Note: Descriptions are shown in the official language in which they were submitted.
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'TITLE
1'~APER SIZING
BACKGROUN17~ OF THE INVENTION
This invention relates to a method of improving high speed precision
conversion
performance of paper by surface treating paper with a reactive sizing agent
and a filler and to
paper so made.
Manufacture of paper produced under alkaline conditions has increased rapidly
in recent
years. Alkaline fine paper generally performs well in most down stream end use
applications,
but high speed converting and high speed reprographic operations often present
severe paper
handling requirements for paper so used, including alkaline fine paper.
15 Precision converting applications for alkaline fine paper, such as forms
bond and copy
paper, can result in high speed runnability problems. Typical handling
problems associated with
high speed converting or high speed reprographic operations using alkaline
fine paper containing
an internal reactive size include reduced operating speeds, double feeds or
jams in high speed
copiers, paper welding, and registration errors on high speed folding
equipment and printing
zo equipment. Alkaline paper grades that are often used in high speed
precision handling
equtprnent include copy paper, forms bond, envelope paper and adding machine
tape. These
paper grades represent a significant segment of the market for alkaline fine
paper so there is a
need for alkaline fine paper suitable for use in high speed precision
converting applications.
including high speed reprographic operations.
zs Sizing agents are typically added to.alkaline fine paper, either as an
internal sizing agent
or as a surface-applied sizing agent to effect changes in the paper's physical
characteristics, e.g.,
the sizing property of the paper, a measure of the resistance of a
manufactured paper to the
penetration or wetting by an aqueous liquid. The sizing property and sizing
agent used can have
a significant impact on the handling characteristics of the paper in
subsequent end use
3o applications such as high speed converting or reprographic operations.
Sizing agents are
therefore often added to alkaline fine paper as internal sizes to improve the
runnability of the
paper-making equipment and of the performance of the resultant paper in end
use applications.
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The two most commonly used internal sizing agents for paper made under
alkaline
conditions are alkyl ketene dimer (AKD) and alkenyl succinic anhydride (ASA).
Both of these
sizing agents are so-called reactive sizes since each has a reactive
functional group that
covalently bonds to cellulose pulp and hydrophobic tails that are oriented
away from the pulp
once the size-cellulose reaction has occurred. The nature and orientation of
the hydrophobic tails
on the reactive sizes provide the water-repellency property in the sized
paper.
AKD- and ASA-based reactive sizing; agents are widely used in commercial
practice for
sizing alkaline fine paper but each has shortcomings that adversely affect the
manufacturing
processes used to make alkaline fine paper internally sized with either of
these sizes. Moderate
to addition levels of ASA as an internal size can cause undesirable deposits
an the papermaking
equipment, web breaks and holes in the paper. Addition levels of ASA-based
sizing agents of
about I .0 - I .25 kg/metric tonne of paper generally lead to unacceptable
papermaking machine
runnability and paper quality problems. However, addition levels greater than
1.0 - 1.25
kg/metric tonne of paper are often required to meet end-use sizing
requirements, especially for
15 high levels of filler added to the paper fumis;h.
AKD-based sizing agents are more satisfactory than ASA-based sizing agents in
these
respects, but AKD sizing agents generally exhibit a slower rate of size
development than ASA
sizing agents. Consequently, an extended period of curing may be required with
alkaline paper
internally sized with AKD before its sizing development is complete. However,
AKD sizing
?o development is generally completed by the time the paper has reached the
reel in the
papermaking process.
Both ASA- and AKD-based sizing agents have been associated with handling
problems
in high speed paper handling applications for alkaline paper internally sized
with these sizing
agents.
'-5 Non-reactive polymeric sizes such as styrene malefic anhydride (SMA) avoid
many of the
paper handling problems on high speed converting equipment and high speed
reprographic
equipment associated with AKD and ASA, primarily due to the high molecular,
weight of such
polymeric sizes. Polymeric sizes are generally applied as a surface size
typically at the size press
in the papermaking process, in contrast to th.e internal addition of ASA- and
AKD-based sizing
o agents.
