US006056816A

United States Patent [19] [11] Patent Number: 6,056,816

Hagens et al. [45] Date of Patent: May 2, 2000

[54] ADHESIVE COMPOSITIONS FOR 5,194,091 3/1993 Laney .................................... .. 106/611

CORRUGATED BOXES 5,571,316 11/1996 Gill ....... .. .. 106/617
5,776,242 7/1998 Gill et al. .............................. .. 106/617
[76] Inventors: Rodger Graham Hagens, 12 Kenmore FOREIGN PATENT DOCUMENTS
Road, Hamilton, Ontario, Canada, L8S
3T7; Michael McDonald, 137 Bowling 1056107 6/1979 Canada.
Avenue, Toronto, Ontario, Canada, M6K 1122817 5/1996 China.
3A9; William Millard, 26 Maple
Avenue South, Mississauga, Ontario, Primary Examiner—Paul Marcantoni
Canada, L5H 2R6 Attorney, Agent, or Firm—Ridout & Maybee
[57] ABSTRACT
[21] Appl. No.2 09/071,880
Novel starch-silicate adhesive compositions are disclosed
[22] F1166]. May 4,1998 Which are of particular advantage in the manufacture of
corrugated board. By the controlled combination of starch,
Related US. Application Data alkali silicate and, optionally, caustic soda and boraX it has
Provisional application No. 60/045,821, May 5, 1997. been found possible to produce useable adhesives having
Int. C1.7 .................................................. .. C09J 103/02 much higher levels of solids content than conventional
U.S.C1. ....................... .. 106/617; 106/206.1; 127/29; starch-based adhesives, thereby alloWing for loWered energy
127/32; 127/71 costs in use of the adhesive formulation to manufacture
[58] Field of Search ................................... .. 106/600, 617, boXboard, as Well as improved product quality. The formu
lation of starch-silicate adhesives according to the invention
106/206.1; 127/29, 32, 71; 536/45, 124
alloWs viscosity, rheological characteristics—in particular
[56] References Cited gelation temperature—and the speed of “green-bond” for
mation to be controlled and adapted to the requirements of
U.S. PATENT DOCUMENTS modern high-speed corrugating equipment.
2,669,282 2/1954 Kreyling.
2,772,996 12/1956 Sams. 14 Claims, N0 Drawings
 6,056,816
1 2
ADHESIVE COMPOSITIONS FOR starch, clay and sodium silicate. U.S. Pat. No. 2,772,996
CORRUGATED BOXES (Sams) teaches a method of producing such an adhesive by
mixing silicate, starch and borax. More recently, Canadian
RELATED APPLICATION Patent No. 1,056,107 (Falcone, 1979) discloses a class of
starch-silicate adhesives in Which some of the starch in
This application replaces Provisional Application Ser. No. conventional starch-based adhesive compositions is
60/045,821 ?led on May 05, 1997 and entitled “Adhesive replaced by alkali silicate, but the total solids content of the
Compositions for Corrugated Boxes”. adhesive compositions is not appreciably changed.
BACKGROUND OF THE INVENTION To date, hoWever, none of the compositions or methods to
10 combine starch and silicate for the manufacture of corru
This invention relates to the manufacture of novel starch gated boxboard has found commercial application because
silicate adhesive compositions. In particular this invention none has proved to be capable of meeting the demanding
concerns the formulation of adhesives for the manufacture requirements of modern high speed corrugating equipment,
of corrugated board by the use of improved mixtures of none of the previous starch and silicate combinations having
starches and alkali metal silicates. 15 demonstrated the ability to impart higher edge crush. The
The art of using soluble alkali silicates as adhesives for principal requisites for such performance features are, ?rstly,
paper and box board has been knoWn for many years. Alkali formulation of adhesives so that their viscosity, rheology
silicates are inexpensive, ?re resistant, vermin resistant, properties, gelation temperature and speed of “green-bond”
recyclable and provide excellent strength to the products in formation are all Within a very tight range. It is thus essential
Which they are used. Among other applications these com 20 that the ?nished adhesive have loW thixotropy and a vis
pounds ?nd use as adhesives for paper products and cosity of betWeen 20—60 Stein-Hall seconds in order to
plyWood, as Well as paper cores and tubes. Alkali silicates do achieve a smooth and rapid transfer of the adhesive from the
hoWever have a number of disadvantages Which have holding tanks to the corrugator adhesive applicator stations.
