Note: Descriptions are shown in the official language in which they were submitted.
-
~r
2 ~ u ~
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CROSS-REFERENCE TO RELATED APPLICATIONS
'-
- This application is a continuation-in-part of
U . S . application (Case No. 2004371) filed May 27, 1992
5 and a continuation-in-part of U . S . application Serial No.
07/714,789, filed June 13, 1991, the disclosures of which
are incorporated herein by reference.
FIELD OF THE INVENTION
This invention relates to compositions useful as
hot melt adhesives and to methods related thereto.
BACKGROUND OF THE INVENTION
' Hot melt adhesives produce a bond by cooling
while in contact with surfaces wetted by a melt of the
adhesive. As defined in S. Temin, "Adhesive
20 Compositions", Encvclopedia of Polymer Science and
Technoloay, vol. 1, pp. 547-577 (John Wiley ~ Sons,
Inc., N.Y., N.Y., rev. ed., 1985), a hot melt adhesive
is a thermoplastic polymer that is heated to obtain a
liquid of flowable viscosity which, after application, cools
25 to form a solid. It is stated that while many of these
adhesivos aro polymers of reasonable molecular weight,
. 9. basod on polyethylene, other polyolefins or
mixturos, ethylene/vinyl acetate copolymers, polyamides,
polyostors, and block copolymer rubbers, it is common to
30 incorporato low molocuiar weight additives for increased
fluidity at application temperatures.
Hot melt adhesives are used for bonding a
var;ety of materials such as paper, wood, plastics,
textiles, and other materials. One common use of hot
2~ rl ~j
- 3 - 2004372
melt adhesives is in the fabrication of corrugated paper
board. Considerations surrounding the use of hot melt
adhesives include the need for a bond having sufficient
strength under conditions of shock, stress, high
5 humidity, and extremes of temperature encountered in
transportation and storage. In addition, considerations
relating to the application of the adhesive include the
melt temperature, wetting time, initial tack, setting time,
pot life and general handling qualities on automated
application machinery.
There is great and still growing interest in the
recycling of materials, particularly those materials that
typically have a limited duration of use, e.g. packaging
materials such as corrugated boxes. see C. Rowland,
"New Corrugated Box Rules . . . ", PulP and Paper,
December 1990, pp. 120-126. Thus, paper and related
pulp products are commonly regarded as recyclable
materials. These materials are generally repulped as
part of the recycling process.
Repulping generally involves heating and
vigorously agitating an aqueous slurry of the paper
material to cause its disintegration into its component
fibers. If the paper material is associated with an
adhesive that is not dispersible in water, the repulping
may be impeded and the paper fibers will tend to break
away from the adhesive leaving large lumps or films of
adhesive mixed with the paper fibers. These lumps or
film~ of adhe~ive can foul the repulping equipment or the
equipment used to make paper from the repulped fibers
and may be retained in the resulting recycled paper as
blotche~ and other irregularities.
2`u~
- 4 - 2004372
U.S. Patent No. 3,891,584 (Ray-Chaudhuri et
al . ) discloses a water-dispersible hot melt adhesive.
The adhesive comprises a graft copolymer of a vinyl
monomer and a polyalkylene oxide polymer with a
5 polymerized ethylene oxide content of at least 50~ by
weight. The patent states that papers coated with such
adhesives are recyclable without adverse effects.
U . S . Patent No. 3,474,055 (Dooley) discloses a
hot melt adhesive containing a high melting polyhydroxy
10 compound. The patent notes the problems associated
-- with repulping corrugated board paper stock that has
been treated with a conventional hot melt adhesive. The
patent states that improved repulpability is obtained by
adding to an otherwise acceptable hot melt from 5 to 50
15 parts by weight of a water soluble crystalline
polyhydroxy compound having a melting point of at least
100C. It is further stated that the polyhydroxy
compound is preferably selected from the group
consisting of polyhydric alcohols and saccharides,
20 sorbitol being an example of the former and D-glucose
being an example of the latter. The patent also states
that higher molecular weight oligosaccharides and
polysaccharides are unsuitable because of amorphous
structure or tendency to decompose under the conditions
25 of preparation and use of the hot melt adhesive.
2 ~ ~J ~ ~ 7 ~
- 5 - 2004372
SUMMARY OF THE INVENTION
This invention relates to a composition useful
- as a hot melt adhesive or component thereof comprising a
5 major amount of a lower alkyl glycoside, and a minor
amount of a polysaccharide derived from starch selected
from the group consisting of pre-gelatinized converted
starches, cold-water soluble dextrins, and maltodextrins,
and mixtures of more than one of such members of said
10 group, wherein:
(i) said major amount of alkyl glycoside is
sufficient to provide a flowable melt of said composition,
- and
(ii) the degree of polymerization and said
15 minor amount of said polysaccharide is sufficient to
tackify said melt, but is insufficient to prevent said melt
from flowing. This invention relates to a heterogeneous
blend comprised of particles of each of the above
ingredients and to a substantially homogeneous
20 melt-processed blend of the ingredients.
It has been found that a hot melt adhesive
blend prepared from the ingredients set forth above has
excellent functionality as an adhesive, particularly when
used to bond paper materials, and yet will readily
25 disperse in the aqueous medium used in repulping of the
paper materials. In addition to acting as the hot melt
adhesiv~l itsolf, the composition is compatible with
convontional ethylene/vinyl acetate copolymers used as
hot melt adhesives and, when used in admixture
30 therewith, will improve the repulpability of paper
materials bonded with the resulting hot melt adhesive.
It wa- found that when dextrose was used alone to
provtde a melt of the polysaccharide, the resulting
2 '~
- 6 - 2004372
adhesive bond was very susceptible to failure under
- conditions of high humidity. Substitution of an alkyl
glycoside for the dextrose has been found to
substantially eliminate adhesive failure under conditions
5 of high humidity.
This invention also relates to a composition
useful as a hot melt adhesive or component thereof
comprising a lower alkyl glycoside, dextrose, and a
polysaccharide derived from starch selected from the
10 group consisting of pre-gelatinized converted starches,
cold-water soluble dextrins, and maltodextrins, and
mixtures of more than one of such members of said
group, wherein:
(i) the amounts of dextrose and lower alkyl
15 glycoside are sufficient to provide a flowable melt of said
composition,
(ii) the amount of said lower alkyl glycoside
is sufficient in relation to the amount of dextrose in said
composition to impart to said composition resistance to
20 adhesive failure when used as a hot melt adhesive under
conditions of elevated humidity, and
(iii) the degree of polymerization and the
amount of said polysaccharide is sufficient to tackify said
melt, but is insufficient to prevent said melt from
25 flowing. This invention relates to a heterogeneous blend
comprised of particles of each of the above ingredients
and to a substantially homogeneous melt-processed blend
of tho ingredionts.