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Despite this apparent advantage of polymeric surface sizes, ASA- and AKD-based
sizing
agents are nevertheless preferred in commercial papermaking processes because
of their cost and
sizing efficiency. Polymeric surface sizes, oru a weight basis, are 50% more
expensive than
AKD- and ASA-based sizing agents. In addition, AKD and ASA exhibit very high
relative
sizing efficiency, being 2-3 times more efficient than a typical polymeric
surface size on an
equal weight basis. These factors make both AKD- and ASA-based sizing agents
far more cost-
effective and efficient for obtaining a given level of sizing development in
paper. Consequently,
there is a need to improve the high speed converting and reprographic
performance of alkaline
fine paper that is sized -with a reactive size, such as AKD, ASA, or the like.
to Reactive sizes such as AKD may be categorized as 2-oxetanone sizing agents,
which
include ketene dimers containing one (3-lactone ring, e.g., alkyl ketene
dimers, and ketene
multimers, containing more than one such ~3-lactone ring, e.g., alkyl ketene
multimers. Such 2-
oxetanone reactive sizing agents and their preparation are described in EP-A1-
0 629 741 of
Zhang et al., in U.S. Patent 5,685,815 of Bottorff et al., and in U.S. Patent
No. 5,846,663 of
Brungardt et al., the disclosures of which are hereby incorporated by
reference.
The present invention provides for improved high speed runnability of alkaline
fine paper
that is surface treated with a reactive size.
SUMMARY OF THE INVENTION
One aspect of this invention is a method of improving high speed precision
paper
2o converting or reprographic operations by surface sizing paper used in high
speed precision
converting or reprographic operations with a reactive sizing agent and an
inorganic filler, the
inorganic filler being applied in an amount effective to improve paper
runnability with the
weight ratio of inorganic filler to surface sizing agent being about 0.1:1 to
about 10:1.
Another aspect of this invention is a method of improving high speed precision
paper
converting or reprographic operations by surface sizing paper used in high
speed precision
converting or reprographic operations with a reactive sizing agent that is a 2-
oxetanone that is a
liquid at 35 °C and an inorganic filler selected from the group
consisting of kaolin, titanium
dioxide, silicon dioxide; bentonite and calcium silicate, the inorganic filler
being applied in an
amount effective to improve paper runnability with the weight ratio of
inorganic filler to surface
sizing agent being about 0.1:1 to about 10:1.
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Still another aspect of this invention is a sizing composition useful as a
surface size for
alkaline fine paper comprising a 2-oxetanone reactive sizing agent that is a
liquid at 35°C and an
inorganic filler, the weight ratio of inorganic; filler to reactive sizing
agent being about 0.1:1 to
about 10:1.
Paper made by the method of this invention is yet another aspect of the
present invention.
DETAILED DESCRIPTION OF THE INVENTION
The method of the present invention provides for the improvement of high speed
precision paper converting performance and reprographic operations with
surface-sized paper
used in such operations by the application of a reactive surface size to
alkaline fine paper in
1o combination with an inorganic filler, both being applied to the surface of
the paper and the
inorganic filler being present in an amount effective to improve paper
runnability with the
weight ratio of inorganic filler to surface sizing agent being about 0.1:1 to
about 10:1.
"Precision" converting, as used herein, refers to precision high speed
converting and
reprographic operations carried out on equipment that handles high throughput
paper volumes,
t5 requiring-precise control during such high rate paper handling. The linear
speed at which paper
is processed through precision converting equipment is high, e.g., about 500
to about 2000
ft/rnin (about I60 to about b60 m/min) being typical, with cut size paper
generally being sheeted
at the lower end of this range, i.e., about 500 to about 850 fUrnin (about 160
to about 280
m/min). Precision high speed reprographic equipment is generally operated at
speeds that
2o process at least about 50 sheets of cut paper per minute. The IBM 3800 high
speed laser printer,
used in the Examples to illustrate high speed reprographic operations,
typically processes about
180 sheets per minute.
The paper sizing agent used as a surface size in this invention is a reactive
sizing agent.