resulted in the discontinuation of their use in certain indus A second essential aspect of starch based adhesive for
trial applications. 25
mulations is the temperature at Which gelation of starch
Aprimary disadvantage of silicate based adhesives is that occurs. This usually occurs at a temperature betWeen 60 and
the adhesive bond forms relatively sloWly. This is a serious 70° C. (140—160° E), operation of modern corrugating
problem in the high speed corrugating machines employed equipment not generally being possible if the gelation tem
today Which require the formation of a strong “green bond” perature is outside this range. Although the aforementioned
30
Within a very feW seconds of the linerboard and the corru Falcone patent reveals that addition of sodium silicate to
gating medium being brought into contact. Another disad starch leads to a dramatic increase in gel temperature, no
vantage of alkali silicates is that they are prone to deposit a teaching has yet been provided of hoW to formulate satis
tough, intractable glass on any surfaces upon Which they are factory starch/silicate compositions having gel temperatures
alloWed to dry. loW enough to be Within an alloWable operating range or a
35
Because starch exhibits performance properties Which are viscosity stability over time at elevated temperature, i.e.
superior in quick bond formation and does not form a tough above 50° F. (1200
deposit, starch has almost completely replaced alkali sili There is yet another aspect of starch gelation of pertinence
cates in the manufacture of corrugated boxboard some years to this invention. During the normal operating procedure the
ago. Starch itself, hoWever, is not a perfect adhesive for this 40
starch based adhesive is maintained in the storage tank at a
application. For one thing, the maximum solids content of temperature of betWeen 38—40° C. (100—104° The
such adhesive compositions usually attainable is in the range stability of conventional starch based adhesives is such that
of 25—30%. Thus some 75% of the adhesive formulation this material is prone to premature gelation due to ?uctua
applied to the boxboard consists of Water, the removal of tions in the temperature of the operating environment, and
Which reduces the operational speed of the corrugating these starch based adhesives can not be stored longer than
45
equipment, and increases the energy costs associated With about 3 days.
Water evaporation. The higher Water content of the adhesive We have discovered that by modifying starch-based adhe
also contributes to loss of paper strength as Well as quality sives by the addition of alkali silicate, in addition to other
problems during the manufacture of boxes such as Warping, ingredients such as caustic soda and borax commonly used
blistering or a “Washboard” effect. in starch adhesives, in a precisely controlled and ordered
It has also long been knoWn that the edge crush strength manner, that it is possible to realiZe all the knoWn advan
of boxes glued With starch based adhesives is not as high as tages of alkali silicates Without incurring the problems With
that Which can be attained by use of silicate. These strength viscosity or elevated gelation temperatures Which prevented
properties are noW of considerable importance, oWing to the the commercialiZation of the earlier disclosures.
fact that the speci?cation of boxes is noW based on their 55 These formulations are also found to exhibit unusually
edge crush strength (Alternate Freight Regulations Rule 41, good high temperature stability. The discovery of high
as described in Tappi test methods T811) rather than basis temperature stability has alloWed for higher temperature
Weight (as Was the case in the past). Use of silicates in the storage Which has help offset the higher gel temperature.
adhesive thus opens the possibility of manufacturing boxes Moreover We also discovered, to our surprise, that the
of equivalent edge crush strength either by using paper of a 60 methods here described alloW the preparation of starch
loWer basis Weight or by using recycled paper of poor based adhesives With very much higher solids content than
quality. previously attainable. As Will be demonstrated in the
A number of attempts have been made to combine alkali examples beloW, this discovery increases the solids content
silicates and starch in adhesives for the fabrication of of such compositions from the 25—30% range achievable
corrugated paperboard boxes and similar applications, in 65 using the conventional technology, to around 45% solids. As
order to realiZe the bene?ts described. Thus U.S. Pat. No. mentioned above, reduction of the Water content in this
2,669,282 (Kreyling) discloses an adhesive mixture of manner leads to signi?cant bene?ts in the operation of
 6,056,816
3 4
corrugating equipment by reducing the strength loss in the In the present invention, “starch” refers to the carbohy
liner and mediums caused by Water addition from the drate reserve of a plant. It is generally deposited in the form
of minute granules 1 to 100 microns and sWells in Water at
adhesive, the amount of steam energy required to evaporate
the Water and the production of boxes With improved 55 to 80° C. While starches are found throughout the plant
dimensional stability. 5 World, those of particular commercial advantage for use in
As the examples given beloW Will shoW, the invention the present invention are corn, Wheat and potato starches,
herein described also lead to improvements both in the
although others could be used, including modi?ed starches.