It has been found that the use of dextrose
30 with an alkyl glycoside to provide a melt will generally
yiold a composition having a lower melt tomperature
This allows for a longer pot life for the resulting
adhesive without degradation of the adhesive
2~
- 7 - 2004372
components. Thus, under production circumstances
which require an extended pot life, the use of dextrose
with an alkyi glycoside is preferred.
This application also relates to a method of
5 adhering a cellulosic material to another substrate
comprising interposing a melt of a blend composition
between a cellulosic material and a substrate such that
the cellulosic material and substrate are in contact with
said melt and cooling said melt while in contact with said
10 cellulosic material and said substrate, wherein said blend
composition comprises:
(a) a major amount of a meltable saccharide
selected from the group consisting of a mono-saccharide,
a di-saccharide, a derivative of a mono-saccharide, a
15 derivative of a di-saccharide, and mixtures of more than
one of such members, and
(b) a minor amount of a polysaccharide
derived from starch selected from the group consisting
of pre-gelatinized converted starches, cold-water soluble
20 dextrins, and maltodextrins, and mixtures of more than
one of such members of said group, wherein:
(i) said major amount of saccharide is
sufficient to provide a flowable melt of said composition,
and
(ii) the degree of polymerization and said
minor amount of said polysaccharide is sufficient to
tackify said melt, but is insufficient to prevent said melt
from flowing.
As used herein, the term derivative as
, 30 applied to mono-saccharides and di-saccharides shall
mean a compound derived from a mono-saccharide or
di-saccharide, respectively. Preferred derivatives of
mono- and di-saccharides are glycoside derivatives or
r- ~
- 8 - 2004372
hydrogenation products, e.g. alkyl glucoside and
sorbitol, respectively.
This invention also relates to a method of
manufacturing a shaped article comprising melting a
5 composition of this invention, shaping said melt into the
form of an article, and cooling said melt while in the
shape of said article and to articles of manufacture
produced by such methods.
h 'i ~--? r?"I S7 ,,~;
- 9 - 2004372
DETAILED DESCRIPTION OF THE INVENTION
One of the components of the composition is a
lower alkyl glycoside. By "lower alkyl glycoside" is
5 meant a composition comprised predominantly of an acetal
or ketal of a monosaccharide with a lower (i . e. C1 -C4)
alkanol. Examples of monosaccharides from which the
glycoside is derived include glucose, fructose, mannose,
galactose, talose, gulose, allose, altrose, idose,
10 arabinose, xylose, Iyxose, and ribose. The preferred
glycosides are glucosides, i.e. derived from glucose, and
most preferred is alpha-methyl glucoside. ~ower alkyl
glycosides are typically manufactured by heating the
monosaccharide in the lower alkanol under conditions
15 which cause the condensation of the alkanol with the
monosaccharide and the liberation of water or by heating
a polysaccharide form of the monosaccharide (e.g. starch
in the case of glucosides) in a lower alkanol to cause a
type of transglycosidation of the polysaccharide to the
20 lower alkyl glycoside. If a lower aliphatic polyol (such
as the diols ethylene glycol and/or propylene glycol and
- the triol glycerol) is used condensed with the
monosaccharide, the product is a lower hydroxy-alkyl
glycoside. As such, lower hydroxy-alkyl glycosides are
25 within the scope of the term "derivative" as applied to
mono-saccharides and di-saccharides as used herein~
Another component of the preferred adhesive
compositlons of this invention is dextrose. Dextrose is
avallable commerclally in the anhydrous or monohydrate
~0 crystalllne form, or as a syrup. Dextrose is obtained
-~ by the hydrolysls of starch, e.g. from corn. ~he
production and properties of dextrose and corn syrups
aro discussed by H. M. Pancoast et al., Handbook of
;
2 ~ ? ~
v u v ~ ~ cJ
- 1 0 - 2004372
Suqars, pp. 157-287 (AVI Publ. Co., Westport,
Connecticut, 2d ed., 1980), the disclosure of which is
incorporated by reference herein. Substantially pure
dextrose, as crystalline monohydrate or high solids
5 syrup (e. 9 . about 70% by weight), is preferred for use
herein. Corn syrups and corn syrup solids are
chara~terized by dextrose equivalent (D. E. ) with the
high conversion syrups having a high D. E. and a high
concentration of dextrose. Lower conversion syrups and
10 corn syrup solids (which are typically of low conversion)
may be useful, but are not preferred.
The polysaccharide component of the
composition is selected from the group consisting of
three individual classes of starch based materials. All of
15 these materials are characterized by having been derived
from starch in a manner such that the native
polysaccharide has been subjected to partial hydrolysis
to lower its molecular weight and, thus, the viscosity of
a melt in which the polysaccharide is dispersed. In
20 general, the polysaccharide will be sufficiently
depolymerized that the melt will exhibit a viscosity of not
more than about 50,000 cps at 135C, preferably not
more than about 10,000 cps, e.g. a dynamic viscosity as
determined by Bohlin Rheometer, model VOR, available
25 from Bohlin Reologi, Inc., Cranbury, New Jersey.
Further, the hrm of the polysaccharide has been
converted from the native granular state to a form which
will ~llow the poly-accharide to disperse in the high
temperature, but low moisture, environment of a melt of
30 the ingredients.
A~ can be appreciated, the higher saccharides
that may be present in the source of the dextrose may
act asi a secondary source of the polysaccharide
r~
2004372
purposely added to the composition. Conversely, the
dextrose that may be present in the source of
polysaccharide, particularly the maltodextrins, may act
as a secondary source of the dextrose of the
5 composition. In the event that such secondary sources
of polysaccharide and dextrose, respectively, are
substantial, such sources should, of course, be taken
into account when selecting the proper amount of the
dextrose or polysaccharide which is purposely added.