The reactive sizing agent is preferably a 2-oxetanone sizing agent. The 2-
oxetanone compound
25 may contain a single ~3-lactone ring, e.g., a ketene dimer, or may contain
two or more ~i-lactone
rings, e.g., ketene multimers. The 2-oxetanone reactive sizing agent of this
invention may be an
alkyl ketene dimer, an alkyl ketene multime:r, an alkenyl ketene dimer, an
alkenyl ketene
multimer, or mixtures of such dimers and/or multimers.
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Commercially available alkyl ketene dimer (AKD) sizing agents are typically
solids at
temperatures of about 20-30°C and are generally made by the
dimerization of two saturated,
straight-chain fatty acid chlorides, e.g., stearic acid chloride and palmitic
acid chloride.
The 2-oxetanone reactive sizing agent of this invention is preferably a liquid
at 35°C,
i.e., it is not a solid at 35°C, preferably is a liquid at 25°C,
and is also preferably a liquid at
20°C. Those 2-oxetanone compounds having these desirable non-solid
(liquid) characteristics at
the specified temperatures are generally characterized by containing
hydrocarbon substituents
with irregularities that may be branched alkyl, linear alkenyl or branched
alkyl. Such liquid 2-
oxetanone compounds generally are mixtures of compounds that contain a
significant
percentage, e.g., at least about 25 wt%, more preferably at least about 50 wt%
and most
preferably at least about 75 wt%, of 2-oxetanone which is liquid at 35
°C (preferably 25 °C or
preferably 20°) containing at least one hydrocarbon substituent with an
irregularity in the
chemical structure of these substituents, such as branching and/or carbon to
carbon double
bonds, i.e., unsaturation. Such liquid 2-oxetanone compounds may be ketene
dimers, ketene
t 5 multimers or mixtures of these.
A general structure of a 2-oxetanone compound useful as a reactive sizing
agent is as
follows:
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in which formula n can be 0 (e.g., a ketene dimer) or n can be 1 or more (
e.g., a ketene
multimer), preferably n being 1 to about 20 and more preferably n being at
least 1 to about 8.
Ketene multimers are typically mixtures, and mixtures of the 2-oxetanone
multimers
typically contain regio isomers of such multimer compounds and typically
contain an average n
of from about 1 to about 8. Such mixtures of 2-oxetanone multimers may also
contain some 2-
oxetanone dimers, i.e., n equals 0 in the general formula noted above, which
is a consequence of
the preparation method conventionally used to make 2-oxetanone multimers. The
2-oxetanone
dimers and multimers may be prepared from reaction of a monoacid component,
e.g., a fatty
acid, and a diacid component, e.g., a dicarboxylic acid.
to In the general formula for 2-oxetanone dimers and multimers, R and R" are
substantially
hydrophobic in nature and rrtay be the same or different. They are typically
acyclic and are
preferably hydrocarbons of at least about 4 carbon atoms in length, preferably
about C 10 - C20
and are preferably independently selected from the group of straight (linear)
or branched alkyl or
straight (linear) or branched alkenyl hydrocarbon substituents. R' is
preferably a straight chain
alkyl, with about C2 - C14 being more preferred and about C4 - Cg being most
preferred. R'
may also be alicyclic (linear, branched or cyclic) having 28-40 carbon atoms,
typically being
derived from a C32 - C~ dicarboxylic acid.
Ketene multimers useful in this invention made be made by conventional
methods, e.g.,
from the reaction of a fatty acid or other monocarboxylic acid with a
dicarboxylic acid.
Reactive sizing agents based on 2-oxetanone compounds and their preparation
are well
known in the paper sizing art. The 2-oxetanone sizing agents used in this
invention, including
the preferred liquid 2-oxetanone compounds, may be made by conventional
methods, such as
those described for solid ketene multimers in U.S. Patent 5,685,815 of
Bottorff et al. , the
disclosure of which is hereby incorporated by reference.