An example of a preferred starch is the cornstarch sold as
strength of the adhesive bond, and in the box itself. The 3005 by Corn Products International, Ill.
examples also demonstrate that these formulations are Soluble alkaline silicates useful in carrying out the present
entirely compatible With a Wide range of operational vari invention include materials in solution as Well as hydrated
ables commonly encountered and Well knoWn to those solids and anhydrous silicates, exhibiting molar ratios of
skilled in the art. SiO2 to M20 in the range of 1.5 to 4.0 Where M is preferably
either sodium or potassium. The disclosure of Canadian
applicable
Formulations
to raWaccording
and modi?ed
to the
starches
presentfrom
invention
a Wide variety
are: Patent No. 1,056,107 is hereby incorporated by reference for
of sources; (ii) compatible With insolubiliZing resins such as its general teaching of alkali metal silicates used in starch
the cross-linked polymers of melamine-formaldehyde, urea silicate adhesive compositions. A particular silicate found
formaldehyde and ketone-aldehyde commonly used to useful in the present invention is N® brand sodium silicate
impart Water resistance to starch based adhesives; and (iii) manufactured by the PO Corporation (valley Forge, Pa.),
amenable to preparation using conventional techniques for Which exhibits a Weight ratio of SiO2 to Na2O of 3.2.
preparing starch-based adhesives, such as the “tWo-stage” DETAILED DESCRIPTION OF THE
(Example 8, beloW), “no carrier” (Example 9, beloW), and INVENTION
“carrier-no carrier” manufacturing processes. Compositions according to the present invention are illus
Although most of the examples presented reveal the trated in Examples 2 and 3 in Which modi?ed and unmodi
preparation of the adhesives using liquid ingredients, ?ed carrier starches respectively are employed to prepare
Example 10 is also presented to demonstrate that similar adhesive compositions according to the invention, Which
results can be obtained if only dry ingredients are employed, exhibit superior bond and paper strength When used in the
this being of potential advantage in the commercialiZation of manufacture of corrugated boxes.
these materials. There is provided a demonstration of the superior heat
Example 11 beloW is presented to demonstrate that When stability of this composition (Example 4), and a method of
these formulations are prepared using recycled Water from varying the gelation characteristics including gel tempera
ture of the starch-silicate adhesives of the invention by
the corrugating print station (so-called “?exo” Water), the changing the relative quantities of caustic soda and borax
concentration of soluble copper in the adhesive is reduced to
an unexpectedly loW level. The importance of this observa used in their preparation (Example 5), this being of particu
lar importance to ensure that the gelation characteristics are
tion arises from the fact that although the use of ?exo Water 35
in the preparation of starch based adhesives is an increas
compatible With the operation of modern corrugating equip
ment.
ingly popular method of recycling Waste streams, the con
ventional starch based compositions employed until noW The prior art relating to starch-silicate adhesive combi
have not been found capable of reducing the solubility of nations is limited to total solids content in the range of 15 to
toxic copper ions or other metal ions present in the Waste 30%, a limit dictated by the high viscosity, instability and gel
Water. The speci?c reduction of copper observed in the temperature Which Were observed in the formulations con
compositions here disclosed is to be attributed to the Well tained Within these earlier disclosures. According to a further
knoWn sequestering properties of alkaline silicates. advantage afforded by the present invention, hoWever, a
silicate-starch adhesive may be manufactured at a solids
Although the focus of this disclosure is directed toWards
content as high as 45%. (Example 6). This grants a number
manufacture of corrugated boxes, it should also be noted that
this is but one of numerous area of potential application of
of signi?cant advantages including:
the silicate-starch compositions herein described. Adhesives (i) realiZation of energy savings as a result of a reduction
according to the invention may be used With other cellulosic of the amount of Water requiring evaporation;
materials, such as Wood and other paper products. (ii) loWer Warpage of glued boxboard product, again
because of loWer initial Water content;
SUMMARY OF THE INVENTION (iii) faster machine speeds; and
With a vieW to providing improved adhesives for the (iv) less liner and medium strength loss due to Water from
manufacture of boxes and other industrial Wood and paper the adhesive.