10Converted pre-gelatinized starches are
typically derived from native starch by hydrolysis, e.g.
with enzymes or aqueous acid. The starch may be in
granular form during hydrolysis with acid, but it is
hydrolyzed to a degree sufficient to reduce the viscosity
15 of an aqueous dispersion of the starch, in which
dispersion the starch is in gelatinized form. In other
words, the starch is made "thin-boiling". Typical acid
hydrolysis conditions will include slurrying starch with
~i water to a slurry density of from about 1.1 g~ml to
20 about 1.2 g/ml and adding sufficient mineral acid (e.g.
hydrochloric acid or sulfuric acid) to reduce the pH of
the slurry to between about 1.5 and about 2.5. The
slurry is then heated under pressure to a temperature
between about 105C to about 125C, for a time
25 sufficient to give the desired degree of thinning (and
which also sorves to gelatinize or liquefy the starch).
Tho starch will typically have a Brookfield viscosity at
about 30~ solids of from about 600 to about 1000 cps.
The starch can be isolated after neutralization of
30 residual minoral acid by drying of the slurry, for
oxample on hoated rolls, to a moderate moisture content
(o.g. 10~ to 12~ by weight).
c~ ,~, .~ ~ ,~ r-
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- 1 2 - 2004372
Another class of materials derived from starch
and which are useful as the polysaccharide are the
cold-water soluble dextrins. As used herein, the term
"dextrin" is meant to refer to the products derived from
5 essentially dry starch by the action of heat, or both
heat and acid. Such materials are also referred to in
the art as "pyrodextrins". The manufacture of dextrins
is extensively discussed in R. B. Evans et al.,
"Production and Use of Starch Dextrins", Starch:
Chemistry and Technoloay, vol . I l, pp . 253-278 ( R . L.
Whistler, ed ., Academic Press I nc ., N . Y ., N . Y ., 1967),
the disclosure of which is incorporated by reference
herein .
There are generally four major steps in the
production of dextrins, i.e. acidification (typically with
about 0.05% to 0.15% of 0.1N HCI), predrying (typically
to about 1-596 moisture), dextrinization (heating at
temperatures of about 95C to 180C) and cooling,
although the class of dextrins known as British gums are
made without acid. Of the two types of dextrins
prepared with acid, the white dextrins are heated at
lower temperatures than the canary dextrins, and thus,
longer periods of roasting of white dextrins are needed
to obtain the same increase in solubility as a canary
dextrin. In general, the cold-water solubility of the
dextrin should be substantial, e.g. greater than 50~,
and the viscosity sufficiently reduced f rom the parent
starch to yTeld the melt viscosity discussed above in
connection wlth pre-gelatinized converted starches.
Tho polysaccharide may also be a maltodextrin.
Maltodextrins are prepared from starch by the hydrolysis
with acid and/or enzyme of starch in an aqueous
medium. Maltodextrins are generally characterized on
fr r) ~l " ~
~ 13 ~ 2004372
the basis of dextrose equivalent (D. E. ) which is an
indication of the totai reducing sugars present calculated
as D-glucose on a dry weight basis. Unhydrolyzed
starch has a D.E. of virtually zero while pure anhydrous
5 D-gls~cose has a D.E. of 100. Maltodextrins have a D.E.
of less than 20 from which it may be inferred that the
average degree of polymerization (DP) of the
- polysaccharide will be greater than about 5
Maltodextrins having a D. E . as low as about 1 (i . e. an
10 average DP of about 100) are commercially available.
Starch hydrolysates having a D . E . above 20, e. 9 . Iow
conversion (D. E. of 20-45) corn syrup solids, may also
be useful as the polysaccharide, particularly in
compositions which otherwise have no added dextrose.
The production of maltodextrins is discussed in
R. L. Whistler, Starch: Chemistrv and Technoloqy, pp.
614-623 (2nd ed ., Academic Press I nc., N . Y ., N . Y .,
1984), the disclosure of which is incorporated herein by
reference. A slurry of starch in water (e.g. at 40~ by
20 weight starch solids) is typically heated to liquefy the
starch and then acid (e. 9 . HCI) is added to lower the
pH of the slurry te.9. to about 2) to catalyze the
hydrolysis of the starch in the hot aqueous solution.
The acid is neutralized and the slurry is typically
25 evaporated to higher solids for further hydrolysis, if
desired, with enzymo, or for drying (e . g . by spray
drying) .
The amounts of the components are chosen in
r~btion to on0 another to yield the desired properties in
30 the resulting hot melt adhesive. The alkyl glycoside,
and dextrose if pr0sent, provides a flowable melt phase
to the adhesive. The flowability of the adhesive melt is
important in allowing the melt to wet the %ubstrate to be
1~\ V ~
- 1 4 - 2004372
bonded. As noted above, the degree of polymerization
of the polysaccharide will affect the viscosity, and thus
flowability, of the melt as well. Thus, the selection of
the precise amount of alkyl glycoside, and dextrose, will
be influenced by the choice of polysaccharide. In
general, the alkyl glycoside will comprise a major amount
by weight (i.e. at least 50~ by weight) of the mixture of
alkyl glycoside and polysaccharide and the
- polysaccharide will comprise a minor amount by weight of
the mixture (i.e. Iess than 50% by weight, typically from
about 15% by weight to about 35% by weight). The
amount of polysaccharide should be sufficient to impart
wet tack to the melt and to prevent excessive migration
of the melt into porous substrates, ~uch as uncoated
- 15 paper. Likewise, in mixtures of alkyl glycoside,
dextrose, and polysaccharide, the combined weight of
the alkyl glycoside and dextrose will be a major amount
by weight of the mixture.
In compositions which contain both alkyl
i 20 glycoside and dextrose, the amount of alkyl glycoside
should be sufficient in relation to the amount of dextrose
to provide the desired degree of resistance to adhesive
failure at elevated temperature and humidity. Such
rosistance can be measured by use of the customary test
methods, e.g. TAPPI Method T 517 om-85 "Dynamic
Strength of Flexible Barrier Material Seals" (Technical
A~ociation of the Pulp and Paper I ndustry, Atlanta,
Georgia, 1985) and TAPPI Useful Method 556 "Static Load
Strength of Flexible Barrier Material Seals", upon
samples tested in an environment having conditions of
elevated temperature and humidity te.g. 100F and 85
r. h . ) . As noted above, the amount of dextrose can be
adjusted to lower the temperature at which the
2 ' ~ ~ ' ` `~ ~'! 'j
- 1 5 - 2004372
compositions form a melt upon heating. This lower melt
temperature will allow the adhesive to be kept at
application temperatures for longer periods with lower
risk of degrading the components of the melt, e.g. the
5 polysaccharide. Generally, the ratio of alkyl glycoside
to dextrose will be at least about 1:1 to about 5:1, and
typically from about 2:1 to about 4:1.