The reactive sizing agent of this invention is generally formulated as an
aqueous
emulsion. Such aqueous emulsions are well known in the paper sizing art and
may contain from
about 1 to about 50 wt% of the sizing agent active component, e.g., 2-
oxetanone compound, and
preferably contain about 5 to about 35 wt% of sizing agent, all percentages
based on the total
weight of the emulsion. Such aqueous emulsions typically contain an
emulsifying agent that is
3o generally employed in an amount in the range of about 0.1 to about 5 parts
by weight, more
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preferably about 0.2 to about 3 parts by weil;ht, all parts being based on the
weight of the sizing
agent. Such emulsions may be prepared by conventional methods, using either
low shear or high
shear techniques, .and these procedures are well known in the papermaking art.
The inorganic filler that is an essential component in the method of this
invention is a
finely divided inorganic material that has a relatively high surface area. The
inorganic filler
preferably has a particle size distribution in which the mean particle size of
less than bout 10
microns, more preferably less than about ~ microns, and most preferably less
than about 2
microns.
The inorganic filler of this invention is preferably kaolin clay (China clay),
titanium
dioxide, silicon dioxide (silica, precipitated amorphous silica, and the
like), bentonite (a
naturally occurring sodium triontmorillonite), calcium silicate (e.g.,
precipitated amorphous
calcium silicate) or mixtures of these. Other inorganic fillers having the
finely divided particle
size and absorptivity characteristics of these preferred fillers may also be
used. Other inorganic
fillers include diatomaceous earth, sodium a.lumino silicates, precipitated
amorphous silicates,
ground calcium carbonate, precipitated calcium carbonate (pcc), talc, i.e.,
hydrated magnesium
silicate, alumina including hydrated alumina, i.e., aluminum hydroxide,
diatomaceous earth, and
the like.
The weight ratio of inorganic filler to reactive surface size that is applied
as a surface
treatment of the paper being treated should be from about 0.1:1 to about 10:1
or higher,
2o preferably from about 0.2:1 to about 5:1. The precise weight ratio selected
for filler to surface
size generally depends on the inorganic fillers used and the physical
characteristics of the
inorganic filler selected. For example, kaolin clay preferably is surface
applied at a weight ratio
of kaolin clay to reactive surface size of at least about 0.5:1. More
preferably, the weight ratio of
kaolin clay filler to surface size is at least about 1:1, up to about 5:1,
more preferably about 1.5:1
?5 to about 3:1. For the preferred silicon dioxide and titanium dioxide
fillers, the weight ratio of
inorganic filler to surface size is at least about 0.5:1, with about 1:1 to
about 5:1 being preferred.
With bentonite as the filler, the weight ratio of bentonite to surface size is
preferably at least
about 0.1:1, more preferably 0.2 to about 10:1, and most preferably about
0.2:1 to about 3:1.
Addition levels of the surface size on the paper being treated are generally
selected to
3o provide the desired sizing characteristics sought for the end-use
applications for such paper.
SU6STiTIrTE SHEET (RULE 26)
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Addition levels of reactive sizes such as the preferred 2-oxetanone reactive
size may range from
about 0.02 to about 5 kg/metric tonne, more' preferably about 0.1 to about 3
kg/metric tonne and
most preferably about 0.5 to about 2 kg/metric tonne of paper, all based on
the weight of dry
paper. These addition rates refer only to surface sizing and do not include
internal size, if any, in
the paper. Addition levels of the inorganic filler will depend on the addition
rate of the reactive
size used and are generally adjusted to provide a weight ratio of inorganic
filler to surface size
within the ranges specified above.
The reactive size and inorganic filler are applied as a surface treatment to
the paper in the
method of this invention. The reactive surface size and inorganic filler are
normally applied as a
to surface treatment to both sides of the paper being treated, but if desired
surface application could
be made to only one side of the paper sheet.
The reactive size and the inorganic filler are preferably applied to the paper
surface
concurrently, e.g., in a single operation, although the two components could
alternatively be
applied as separate treatments, e.g., in separate steps. A preferred method of
application is by
t 5 use of a conventional size press. The reactive size and inorganic filler
are preferably applied to
the surface of the paper being treated via a size press, with both the
reactive size and the filler
being introduced into the size press solution. The inorganic filler may be
introduced to the size
press solution (or other aqueous medium) as a dry powder or as an aqueous
slurry containing the
filler.