products, based on combinations of silicate and starch but A currently preferred embodiment of the process of the
affording the requisite control of adhesive viscosity and gel 55 invention, comprises the folloWing steps for preparing neW
temperature to permit use of the adhesives in corrugating and useful starch silicate adhesives:
equipment, the invention is directed in one aspect to adhe (a) preparing a gelled carrier portion by addition of 1.5 to
sive compositions having solids content of 30 to 45% by 10% starch by Weight of the ?nal adhesive composition
Weight and consisting essentially of: to 20 to 45% by Weight of Water, mixing until the starch
(i) 12 to 35% by Weight of a starch; 60 is dispersed in the Water, and then adding of 0.25 to
(ii) 1.5 to 12% of soluble alkali metal silicate; 2.5% by Weight of sodium or potassium hydroxide,
(iii) 0.25 to 2.5% by Weight of alkali hydroxide; after Which the composition is mixed or preferably
(iv) optionally, up to 2% borax (anhydrous or hydrated form) sheared, until a complete gel and constant viscosity of
or boric acid); and this carrier portion is obtained;
(v) 55 to 70% Water by Weight, and in another aspect, to (b) adding 10 to 30% by Weight of liquid sodium or
processes for preparing improved starch-silicate adhe potassium silicate to the carrier portion and shear
sives of this kind. mixing until homogeneous;
 6,056,816
5 6
(c) optionally, adding to the mixture produced in step (b) position demonstrates superior bond strength and edge crush
up to 2.5% by Weight of sodium or potassium strength of corrugated board made With starch/silicate.
hydroxide, after Which the material is mixed or sheared
The carrier portion of the starch/silicate adhesive is pre
until homogenous;
pared by combining 36.1 pbW Water With 4.9 pbW modi?ed
(d) optionally, adding up to 2% by Weight of borax
folloWed by mixing or shearing to constant viscosity; corn starch (Corn Products International, Surebond®) fol
(e) adding of 3 to 20% by Weight of Water and mixing or loWed by 1.0 pbW caustic (50%). The resulting slurry Was
shearing until homogenous; and held at 55° C. (131° and is alloWed to gel under loW shear
(f) adding 2 to 35% starch by Weight and shear mixing to mixing. Upon reaching a stable viscosity, 18.9 pbW sodium
constant viscosity to produce the ?nal adhesive com 10 silicate (Silicate N®, PQ Corporation) is added and mixed
position. until homogenous. 1.4 pbW caustic (50%) is added to the
As Will also be shoWn in the examples Which folloW, these mixture and mixed until homogeneous. 0.37 pbW borax
compositions are also compatible With various other chemi (pentahydrate) is added to the mixture and mixed to a stable
cals and industrial processes Well knoWn to those skilled in viscosity. 15.7 pbW Water is added and mixed until homo
the art of adhesive manufacture, such as insolubiliZing resins 15
geneous. 21.6 pbW prime (unmodi?ed) corn starch (Corn
(Example 7); the “tWo-stage” addition process (Example 8) Products International, 3005) is added to the mixture and
and “no-carrier” methods Well knoWn to those skilled in the mixed to steady viscosity. Upon completion the temperature
art (Example 9). Results
of the starch/silicate adhesive is 45° C. (113°
According to a further aspect of this invention, silicate
starch adhesives of this type can be prepared as a pre-mixed 20
dry blend by the use of a dry form of alkali silicate (Example Initial
gel
solids—35%
temp.—71°
Stein-HallC.viscosity—35s
(160° @ 51° C. (124°
10). Finally, a still further aspect of this invention illustrated
in Example 11, reveals that use of recycled “?exo” Water
results in a composition containing signi?cantly loWer levels
of soluble copper. 25
Those skilled in the art Will also be aWare that the Edge Crush of Production Board
formulating procedures herein described also apply to other
types of starches (such as acid-stable starches) as are com starch
monly used in adhesive compositions. Nor are these starch silicate
30 box type adhesive example #2
examples meant to preclude the use of other common
additives such as surfactants, or polymers such as polyvinyl lightweight 27.5 lb/in 37.9 lb/in
alcohol Which are used from time to time to enhance the medium Weight 34.5 49.2
performance of such adhesives. heavy Weight 53 73.3

EXPERIMENTAL EXAMPLES 35
In the folloWing examples, certain embodiments of the
invention are illustrated and compared to the prior art. All Example 3
proportions used in the examples are parts by Weight (pbW) The formula in Example 2 Was used to prepare a lab sample
unless otherWise noted. The ratios of the silicates are Weight to test greenbond strength (duplication of the bond strength
ratios of SiOZ/NaZO, sodium generally being the alkali metal 40 immediately off the single facer) The lab prepared sample
of choice. demonstrated signi?cantly higher green bond strength.