The above components of the adhesive
composition are commercially available as powdered,
- 10 crystalline or granulated solids which are substantially
dry, e.g containing no more than about 15% moisture.
The crystalline monohydrate form of dextrose, when
substantially dry, will contain about 9% by weight
moisture held within the crystal lattice. The
15 polysaccharide will generally contain substantial
moi~ture, e.g. 8~ to 12% by weight, although a dextrin
may have substantially less moisture, e.g. 3-5%. Thus,
a melt of the ingredients will generally contain, at most,
a nominal or trace amount of water, preferably less than
20 5% by weight. In certain embodiments, this invention
relates to a mixture of the components in the form of a
blend of particles, each particle comprised of one of the
individual components, and thus, the blend is
heterogeneous in nature. Such a blend is prepared by
25 ~imply dry mixing Individual dry ingredients. This dry
blend can be used as a hot melt adhesive directly or it
c-n be mixed with other additives or hot melt adhesives.
In other embodiments, this invention relates to
a melt processed blend of the ingredients which, as a
30 result of the melt processing, is a substantially
homogeneou~ mixturo. In this embodiment, the
compo~ition may be in the form of rods, pellets,
granules, or powders. The melt processed blend is
- Q ~ ` A r ~
- 1 6 - 2004372
prepared by heating a mixture of the desired amounts of
the components to form a melt, e . g . to a temperatu re of
from about 100C to about 200C, and stirring of the
melt to achieve substantial homogeneity. The melt
chamber is preferably vented to allow evaporation of the
water that may be present in the composition.
Alternatively, the process may comprise first melting the
alkyl glycoside and/or dextrose followed by the addition
of the polysaccharide. In the event a syrup is used as
a source of the dextrose, most, if not all, of the water
of the syrup will be evaporated during this melt blend
processing. The melt is then cooled below its melting
range to solidify. Such processing may be batch or
continuous .
For example, the components can be fed to an
extruder, e.g. a vented, single-screw extruder, with a
heating zone to melt the composition followed by a
cooling zone to solidify the composition. Upon exit from
the extruder barrel, the composition can be deposited as
a rod for use as an adhesive or the composition can be
, pelleted, e.g. through the use of a reciprocating or
rotating knife positioned at the mouth of the extruder
barrel. The composition can then be packed and/or
storod, as desired, prior to reheating for use as a hot
molt adhosivo.
- Tho hot molt adhesivo may contain additional
compononts. Typlcal additives include tackifying resins
(o. 9. torpono rosins and/or rosin derivatives),
plasticlzor~, flow modifiers, fillers, pigments, and/or
dyostuffs, gonorally in a minor amount by weight (i. e.
Ioss than 50~ by woight of the adhesive). Particularly
usoful additivos aro waxos or oils. Particularly preferred
waxos are the hydrocarbon waxes such as paraffin
~ ~ 7j V ~
- 1 7 - 2004372
waxes, microcrystalline waxes, polyethylene waxes,
Fischer-Tropsch waxes, and/or chemically modified
hydrocarbon waxes (e.g. oxidized polyethylene waxes).
Waxes and their sources are more particularly described
in EncycloPedia of Chemical Technolo~y, vol. 24, pp.
466-481 (Kirk-Othmer, eds., John Wiley ~ Sons, Inc.,
N.Y., N.Y., 3rd ed., 1984), the disclosure of which is
incorporated herein by reference. The amount of wax
added, if any, will typically range from about 5% to
about 20% by weight of the hot melt adhesive.
Further, the hot melt compositions of this
invention can be used in admixture with conventional hot
melt adhesives, i.e. thermoplastic polymers, e.g.
ethylene/vinyl acetate copolymers (e. g . ELVAX, available
from E.l. DuPont de Nemours, Wilmington, Delaware),
polyethylene, other polyolefins, polyamides, polyesters,
and block copolymer rubbers. Such conventional hot
melt adhesives will generally comprise a minor amount by
weight of the hot melt adhesive (i . e. Iess than 5ali by
weight), but may be present in a major amount
depending upon the properties desired in the hot melt
and the degree of repulpability that is needed in the
chosen use of the adhesive. Such thermoplastic
polymers will generally have a melting point between
2S about 100C and about 200C.
The compositions of this invention are used as
a hot molt adhosive. The composition, while in the form
of a flowablo molt, it interposed between two surfaces to
bo bonde~. Tho two surfaces are mated and the
composition is allowed to at least partially solidify after
wotting the two surfaces and thus form a bond between
the surfaces. The precise amount of adhesive applied
per unit of area of the bond will vary, but typlcal
9 ~ r! r~
- 1 8 - 2004372
values range from about 0.1 to about 0.3 grams per
square inch of adhesive bond, most typically from about
0.15 to about 0.25 g/sq. in. Of course, it should be
noted that the surface of the substrate actually bonded
is typically only a fraction, e.g. 10%, of the area of the
surfaces that are mated as a result of the bond, e.g. in
a closure of box flaps. The temperature to which the
composition need be heated to form a flowable melt will
also vary depending upon the precise formulation
10 thereof, but will typically be between about 100C to
about 200C.
Various techniques may be used to obtain a
melt of the adhesive interposed between the surfaces to
be bonded. Techniques of bonding with hot melts are
discussed in Encvclopedia of Polvmer Science and
Enaineerinq, vol. 1, pp. 547-552 (John Wiley ~ Sons,
Inc., N.Y., N.Y. 1984), and EncvcloPedia of Chemical
TechnoloaY, vol. 1, pp. 499-501 (Kirk-Othmer eds.,
John Wiley ~ Sons, Inc., N.Y., N.Y., 3rd ed., 1904),
20 the disclosures of which are incorporated herein by
reference. In general, the adhesive is applied to the
substrates by one of three general methods, or
variations thereof.