Zo Other surface application methods may also be used to apply the reactive
size and the
inorganic filler to the surface of the paper being treated, such as
conventional coating or spraying
techniques, and surface application may also be made at points other than the
size press in the
papermaking process, e.g., at the calender stack. After surface application of
the reactive size
and the inorganic filler in this invention, the surface treated paper is dried
by conventional
25 methods. The desirable characteristics of alkaline paper treated according
to this invention are
discussed below.
The reactive sizing agents of this invention applied as a surface size may
also contain or
be used in combination with water soluble inorganic salts. Such water soluble
inorganic salts
may include a calcium halide, a magnesium halide, a sodium halide or the like.
Calcium
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chloride, magnesium chloride and sodium chloride are particularly preferred as
the water soluble
inorganic salt.
Other optional components conventionally used in surface sizing or surface
treatment
techniques may be used. Such additives conventionally used in paper making
include starch,
polymeric surface sizing agents, and the like. The method of this invention
may be used with or
without commonly used size press starches. Such size press starches may
include ethylated
starch, enzyme-converted starch, cationic starch, oxidized starch and pearl
starch. Starch
addition levels useful with this invention ma:y range from 0 to 100 kg/rnetric
tonne of paper, and
such starch addition may be made via the size press. Polymeric surface sizing
agents that may
be used in combination with this invention include styrene rnaleic anhydride
copolymers and
styrene acrylates. The water-soluble inorganic salts mentioned above may be
used in
combination with the reactive surface size and/or inorganic filler and/or
other conventional paper
processing components.
In one preferred embodiment a 2-oxetanone sizing agent which is liquid at
35°C,
preferably 20°C, such as alkenyl or branched alkyl ketene diner is used
in combination with at
least one other sizing agent. Useful other sizing agents include alkenyl
succinic anhydride (see,
e.g., U.S. Patent No. x,766,417) and straight chain alkyl ketene diner (see,
e.g., U.S. Patent No.
5,725,731). Sizing agents comprising ?-oxetanones of different types useful in
such an
embodiment can be prepared by mixing fatty acids and forming the 2-oxetanones
or blending 2-
zo oxetanones.
The paper used in the method of this invention is not critical and may be any
paper grade
that requires sizing in its normal end-use application. The present invention
is intended for use
with alkaline, including neutral, paper that is made by an alkaline or neutral
papermaking
process, and such papermaking processes arE: well known to those in the
papenmaking art.
The invention is most useful with precision paper handling grades of paper,
particularly
alkaline fine paper. These grades include forms band, cut size paper, also
called cut sheet paper,
copy paper, envelope paper, adding machine; tape, and the like. The basis
weight of the alkaline
paper used in this invention may range from about 30 to about 200 g/m~ and is
preferably within
a range of about 40 to about 100 g/m~.
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The paper used in this invention may be made with or without conventional
internal sizes
being present. Internal sizing agents, if used, may be present at addition
levels ranging from
about 0.02 to about 4 kg/mefric tonne of paper, more preferably about 0.25 to
2.5 kglmetric
tonne and most preferably about 0.5 to about 2.0 kg/metric tonne of paper.
Conventional
internal sizes may be used and these include alkenyl succinic anhydride (ASA)
sizing agents and
2-oxetanone sizing agents, e.g., alkenyl ketene dimer and multimer sizing
agents being preferred,
as well as other reactive and non-reactive in.temal paper sizing agents. Such
internal paper sizes
may include and/or be identical to the reactive surface sizes used in the
present invention.
Paper made by the method of this invention exhibits excellent paper handling
1o performance, particularly in applications inwolving high speed precision
conversion or high
'speed precision reprographic operations. Fine paper grades that require good
runnability on high
speed paper handling equipment may be surface treated with reactive size in
the method of this
invention to provide increased sizing agent efficiency, improved ink jet print
quality, and a
reduction of the amount of internal sizing agent added at the wet end of a
paper making process.