The ?rst example shoWn illustrates the preparation of a
typical starch based adhesive commonly used in industrial control (example #1)—332 grams of force
applications, the method of preparation of this standard starch/silicate (example #3)—449 grams of force
composition Which Will be used as a control is as folloWs: 45
Example 1 Example 4
Preparation of conventional starch based adhesive for use in Preparation of silicate-starch adhesive demonstrating high
the manufacture of corrugated boxes. temperature stability.
The carrier portion of a pure starch adhesive is prepared
The carrier portion of the starch/silicate adhesive is pre
by combining 39.2 pbW Water With 5.2 pbW modi?ed corn
pared by combining 36.0 pbW Water With 3.0 pbW modi?ed
starch (manufactured by Corn Products International under
the name Surebond®) folloWed by 1.1 pbW sodium hydrox corn starch (Corn Products International, Surebond®) fol
ide (50% solution). The resulting slurry is held at 45° C. loWed by 1.0 pbW caustic (50%). The resulting slurry is held
(1150 and is alloWed to gel While mixing under high at 60° C. (140° and is alloWed to gel under high shear
55 mixing. Upon reaching a stable viscosity, 20.0 pbW sodium
shear. Upon reaching a stable viscosity, 0.39 pbW of borax
(pentahydrate) is added to gel mixture and mixed to a stable silicate (Silicate N®, PQ Corporation) is added and mixed
viscosity. 31.41 pbW Water is added to the mixture and until homogeneous. 1.5 pbW caustic (50%) is added to the
mixed until homogeneous. 22.7 pbW prime (unmodi?ed) mixture and mixed until homogeneous. 0.37 pbW borax
corn starch (Corn Products International, 3005) is added to (pentahydrate)is added to the mixture. Upon reaching a
60
the mixture and mixed until homogeneous. stable viscosity 11.13 pbW Water is added and mixed until
Initial Stein-Hall Viscosity—25—35 seconds at 38° C. (1000 homogeneous. 27.0 pbW prime (unmodi?ed) corn starch
(Corn Products International, 3005) is added to the mixture
gel temperature—61° C. (142° and mixed to steady viscosity.
Example 2 65
An adhesive composition prepared under commercial con Initial
gel temperature—72.5°
solids Stein-Hall
content—39.1%
Viscosity—23
C. (162°seconds @ 45° C. (113°
ditions using a modi?ed carrier starch. The adhesive com
 6,056,816
8
initial
gel
solids—44.9%
temp—73°
Stein-HallC.viscosity—39
(163° seconds @45° C. (113°

Viscosity Stability
Example 7
60 min 120 min 4 hrs 7 hrs Compatibility and effectiveness of silicate-starch composi
@ @ @ @ tions with water proo?ng resins.
initial 55° C. 55° C. 55° C. 55° C.
The carrier portion of the starch/silicate adhesive is pre
example #1 50 s @ 40° C. 118 s 342 s >10 min NA pared by combining 36.1 pbw water with 4.3 pbw modi?ed
example #4 23 s @ 55° C. 22 s 22 s 23 s 22 s
10 corn starch (Corn Products International, Surebond®) fol
lowed by 1.00 pbw caustic (50%). The resulting slurry is
held at 55 ° C. and is allowed to gel under high shear mixing.
Example 5 Upon reaching a stable viscosity, 18.9 pbw sodium silicate
A method of varying the gelation characteristic of silicate (Silicate N®, PQ Corporation) is added and mixed until
starch adhesives by changing the quantities of caustic soda homogeneous. 1.4 pbw caustic (50%) is added to the mix
and borax used in their preparation. Adhesive was prepared 15
ture and mixed until homogeneous. 0.37 pbw borax
using unmodi?ed starch as the carrier. (pentahydrate)is added to the mixture. Upon reaching a
The carrier portion of the starch/silicate adhesive is pre stable viscosity 15.83 pbw water is added and mixed until
pared by combining 39.2 pbw water with 3.7 pbw prime homogeneous. 22.1 pbw prime (unmodi?ed) corn starch
(unmodi?ed) corn starch (Corn Products International, (Corn Products International, 3005) is added to the mixture
20
3005) followed by 0.78 pbw caustic (50%). The resulting and mixed to steady viscosity.