In the first method, a melt of the adhesive is
25 applied to one of the surfaces to be bonded, and the
second surface is then mated to the first with the melt
positioned between the surfaces. The mode of
application of the melt may vary, depending upon the
dosired pattern of adhesive and the viscosity of the
30 melt, e.g. melts of relatively low viscosity may be
applieci by spraying, melts of moderate viscosity may be
applied by extrusion, and melts of high viscosity may bs
applied by roll coating . I n the second method, the melt
2 ~ 3 r~ ~ r~ ~j
- 1 9 - 2004372
is fed between prepositioned surfaces by gravity,
capillary wicking, pressure, or vacuum feeding
techniques. In the third method, a solid form of the
adhesive, e. g . a powder of film, is placed between the
surfaces and heat is applied to the adhesive to melt it.
In the broadest embodiments of the method of
this invention, the composition used as an adhesive is a
mixture of a major amount of a meltable saccharide and a
minor amount of a polysaccharide. The group of
meltable saccharide includes the alkyl glycosides and the
saccharides discussed above. This group also includes
other sugars, e. 9. sucrose, fructose, lactose, and
maltose, and the sugar alcohols, e.g. sorbitol, mannitol,
xylitol, dulcitol, mannitol, and lactitol. Methods of
obtaining sugar alcohols are described in F. Benson,
"Alcohols, Polyhydric (Sugar)", Encvclopedia of Chemical
Tochnolo~v, vol. 1, pp. 754-778, (John Wiley ~ Sons,
Inc. N.Y., N.Y., Kirk-Othmer, eds., 3d ed., 1978),
the disclosure of which is incorporated by reference.
The compositions of this invention may be used
to bond a variety of substrates, but are most
advantageously used to bond cellulosic substrates, e.g.
paper, paperboard, corrugated board, chipboard, and
the like. The adhesive finds particular utility in case
and carton sealing applications wherein the adhesive is
u~od to bond tho flaps of paperboard or corrugated
board containor~ and thereby close the case or carton.
Tho case or carton, after use, is then particularly
su~ceptible to repulping.
- 30 The compositions of this invention can also be
u~od to prepare shaped articles that are largely
biodogradablo. By shaped articles is meant items that
havo utllity by virtue of their structural dimensions of
r ! ~
- 20 - 2004372
height, width and depth. Such articles may have a
variety of geometric shapes and may be either solid,
hollow, open-celled foams, closed-cell foams, and the
like. Such articles include bottles, sheets, films,
5 wrappings, pipes, rods, spheres, cubes, squares, tiles,
mats, laminated films, bags, capsules (e.g.
pharmaceutical capsules), granules, powders, or foams.
The techniques employed to form such articles may
include casting, injection molding, blow molding,
10 extrusion, co-extrusion, spray coating, dip coating,
roller coating, curtain coating, and the like. Further,
ingots, rods, or films of the composition can, if heated
above their glass transition temperature, but below their
melt temperature, be physically manipulated (e.g. by roll
15 forming, stamping and so on) and, thus, articles can be
formed in this manner.
In particular embodiments, the compositions of
this invention will be melted, molded, and cooled to form
solid cylinders that are useful as hot melt glue sticks.
20 Such cylinders are typically from about 2 mm to about 2
cm in diameter and from about 2 cm to about 20 cm in
length. These cylinders can then be inserted into
commercially available hot melt glue "guns" which have a
heated chamber that receives the cylinder. In
: 25 operation, the cylinder is heated in the chamber and the
- melt dispensed from the "muzzle" of the gun.
The following examples will illustrate the
invontion and should not be construed to limit the scope
thereof. All parts, percentages and ratios recited in
30 this spocification are by weight unless otherwise noted in
context.
r ~, ~
- 2 1 - 2004372
EXAMPLES
In all of the examples, the following
procedures of adhesive preparation, application and
5 testing were employed.
All of the ingredients were first dry blended
until well mixed. After dry blending, the mixture was
fed at maximum rate into a four stage, single screw
extruder available as the Bonnot Model 2 and 1/4" from
10 The Bonnot Co., Kent, Ohio. This extruder had a
barrel length of 44 inches, a screw diameter of 2 and
1/4 inches, and a screw speed of 36 rpm. The
temperature within the extruder was at 60C in the first
stage and 163C in the remaining three stages. The
15 extrudate was collected on a stainless steel plate or
cooling belt.
The melt range reported in the examples is the
range over which the melt processed blend first began to
soften to the temperature at which the melt was fully
20 liquified. The softening points reported in the examples
were measured according to ASTM Method E28 "Test
Method for Softening Point by Ring-and-Ball Apparatus"
(American Society for Testing and Materials,
Philadelphia, Pennsylvania, 1982). The melt viscosity
25 was a dynamic viscosity as measured by Bohlin
Rheomoter, model VOR, available from Bohlin Reologi,
Inc., Cranbury, New Jersey.
Bond~ for shear test;ng were prepared by
r~nelting the adhesive to a temperature above its melt
30 rango, and applying the melt between coated cereal box
~tock bondod coated side to uncoated side to simulate a
flap closuro of a cereal box. The adhesive was applied
at tho rate of approximately 0.2 grams per square inch.
h iJ u~ 3
- 22 - 2004372
The shear testing for Examples 1-14 was performed in
accordance with TAPPI Method T 517 om-85 Dynamic
Strength of Flexible Barrier Material Seals and TAPPI
Useful Method 556 Static Load Strength of Flexible
5 Barrier Material Seals . The Dynamic Shear value
reported below is the average load needed to cause
failure and the Static Load Shear value reported below is
the time until failure of a one square inch bond tested
with a load of 300 grams. The peel and shear testing
10 for Examples 23-30 was performed in accordance with
Modified TAPPI Methods T8145su-71 from Testing of
Adhesives, TAPPI Monograph series No. 35 (R.G. Meese,
ed., Mack Printing Co., Easton, Pennsylvania, 1974).
The following identifies the materials listed in
the formulations set forth in the examples.
- Dextrin 230: a pyrodextrin available from
A.E. Staley Mfg. Co., Decatur, Illinois, as
20 STADEX~ 230.
Dextrin 94: a pyrodextrin available from A.E.
Staley Mfg. Co., Decatur, Illinois, as STADEX0 94.
~'
Acid-modified Starch: an acid depolymerized
starch available from A. E. Staley Mfg. Co. as KOLDEX0
,: 60.
Maltodextrin 10: a 10 D. E. maltodextrin
30 availablo from A.E. Staley Mfg. Co. as STAR-DRI0 10.
Maltodoxtrin 1: a 1 D. E. maltodextrin
avallablo from A.E. Staley Mfg. Co. as STAR-DRI0 1.
:
~`J ~
- 23 - 2004372
Corn Syrup Solids 24: a low conversion corn
syrup solids having a D. E. of 24 available from A. E.
