38 1 61 9 63
C2 2SOO 35 1 71 9 63
C3 3OOO 38 1 73 5 67
4 37000 58 9 3 896 16
5 8750 57 3 9 163 17
6 147SO 72 2 O 490 11
7 10750 >240 2 5 270 8
8 13OOO 73 2 4 341 9
C4 195OOO 68 too visc to measure 22 705 77
C5 41SOO 85 27 33 192 82
C6 8SOO 63 5 68 34 8O
C7 6OOO 105 2 115 29 88
C8 222SO 48 15 6 157 22
C9 25500 42 11 3 249 22
C10 23750 53 12 6 314 24
C11 11SOO 45 10 O 194 15

'data taken with Brookfield RVT, spindle #6, 20 rpm, except C4 measured at 5 rpm

The complete disclosure of all patents, patent documents, 7. An adhesive composition according to claim 6, wherein
and publications cited herein are incorporated be reference. 60 the alkali swellable thickener is present in the adhesive
The foregoing detailed description and examples have been composition at 0.1 to 3 wt %.
given for clarity of understanding only. No unnecessary 8. An adhesive composition according to claim 1, wherein
limitations are to be understood therefrom. The invention is the alkali swellable thickener is an anionic alkali Swellable
not limited to the exact details shown and described, for as acrylic thickener.
variations obvious to one skilled in the art will be included 9. An adhesive composition according to claim 1, wherein
within the invention defined by the claims. the composition has a total solids content of 5 to 85%.
 US 7,348,378 B2
13 14
10. An adhesive composition according to claim 1, 26. An adhesive composition according to claim 18,
wherein the composition has a total solids content of 30 to wherein the composition has a total solids content of 5 to
85%. 85%.
11. An adhesive composition according to claim 1, 27. An adhesive composition according to claim 18,
wherein the composition has a total solids content of 60 to wherein the composition has a total solids content of 30 to
80%. 85%.
12. An adhesive composition according to claim 1,
wherein the adhesive composition has a phase lag of 30 28. An adhesive composition according to claim 18,
degrees or less. wherein the composition has a total solids content of 60 to
13. An adhesive composition according to claim 7. 10 80%.
wherein the adhesive composition has a phase lag of 20 29. An adhesive composition according to claim 18,
degrees or less. wherein the adhesive composition has a phase lag of 30
14. An adhesive composition according to claim 1, degrees or less.
wherein the adhesive composition has a sag distance of 2 30. An adhesive composition according to claim 18,
mm or less. 15
15. An adhesive composition according to claim 1, wherein the adhesive composition has a phase lag of 20
degrees or less.
wherein the adhesive composition has a sag distance of 5 31. An adhesive composition according to claim 18,
mm or less.
16. An adhesive composition according to claim 1, wherein the adhesive composition has a sag distance of 2
mm or less.
wherein the adhesive composition has a phase lag of 45
degrees or less, a viscosity of 3,000 to 50,000 cp a complex 32. An adhesive composition according to claim 18,
shear modulus of 50 to 1000 Pa, and a sag distance of 10 mm wherein the adhesive composition has a sag distance of 5
or less. mm or less.
17. An adhesive composition according to claim 1, 33. An adhesive composition according to claim 18,
wherein the source of alkaline material is selected from the 25 wherein the adhesive composition has a phase lag of 45
group consisting of ammonia, triethanol amine, phosphates, degrees or less, a viscosity of 3,000 to 50,000 cp a complex
and mixtures thereof. shear modulus of 50 to 1000 Pa, and a sag distance of 10 mm
18. An adhesive composition consisting of: or less.
a vinyl acetate-ethylene copolymer; 34. The adhesive composition of claim 18, wherein the
an alkali Swellable thickener; 30 one or more fillers are selected from the group consisting of
water; one or more antioxidant, one or more stabilizer, one or more
a source of alkalinity; and antiozonant, one or more plasticizer, one or more dye, one
one or more fillers; or more U.V. absorber, one or more HALS, one or more
wherein the vinyl acetate-ethylene copolymer is dispersed pigment, and one or more glitter material.
within the water and the adhesive composition has a pH 35
35. An adhesive composition according to claim 18,
of 4 to 10; and wherein the adhesive composition has wherein the source of alkaline material is selected from the
a stringing length of 9 cm or less, a set time of 180 group consisting of ammonia, triethanol amine, phosphates,
seconds or less, and one or more of the following and mixtures thereof.
properties:
a phase lag of 45 degrees or less; 40 36. An adhesive composition consisting of:
a viscosity of 3,000 to 50,000 cF: one or more vinyl acetate-ethylene copolymers;
a complex shear modulus of 50 to 1000 Pa; and one or more alkali swellable thickeners;
a sag distance of 10 mm or less. water;
19. An adhesive composition according to claim 18, one or more sources of alkalinity; and
wherein the vinyl acetate-ethylene copolymer is present in 45
the adhesive composition at 5 to 75 wt %. one or more fillers;
20. An adhesive composition according to claim 19 wherein the vinyl acetate-ethylene copolymer is dispersed
wherein the alkali swellable thickener is present in the within the water and the adhesive composition has a pH
adhesive composition at 0.1 to 10 wt %. of 4 to 10; and wherein the adhesive composition has
21. An adhesive composition according to claim 18, 50 a stringing length of 9 cm or less, a set time of 180
wherein the vinyl acetate-ethylene copolymer is present in seconds or less, and one or more of the following
the adhesive composition at 20 to 75 wt %. properties:
22. An adhesive composition according to claim 21, a phase lag of 45 degrees or less;
wherein the alkali swellable thickener is present in the a viscosity of 3,000 to 50,000 cF:
adhesive composition at 0.1 to 5 wt %. 55
a complex shear modulus of 50 to 1000 Pa; and
23. An adhesive composition according to claim 18,
wherein the vinyl acetate-ethylene copolymer is present in a sag distance of 10 mm or less.
the adhesive composition at 50 to 75 wt %. 37. An adhesive composition according to claim 36,
24. An adhesive composition according to claim 23, wherein the adhesive composition has a phase lag of 45
wherein the alkali swellable thickener is present in the 60 degrees or less, a viscosity of 3,000 to 50,000 cp a complex
adhesive composition at 0.1 to 3 wt %. shear modulus of 50 to 1000 Pa, and a sag distance of 10 mm
25. An adhesive composition according to claim 18, or less.
wherein the alkali swellable thickener is an anionic alkali
swellable acrylic thickener.
 UNITED STATES PATENT AND TRADEMARK OFFICE
CERTIFICATE OF CORRECTION

PATENT NO. : 7,348,378 B2 Page 1 of 1

APPLICATIONNO. : 10/8843.02
DATED : March 25, 2008
INVENTOR(S) : Kurt C. Melancon

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

Column 4
Line 25, delete “arnides and insert -- amides: --, therefor.
Line 27, delete “acrylanide and insert -- acrylamide --, therefor.
Line 44, delete “ELVACETM 736' and insert -- ELVACT 736
Line 47, delete one “DUR-O-SET E-200
Column 9
Line 47-49, delete “Rhoplex" ASE-60, alkali swellable associative thickener supplied
at 28% solids, Rohm and Haas Co., Philadelphia, Pa. and insert the same on Col. 9,
Line 48, below “N.C. as new paragraph.
Line 50, delete “NH3 and insert -- NH --, therefor.
Column 12
Line 18 (Approx.). In Claim 2, delete “A” and insert -- An --, therefor.

Signed and Sealed this

Twenty-fourth Day of June, 2008

WDJ
JON. W. DUDAS
Director of the United States Patent and Trademark Office