slurry is held at 45° C. (113° and is allowed to gel under Two of the more common water proo?ng resins, a
high shear mixing. Upon reaching a stable viscosity, 20.0 melamine-formaldehyde resin (Corn Products International,
pbw sodium silicate (Silicate N®, PQ Corporation) is added Coragum®) and a ketone-formaldehyde resin (Cellbond
and mixed until homogeneous. Caustic (50%) is added to the Inc., Watertite®) were post added to the prepared starch/
amount shown in the Table, and mixed until homogeneous, 25
silicate adhesive. As is the common practice in the corru
after which borax (pentahydrate)is added to the mixture as gating industry, the post addition of resin is measured as a
shown in the Table. Upon reaching a stable viscosity 12.2 percentage of starch solids.
pbw water is added and mixed until homogeneous. 23.7 pbw Starch/silicate showed no compatibility problems with
prime (unmodi?ed) corn starch (Corn Products either Coragum® or Watertite®. In the speci?c case of
30
International, 3005) is added to the mixture and mixed to Coragum®, the viscosity was monitored for 24 hrs.
steady viscosity. Gelation characteristics are determined
using a Brabender instrument.

Stability of Starch/Silicate
35 with 6% Coragum ® post added
BRABENDER RESULTS
initial 24 hour
elapsed visc @ visc @
start time to 45° C. 45° C.
2nd of maximum
NaOH borax gel viscosity brabender gel 40 starch/silicate 24 s 21 s
(pbw) (pbw) (minutes) (minutes) Visc. slope starch/silicate + 30 s 23 s"
melamine-formaldehyde
starch 0 0.25 13.5 18.5 560 112 resin
adhesive
starch/ 0.875 0.25 14.5 22 550 73.3 *sample was shear mixed for 1 minute
silicate 45
starch/ 1.75 0.25 13.0 20 920 131.4 The water resistance of starch/silicate with resin was mea
silicate sure two ways:
starch/ 1.75 0 14.0 21 660 94.3
silicate
Starch/silicate with 6% post added Coragum® was tested
by gelling the adhesive samples, submersing the samples
under water and then observing the rate of breakdown of the
gelled samples. Results showed a much slower rate of gel
Example 6 breakdown of starch/silicate with Coragum®.
A process for preparing a stable adhesive composition i. Starch/silicate with 5% post added Watertite® was tested
having a very high solids content. using TAPPI T812 and passed with equal resistance over 24
The carrier portion of the starch/silicate adhesive is pre hrs as that of the starch adhesive with 5% post added
pared by combining 36.0 pbw water with 3.0 pbw modi?ed 55
Watertite®.
corn starch (Corn Products International, Surebond®) fol
lowed by 1.00 pbw caustic (50%). The resulting slurry is Example 8
held at 60° C. (140° and is allowed to gel under high Starch/silicate adhesive prepared using the two-stage Stein
shear mixing. Upon reaching a stable viscosity, 22.0 pbw Hall method.
sodium silicate (Silicate N®, PQ Corporation) is added and 60 This method is conventionally used in preparing starch
mixed until homogeneous. 1.5 pbw caustic (50%) is added only adhesives for making corrugated boxboard. We have
to the mixture and mixed until homogeneous. 0.40 pbw found that it can readily be adapted to the making of
borax (pentahydrate)is added to the mixture. Upon reaching starch-silicate adhesives according to the present invention
a stable viscosity 4.1 pbw water is added and mixed until by process steps such as the following:
homogeneous. 32.0 pbw prime (unmodi?ed) corn starch 65 The ?rst stage is prepared by combining 13.31 pbw water
(Corn Products International, 3005) is added to the mixture with 3.63 pbw modi?ed corn starch (Corn Products
and mixed to steady viscosity. International, Surebond®) followed by 1.03 pbw caustic
 6,056,816
9 10
(50%). The resulting slurry is held at 57° C. (135° and is modi?ed corn starch (CPC surebond®) folloWed by 1.0 pbW
allowed to gel under high shear mixing, after Which 9.70 caustic (50%). The resulting slurry is held at 55° C. and is
pbW Water is mixed into the gel. alloWed to gel under high shear mixing. Upon reaching a
The second stage is prepared by combining 34.87 pbW stable viscosity, 18.9 pbW sodium silicate (Silicate N®, PQ
Water With 15.98 pbW sodium silicate (Silicate N®, PQ Corporation) is added and mixed until homogeneous. 1.4
Corporation) folloWed by 0.73 pbW caustic (50%) and then pbW caustic (50%) is added to the mixture and mixed until
0.41 pbW borax (decahydrate)and ?nally 20.34 pbW prime homogeneous. 0.37 pbW borax (pentahydrate)is added to the
(unmodi?ed) corn starch (Corn Products International, mixture. Upon reaching a stable viscosity 15.83 pbW ?exo
3005). Water is added and mixed until homogeneous. 22.1 pbW
The ?rst stage mix is dropped into the second stage mix 10 prime (unmodi?ed) corn starch (CPC 3005) is added to the
over a 20 minute time period. The combined mixes are mixture and mixed to steady viscosity.