15 Surface application of reactive sizing agents, to reduce or eliminate the
amount of
internal sizing agent required for such paper, improves paper making
efficiency by eliminating
the associated wet end deposits from such i:nternai sizing agents. Even
moderate addition levels
of reactive sizes, particularly alkenyl succinic anhydride sizing agents, can
cause deposits on the
paper machine, web brakes and holes in the paper. Addition levels of ASA as an
internal size
?0 greater than about 1 - 1.25 kglmetnic tonne are often required to meet end
use sizing
requirements, but such internal size additional levels generally lead to
unacceptable paper
machine ntnnability and paper quality problems. The method of the present
invention reduces or
eliminates the need for such internal size addition by providing for the
surface treatment of paper
using reactive surface sizes, to provide the desired sizing characteristics
and other physical
?~ properties sought for such paper, but without compromising or deteriorating
high speed
convertibility and runnability for such surface-sized paper on high speed
paper handling
equipment.
The method of the present invention permits the use of 2-oxetanone reactive
sizing
agents such as alkyl ketene dimers and/or rnultimers and alkenyl ketene dimers
and/or multimers
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as surface sizes, and concomitantly provides for good runnability of such
surface-sized paper on
high speed paper handling equipment.
The method of this invention is particularly useful for 2-oxetanone reactive
sizing agents
that are liquids at temperatures of about 20°(: to about 30°C,
e.g., alkenyl ketene dimer and/or
multimer sizing agents. The method of this invention permits the addition of
these and other
reactive 2-oxetanone sizing agents as surface sizes, e.g., via addition at the
size press, to provide
the desired sizing performance characteristics required for alkaline fine
paper. Although use of
such 2-oxetanone reactive sizes as surface treatments for paper ordinarily can
lead to reduced
running speeds in high speed precision converting and reprographic operations
for such surface-
t0 sized paper (or, alternativeiy,'an increase in handling problems at normal
high speed operation of
such equipment), the use of the inorganic filler in the method of this
invention provides good
runnability for such surface sized paper on high speed precision paper
handling equipment.
The following non-limiting Examples described below illustrate various aspects
of the
present invention.
t s E~;A.MPLES
The procedures used in the Examples are pilot scale procedures that mimic a
full
scale paper machine size press application. 'fhe paper in the following
Examples was prepared
on a pilot paper machine at Western Michigan University. A representative fine
paper furnish
was used with the Western Michigan University paper machine, to make a typical
forms bond
?4 paper-making stock. The pulp furnish (three parts hardwood kraft pulp and
one part softwood
kraft pulp) was refined to 425 ml Canadian Standard Freeness (C.S.F.) using a
double disk
refiner. Prior to the addition of the filler to the pulp furnish, the pH (7.8 -
8.0), alkalinity ( 150 -
200 ppm) and hardness (100 ppm) of the paper making stock were adjusted using
appropriate
amounts of NaHC03, H~S04 and NaOH. The filler added to the pulp furnish was
10% medium
z5 particle-size precipitated calcium carbonate, in particular, Albacar~ 5970
precipitated calcium
carbonate (available from Specialty Minerals Inc., Bethlehem, PA) which was
added at a rate of
100 kg/metric tonne and was added at the machine chest.
Wet-end additions of internal sizing agents were made as follows:
2-oxetanone reactive size (i.e., alkenyl keten:e dimer unless noted otherwise)
was added at the
3o second mix box at a rate of 0.47 kg/metric tonne; quaternary amine-
substituted cationic starch
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(STA-L~K= 400 starch, available from A.E. Staley Company, Decatur, Illinois)
was added at
the first mix hox overflow at a rate of 5.0 kg/metric tonne; and alum was
added at the second
mix box overflow at a rate of 2.0 kg/metric tonne. Stock temperature at the
whitewater tray was
controlled at 49°C.
The wet presses were set at 207 cm I-Ig. A drier profile that gave 2-3%
moisture at the
size press and 4-6% moisture at the reel was used, and the paper machine speed
was 0.39
meter/sec.
Approximately 20 kg/metric tonne of oxidized corn starch (GPCJ
D-15F corn starch, available from Grain Processing Company, Muscatine, Iowa)
and 2.5
t4 kg/metric tonne ofNaCl were added at the size press (54°C, pH 7.5 -
8.0). All alkaline paper
used in the Examples described below was surface treated with the starch-
containing size press
solution, unless noted otherwise (e.g.. conventional acid paper being an
exception). In addition
and as described in the Examples, a 2-oxetanone reactive size and/or filler
were also added at the
size press, to evaluate the effect of these components on the convertibility
performance of the
IS surface treated paper. Calender pressure and reel moisture were adjusted to
obtain a Sheffield
smoothness of 150 flow units at the reel (column no. 2, felt side up).