Staley Mfg. Co. as STAR-DRI 24R
Corn Syrup Solids 35: a low conversion corn
syrup solids having a D. E. of 35 available from A. E.
Staley Mfg. Co. as STAR-DRI 35R
Corn Syrup Solids 42: a low conversion corn
syrup solids hav;ng a D. E. of 42 available from A. E.
Staley Mfg. Co. as STAR-DRI 42C
Methyl Glucoside: alpha-methyl glucoside
available from Grain Processing Corporation, Muscatine,
lowa, as STA-MEG'ID 104.
Dextroso: dextrose monohydrate available from
A.E. Staley Mfg. Co. as STALEYDEX~ 333.
,
Paraffin Wax: a paraffin wax having a melt
range of from 48C to 68C, available from
Boyle-Midway, Inc., N.Y., N.Y.
.
C-4040 Wax: a saturated straight chain
hydrocarbon polymer available from Petrolite Corporation,
Tulsa, Oklahoma, as PETROLITE C-4040 crystalline
polymer.
C-5500 Wax: an oxidized hydrocarbon available
from Petrolite Corporation as PETROLITE~9 C-5500.
~ U ~
- 24 - 2004372
EVA 1: an ethylene/vinyl acetate copolymer
available from DuPont, Wilmington, Delaware, as ELVAX
205W.
EVA 2: an ethylene/vinyl acetate copolymer
available from DuPont, Wilmington, Delaware, as ELVAX
210.
EBAC: an ethylene/n-butyl acrylate copolymer
10 available from Quantum Chemical Corp., Cincinnati,
Ohio, as EA ô9822.
., .
r
: 25
1 n ~ I rl ~;
- 25 - 2004372
EXAMPLE 1
Fonnulation:
Pa rts
Inqredient by Wei~ht
Methyl Giucoside 70
Acid-Modified Starch 30
ProPertbs:
Dynamic Shear:
at 72F/50% r.h./24 hrs.: ôô.8 Ibs./sq. in.
at 100F/85% r.h./24 hrs.: 74.4 Ibs./sq. in.
Static Load Shear:
at 100F/8596 r.h./300 gm. wt.: Failed at 97 hrs.
t Visco~ity:
at 135C: --
' at 15ûC: 21,100 cps
Melt Range: 160-163C
Softening Point: 155C
-
7~r'
h ~J ` . J!
- 26 - 2004372
EXAMPLE 2
Formulation:
Pa rts
In~redient by Wei~ht
Dextrin 20
Methyl Glucoside 40
Dextrose 10
C4040 Wax 5
C5500 Wax 10
Properties:
Dynamic Shear:
at 72F/50~ r.h./24 hrs.: 101.6 Ibs./sq. in.
at 100F/85% r. h./24 hrs.: 44.1 Ibs./sq. in .
Static Load Shear:
at 100F/85% r.h./300 gm. wt.: Failed at 54 hrs.
Viscosity:
at 135C:39,200 cps
at 150C:1,470 cps
-
Melt Range: 115-123C
Softening Point: 126.5C
v ~
- 27 - 2004372
EXAMPLE 3
Formulation:
Parts
In~redient b`~ Wei~ht
Dextrin 20
Methyl Glucoside 50
Dextrose 15
- C4040 Wax 5
C5500 Wax 10
- Properties:
Dynamic Shear:
' at 72F/50% r.h./24 hrs.: 99.3Ibs./sq. in.
at 100F/ô5% r.h./24 hrs.: 49.3 Ibs./sq. in.
.~ .
Static Load Shear:
at 100F/8591~ r.h./300 gm. wt.: Failed between 3
days and 5 days
Vi s cos ity:
at 135C: 2,240 cps
at 150C: 1,120 cps
.
25Melt Range: 116-122C
Softening Point: 135.5C
.
r~
- 28 - 2004372
EXAMPLE 4
;
Formulation:
Parts
In~redient by Wei~ht
Dextrin 25
Methyl Glucoside 50
Dextrose 20
C4040 Wax 5
ProPerties:
Dynamic Shear:
at 72F/50% r.h./24 hrs.: 92.8 Ibs./sq. in.
at 100F/854~ r.h./24 hrs.: 0 Ibs./sq. in.
Static Load Shear:
at 100F/859~ r.h./300 gm. wt.: ~2 hrs. to failure
Viscosity:
at 135C: 17,800 cps
at 150C: 538 cps
Melt Range: 109-119C
O
Softening Polnt: 130 C
- 29 - 2004372
EXAMPLE 5
Formulation:
Pa rts
Inqredient bY Weiqht
Dextrin 25
Methyl Glucoside 50
Dextrose 25
10ProPerties:
Dynamic Shear:
at 72F/50% r.h./24 hrs.: 79.5 Ibs./sq. in.
at 100F/85% r.h./24 hrs.: 0 Ibs./sq. in.
Static Load Shear:
at 100F/859~ r.h./300 gm. wt.: '1 hr. to failure
Viscosity:
at 135C: 8,980 cps
at 150C: 670 cps
Melt Range: 117-126C
Softening Point: 134C
2 ~ ~ ~ 7 ~;
- 30 -2004372
EXAMPLE 6
Formulation:
Pa rts
Ingredient by Wei~ht
5 Dextrin 20
Methyl Glucoside 20
Dextrose 10
C4040 Wax 10
C5500 Wax 10
EVA 1 30
Properties:
Dynamic Shear:
' 15 at 72F/50% r.h./24 hrs.: 81.2 Ibs./sq. in.
at 100F/85% r.h./24 hrs.: 44.2 Ibs./sq. in.
- Static Load Shear:
at 100F/85% r.h./300 gm. wt.: >10 days with no
failu re
.
Viscosity:
at 121C: 12,800 cps
at 135C: 7,590 cps
at 150C: --
Melt Range: 108-129C
Softening Point: 103.5C
J
. .
.v
-
f~ u ~ .J ,. ~ ~`?
- - 31 - 2004372
EXAMPLE 7
- Formulation:
Pa rts
Inqredient by Wei.~ht
Methyl Glucoside 72.2
Maltodextrin 10 27.8
ProPerties:
Dynamic Shear:
at 72F/5096 r.h./24 hrs.: 83.1 Ibs./sq. in.
at 100F/85% r.h./24 hrs.: 88.3 Ibs./sq. in.