stirred to steady viscosity
pH—11.2
24
Initial
gel hour
temperature—72°
Stein-Hall
viscosity Viscosity—24
at 120F—29
C. (162° seconds
seconds @
@ 45°
45° C. (113°
initial
gel
solids
temperature—68°
Stein-Hall
content—31.2%
Viscosity—62s
C. (1540 @34° C. (94°
15
green bond strength—475 grams of force solids—35 . 1 %
This results in a composition containing loWer levels of
Example 9 soluble copper as measured by atomic absorption spectrom
The “No carrier” technique used in manufacturing starch etry.
adhesives is characteriZed by the fact that controlled sWell 20 Starch/silicate—31 ppm measurable copper
ing of all of the starch is determinative of the ?nished
adhesive viscosity. As adapted to the preparation of starch “?exo” Water*—56 ppm measurable copper
silicate adhesives according to the present invention, vis What is claimed is:
cosity increase is terminated by the addition of a second 1. A process for preparing an adhesive composition,
portion of silicate. comprising the steps of:
25
The starch/silicate adhesive is prepared by combining (a) preparing a gelled carrier portion, by adding from 1.5
40.0 pbW Water With 9.5 pbW sodium silicate (Silicate N®, to 10% by Weight of a starch, based on the Weight of
PQ Corporation) folloWed by 2.5 pbW caustic (50%)and said adhesive composition, to 20 to 40% by Weight of
then 0.37 pbW borax (pentahydrate). To the resulting solu Water, mixing to disperse the starch in the Water, then
tion is added 25.0 pbW prime (unmodi?ed) corn starch (Corn 30
adding from 0.25 to 2.5% by Weight of NaOH or KOH
Products International, 3005) under agitation. Upon reach and mixing to constant viscosity to produce the gelled
ing a viscosity of ~7000 cps @ 35° C. (95° the viscosity carrier portion;
advancement is halted by the addition of 10.5 pbW sodium (b) adding to said gelled carrier portion from 10 to 30%
silicate (Silicate N®, PQ Corportation). 12.13 pbW Water is by Weight of a Water-soluble alkali metal silicate char
added to further reduce viscosity. 35 acteriZed by a molar ratio SiO2:M2O in the range from
1.5 to 4.0, Where M is Na or K, then mixing the Whole
Initial
gel
18 hrtemperature—74°
viscosity
viscosity—21s
(stored@
C.at 36°
(165°
50° C. (97°
)—21s @ 45° C. (113° until substantially homogeneous;
(c) adding a further 3 to 20% by Weight of Water and
Example 10 mixing until homogeneous; and
Silicate-starch adhesives prepared as a dry blend by the use 40 (d) adding a further 2 to 25% by Weight of starch and
of a solid form of alkali silicate. mixing until viscosity is substantially constant to pro
Prior to making the adhesive mix, a dry blend is prepared duce a ?nal adhesive composition having a solids
by combining 72.29 pbW prime (unmodi?ed) corn starch content betWeen 31.2% and 45% by Weight.