Static Load Shear:
at 100F/85% r.h./300 gm. wt.: Failed at 20 hrs.
Viscosity:
at 135C: --
at 150C: 1,230,000 cps
at 163C: 2,960 cps
Melt Range: 147-154C
Softening Point: 145C
Q ~
~ ~, c v ~ d J
- 32 - 2004372
EXAMPLE 8
Forrnu lation:
Pa rts
Inqredient by Wei~ht
Methyl Glucoside 70.05
Acid-Modified Starch 23.70
Paraffin Wax 6.25
Properties:
Dynamic Shear:
at 72F/50% r.h./24 hrs.: 88.6 Ibs./sq. in.
at 100F/85% r.h./24 hrs.: 82.3 Ibs./sq. in.
Static Load Shear:
at 100F/85% r.h./300 gm. wt.: >2 months with no
failure
Viscosity:
at 135C: --
at 150C:16,500 cps
Melt Range: 149-155C
Softening Point: 155C
h ~a . ~, e ,;
- 33 - 2004372
EXAMPLE 9
Formulation:
Pa rts
Inaredient bv Weiaht
Methyl Glucoside 65
Maltodextrin 1 30
Paraffin Wax 5
Properties:
Dynamic Shear:
at 72F/5096 r.h./24 hrs.:85.0 Ibs./sq. in.
at 100F/85% r.h./24 hrs.:75.2 Ibs./sq. in.
Static Load Shear:
at 100F/85~ r.h./300 gm. wt.:'2 months with
no failure
Viscosity:
at 135C: --
at 150C:150,000 cps
at 163C:5,260 cps
Melt Range:149-152C
Softening Point: 156C
rl ~
v ~ ~ t,i
- 34 - 2004372
EXAMPLE 10
Formulation: Parts
Inaredient by Weiaht
Methyl Glucoside 66.7
Acid -Modif ied Sta rch 33.3
Properties:
Dynamic Shear:
at 72F/50% r.h./24 hrs.: 90.9 Ibs./sq. in.
at 100F/85% r.h./24 hrs.: 81.5 Ibs./sq. in.
Static Load Shear:
15at 100F/85%r.h./300 gm. wt.: ~10 days with
no failure
Viscosity:
at 135C: 150,000 cps
20at 150C: 86,000 cps
at 163C: 25,000 cps
Melt Range: 142-152C
Softening Point: 154.5C
~ V V ~
- 35 - 2004372
EXAMPLE 11
Formulation:
Pa rts
Inaredient by Weiaht
Methyl Glucoside 50
Acid-Modified Starch 25
EBAC 25
Properties:
Dynamic Shear:
at 72F/50% r.h./24 hrs.: 99.6 Ibs./sq. in.
at 100F/85% r.h./24 hrs.: 83.4 Ibs./sq. in.
Static Load Shear:
at 100F/85% r.h./300 gm. wt.: '10 days with
no failure
Viscosity:
at 135C:3,590,000 cps
at 150C:-- cps
at 163C:76,300 cps
Melt Range: 148-155C
Softening Point: 155C
~ tJ ~
- 36 - 2004372
EXAMPLE 12
Formulation:
Pa rts
Inqredient bv Weiqht
Methyl Glucoside 50
Acid-Modified Starch 25
Dextrose 20
Paraffin Wax 5
Properties -
Dynamic Shear:
at 72F/50~ r.h./24 hrs.: 86.8 Ibs./sq. in.
at 100F/85% r.h./24 hrs.: 79.5 Ibs./sq. in.
Static Load Shear:
at 100F/85% r.h./300 gm. wt.: >10 days with
no failure
Viscosity:
at 135C: --
at 150C: 15,100 cps
Melt Range: 140-150C
Softening Point: 138.5C
- 37 - 2004372
EXAMPLE 13
For~nulation:
Pa rts
Inaredient bv Wei~ht
Methyl Glucoside 55.6
Acid-Modified Starch 27.8
EVA 2 16.6
10 Properties:
Dynamic Shear:
at 72F/50% r.h./24 hrs.: 97.6 Ibs./sq. in.
at 100F/85% r.h./24 hrs.: 83.3 Ibs./sq. in.
Static Load Shear:
at 100F/85% r.h./300 gm. wt.: >10 days with
no failure
Viscosity:
20 at 135C: --
at 150C: 47,300 cps
at 163C: 31,51)0 cps
Melt Range: 140-150C
Softoning Point: 151C
~ 'J~ _ ~f .~
- 38 - 2004372
- EXAMPLE 14
Formulation:
Pa rts
In~redient by Wei~ht
Dextrin 47.5
Dextrose 47.5
Paraffin wax 5.0
ProPerties:
Dynamic Shear:
at 72F/50% r.h./24 hrs.: --
at 100F/85~ r.h./24 hrs.: Failed before 24 hrs.
Static Load Shear:
at 100F/85% r.h./300 gm. wt.: Failed at ~1/2 hr.
Viscosity:
at 135C: 45,200 cps
at 150C: Foams
Melt Range: 105-116C
Softening Point: 88.5C
- 39 -2004372
EXAMPLE 1 5
Formulation:
Pa rts
Inaredient by Wei~ht
Dextrin 94 50
Dextrose 1 5
Sucrose 35
EXAMPLE 16
Fonnulation:
Pa rts
Inqredient by Weiaht
Maltodextrin 10 50
Sucrose 50
EXAMPLE 17
Fonnulation:
Parts
In~redient bv Wei.qht
Dextrin 94 50
Dextrose 25
Sucrose 25
r~r~ ~
- 40 - 2004372
EXAMPLE 18
Formulation:
Pa rts
Inaredient by Weiqht
Dextrin 230 40
Dextrose 35
Fructose 'O
Corn Syrup Solids 24 15
EXAMPLE 19
Formulation:
- Parts
In~redient bY Weiqht
Dextrin 230 48
Dextrose 32
Fructose 10
Corn Syrup Solids 24 10
EXAMPLE 20
Formulation: Parts
In~redient bv Weiqht
Dextrin 230 40
Dextrose 40
Corn Syrup Solids 35 20
2 ~ r~
- 41 - 2004372
EXAMPLE 21
Formulation: Parts
Inqredient bv Wei.qht
5Dextrose 60
Maltodextrin 1 40
EXAMPLE 22
Fonnulation: Pa rts
Inaredient bv Weiaht
Dextrose 50
15Maltodextrin 1050
r~ ~,
; J ~ i3
- 42 - 2004372
EXAMPLE 23
Formulation:
Pa rts
Inqredient bY Wei~ht
Methyl Glucoside 50
Corn Syrup Solids 42 50
ProPerties
Dynamic Shear:
at 72F/5096 r.h-
First replicate: 40.85 Ibs.tsq. in.
Second replicate: 41.66 Ibs./sq. in.
Percent Dynamic Shear
15 Retained on Conditioning: 99.47
Peel: 66C
Shear: >82C
Softening Point: 95C
Viscosity:
at 149C: 875 cps
at 143C: 1,238 cps
at 138C: 6,550 cps
at 133C: offscale
- 43 - 2004372
EXAMPLE 24
Formulation:
Pa rts
In~redient bY Weiaht
Methyl Glucoside 50
Corn Syrup Solids 42 30
Dextrin 230 20
Properties
Dynamic Shear:
at 72F/50% r.h.
First replicate: 39.69 Ibs./sq. in.
Second replicate: 36.44 Ibs./sq. in.
15 Percent Dynamic Shear
Retained on Conditioning: 91.78
Peel: 63C
20 Shear: >82C
Softening Point: 151C
Viscosity:
at 149C: 2,375 cps
at 143C: 3,250 cps
at 138C: 6,213 cps
at 133C: offscale
. ~ g A ~ r~r;
- 44 - 2004372
EXAMPLE 25
Fonnulation:
Pa rts
In~redient by Wei~ht
Methyl Glucoside 50
Corn Syrup Solids 35 50
Properties
Dynamic Shear:
at 72F/50% r.h.
First replicate:27.23 Ibs./sq. in.
Second replicate: 37.91 Ibs./sq. in.
Percent Dynamic Shear
Retained on Conditioning: 78.53
.
Peel: 60C
Shear: >82C
Softening Point: 147C
Viscosity:
at 149C: 1,288 cps
at 143C: 1,963 cps
at 138C: off scale
at 133C: Off ~cale
- 45 - 2004372
EXAMPLE 26
Fonnulation: -
Pa rts
In~redient by Weiqht
Methyl Glucoside 50
Corn Syrup Solids 24 50
Properties
Dynamic Shear:
at 72F/50% r. h .
First replicate: 38.04 Ibs./sq. in.
Second replicate: 40.67 Ibs./sq. in.
Percent Dynamic Shear
15 Retained on Conditioning: 94.89
Peel: 41 C
Shear: ~62C
Softening Point: 107C
Viscosity:
at 149C: 8,638 cps
at 143C: 127,500 cps
at 138C: off scale
at 133C: off scale
~ U ~ v- 1~
- 46 - 2004372
EXAMPLE 27
Fonnulation: Parts
In~redient by Weiqht
Methyl Glucoside 50
Corn Syrup Solids 24 35
Dextrose 15
Properties
Dynamic Shear:
at 72F/50~ r.h.
First replicate:30.78 Ibs./sq. in.
Second replicate: 21.28 Ibs./sq. in.
Percent Dynamic Shear
Retained on Conditioning: 62.76
Peel: 77C
Shear: >82C
Softening Point: 103C
Viscosity:
at 149C: 650 cps
at 143C: 900 cps
at 138C: 1,638 cps
at 133C: off scale
- 47 - 2004372
EXAMPLE 28
, .
Formulation:
Pa rts
In~redient by Wei~ht
Methyl Glucoside 50
Corn Syrup Solids 24 35
S ucrose 15
Properties
Dynamic Shear:
at 72F/5096 r.h.
First replicate: 103.10 Ibs./sq. in.
Second replicate: 120.10 Ibs./sq. in .
Percent Dynamic Shear
Retained on Conditioning: 102.51
Peel: 57C
Shear: >82C
Softening Point: 79C
Viscosity:
at 149C: 1,400 cps
at 143C: 2,125 cps
at 138C: 5,625 cps
at 133C: off scale
. ~
- 48 - 2004372
EXAMPLE 29
Formulation:
Pa rts
Inaredient bY Wei.aht
Methyl Glucoside 50
Corn Syrup Solids 24 35
Sorbitol 15
Properties
Dynamic Shear:
at 72F/50~ r.h.
First replicate: 96.50 Ibs./sq. in.
Second replicate: 91.55 Ibs./sq. in.
Percent Dynamic Shear
Retained on Conditioning: 86.37
Peel: 38C
Shear: >82C
Softening Point: 77C
Viscosity:
at 149C: 625 cps
at 143C: 800 cps
at 138C: 1,375 cps
at 133C: 147,000 cps
~ 3 c~
- 49 - 2004372
EXAMPLE 30
Formulation:
Parts
In,qredient by Weiqht
Methyl Glucoside 50
Corn Syrup Solids 24 35
Fructose 15
10 Properties
Dynamic Shear:
at 72F/50~ r.h.
First replicate: 49.ô2 Ibs./sq. in.
Second replicate: 92.75 Ibs./sq. in.
Percent Dynamic Shear
Retained on Conditioning: 65.43
Peel: 52C
Shear: >ô2C
~; Softening Point: ô9C
Viscosity:
at 149C:775 cps
at 143C:963 cps
at 138C: 1,250 cps
at 133C: 2,525 cps
.
-
~ v ~
- 50 - 2004372
EXAMPLES 31-42
A series of mixtures were prepared and melt
processed substantially as described above. The
5 ingredients and properties are set forth below.
Dextrose Methyl
Example Dextrose W Glucoside
Parts by Wei~ht
31 20 23 57
32 30 30 40
33 20 15 65
34 10 23 67
36 30 15 55
37 10 15 75
38 20 23 57
39 10 30 60
23 47
41 17 25 58
42 25 25 50
v~
- 51 - 2004372
Bond Humidity
Strength, Resistance,
Instron, Static Load, Soft-
70F, 300 gm. wt., ening
Viscosity 50~ r.h., 100F, Point
Example at 300F Ibs./sq. in. ô5~ r.h. (C)
31 387.537.63 45 139.1
32 1412.539.13 45 104.4
33 225.038.14 60 138.5
34 537.537.94 125 154.0
612.538.29 63 127.6
36 312.535.63 75 125.5
37 325 38.96 75 155.~
38 412.538.38 43 136.2
39 825 36.27 100 144.1
425 38.19 60 120.3
41 937.536.83 75 138.8
42 975 37.97 45 134.9
'