(Corn Products International, 3005) With 26.50 pbW sodium 2. A process according to claim 1, comprising the addi
silicate poWder (Silicate G®, PQ Corporation) and 1.21 45 tional step, subsequent to step (b) and before step (c), of
borax (pentahydrate). adding further NaOH or KOH up to 2.5% by Weight and
The carrier portion of the starch/silicate adhesive is pre mixing to homogeneity.
pared by combining 36.1 pbW Water With 4.3 pbW modi?ed 3. A process according to claim 1, comprising the addi
corn starch (CPC surebond®) folloWed by 1.0 pbW caustic tional step, subsequent to step (b) and before step (c), of
(50%). The resulting slurry is held at 55° C. (131° and is adding up to 2% by Weight of borax and mixing to homo
alloWed to gel under high shear mixing. Upon reaching a geneity.
stable viscosity the gel is diluted With 26.22 pbW Water. To 4. A process according to claim 1, comprising the addi
the diluted gel is added 30.57 pbW of the previously pre tional steps, subsequent to (b) and before step (c), of adding
pared of starch/sodium silicate/borax dry mix. After thor further NaOH or KOH up to 2.5% by Weight, mixing to
oughly mixing until homogeneous, 1.81 pbW high alkaline 55 homogeneity, then adding up to 2% by Weight of borax and
sodium silicate (metso pentabead®, PQ Corportation) is again mixing to homogeneity.
added to the mixture and mixed to steady viscosity. 5. Aprocess according to claim 4, Wherein said starch is
selected from the group consisting of corn starch, Wheat
gel
Initial
temperature—73°
Stein-Hall viscosity—35s
C. (163° at 45° C. (113° starch, potato starch and modi?ed starches.
pH—11.2 60 6. Aprocess according to claim 5, Wherein said starch is
corn starch.
solids—37.2%
7. Aprocess according to claim 5, Wherein said starch is
Example 11 SUREBOND (trade-mark) modi?ed corn starch (Corn Prod
Preparation of silicate-starch adhesives using recycled Water ucts International).
from corrugator print station. ie. “?exo” Water. 65 8. A process according to claim 4, Wherein said alkali
The carrier portion of the starch/silicate adhesive is pre metal silicate is sodium silicate exhibiting a Weight ratio of
pared by combining 36.1 pbW “?exo” Water With 4.3 pbW SiO2:Na2O of about 3.2.
 6,056,816
11 12
9. A process for preparing an adhesive composition, (b) adding to the solution produced in step (a) from 20 to
comprising the steps of: 30% by Weight of starch under agitation and monitor
(a) preparing a gelled carrier portion by adding from 1.5 ing the increasing viscosity;
to 10% by Weight of a starch, based on the Weight of (c) adding betWeen 8 to 15% by Weight of sodium silicate
said adhesive composition, to 20 to 40% by Weight of to terminate the increase in viscosity; and
Water, mixing to disperse the starch in the Water, then (d) adding up to 15 % by Weight of Water to adjust the ?nal
adding from 0.25 to 2.5% by Weight of NaOH or KOH
viscosity to betWeen 20 and 60 Stein-Hall seconds and
and miXing to constant viscosity; and
the solids content of the adhesive composition to a level
(b) adding to said gelled carrier portion about 30% by betWeen 31.2% and 45% by Weight.
Weight of a dry-blended mixture comprising about 72 11. An improved adhesive composition for cellulosic
parts by Weight of corn starch, about 26 parts by Weight materials, having a solids content of betWeen 31.2 and 45
of Water-soluble sodium silicate poWder and the bal percent and consisting essentially of:
ance boraX pentahydrate poWder, then shear miXing the
dry-blended miXture into said gelled carrier portion (i) 12 to 35% by Weight of a starch;
15 (ii) 1.5 to 12% by Weight of a soluble alkali metal silicate;
until a steady viscosity is reached, to produce a ?nal
adhesive composition having a solids content betWeen (iii) 0.25 to 2.5% by Weight of an alkali hydroXide;
31.2% and 45% by Weight. (iv) from 55 to 70% by Weight Water.
10. A process for preparing an adhesive composition, 12. An adhesive composition according to claim 10,
comprising the steps of: further comprising up to 2% of boraX or boric acid.
20
(a) preparing a solution containing 35 to 55% by Weight 13. An adhesive composition according to claim 11,
of Water, based on the Weight of said adhesive Wherein said starch is corn starch.
composition, With 7.5 to 12.5% by Weight of sodium 14. An adhesive composition according to claim 11,
silicate and subsequently adding from 1 to 2% by Wherein said silicate is sodium silicate.
Weight of sodium hydroXide or potassium hydroXide,
then adding up to 2% by Weight of boraX;