A 35 minute roll of paper at each paper making condition was collected and
converted on
a commercial forms press to two boxes of standard 8~ x 1 I" forms. Samples
were also collected
before and after each 35-minute roll for a determination of basis weight
(generally 46 lbs/3000
Zo sq.ft. (75 kg11000 m'-)) and smoothness.
In order to evaluate various surface treatments and their effect in preventing
difficulties
in converting operations, the paper was made. on the Western Michigan
University pilot paper
machine, converted into forms, and then printed on a IBM 3800 high speed
continuous forms
laser printer, as a measure of its converting performance. The converted paper
was allowed to
?5 equilibrate in the printer room for at least one day prior to evaluation.
Each box of paper provided an amount of paper sufficient to allow a 10-14
minute ( at 67
meters/min.) evaluation on the IBM 3800 high speed laser printer, which served
as an effective
testing device for determining convertibility performance for the surface-
treated paper on state of
the art converting equipment. In particular, the phenomenon of "billowing"
gives a measurable
3o indication of the extent of slippage on the IBM 3800 printer between the
undriven roll beyond
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the fuser and the driven roll above the slacker. Such billowin5 involves a
divergence of the
paper path from the straight line between the rolls. which is ? inches (~ cm)
above the base plate,
causing registration errors and dropped folds in the slacker. The billowing
during steady-state
running time is measured as the billowing height (in inches or centimeters)
above the straight
line paper path after 600 seconds (10 min.) of running time. The faster and
higher the sheet
billows, the worse the converting perforrnanc;e for such paper. ~ All samples
reported in the
Examples were tested in duplicate, since two boxes from each run (roll) were
available for
testing.
Example 1
to Example 1 describes the evaluation of high speed precision converting
performance of
paper made as described above and surface treated with a 2-oxetanone reactive
size in
combination with various inorganic fillers. Fiigh speed converting performance
was measured
using an IBM 3800 high speed Iaser printer, in which the maximum billowing
height was
determined after 10 minutes of operation using the paper being evaluated.
Results of all
IS evaluations described in this Example 1 are summarized in Table 1 below.
Two baseline control examples were carried out. Control 1 A was an evaluation
of a prior
art acid fine paper made in a conventional manner with rosin and alum as the
internal size and
with no surface treatment being carried out. Evaluation of the high speed
converting
performance for the acid fine paper of Control lA gave a billowing maximum
height after 10
2o minutes of 2.5 - 2.75 inches (6.4 - 7.0 cm), indicating excellent high
speed runnability.
Control 1B, the second benchmark control, was an alkaline paper made as
described
above with an internal size that was an alkenyl ketene dimer added at the wet
end at a rate of
0.47 kglmetric tonne of paper. This alkaline fine paper was prepared as
described above on the
Western Michigan University pilot paper machine. The addition rate of internal
size used in the
?s alkaline fine paper for this and subsequent Examples (0.47 kg/metric tonne)
represents a
relatively light internal sizing rate for the alk.enyl ketene dimer used as an
internal size.
The internally sized alkaline paper in this Control 1B was not subjected to a
surface
treatment with either a 2-oxetanone reactive size or an inorganic filler.
Evaluation of this paper
on the IBM 3800 high speed laser printer resulted in a billowing maximum
height after 10
3o minutes of 2.5 - ?.75 inches (6.4 - 7.0 cm), the same results as obtained
with the acid fine paper
SU>BST1TUTE SHEET (RULE 26)
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in Control lA. Without any surface size, both the internally sized acid fine
paper and the
internally sized alkaline fine paper gave excellent high speed converting
performance, as noted
above.
Control IC, a third control, was carried out using the same internally sized
alkaline fine
paper used in Control 1B but surface sized with a reactive 2-oxetanone size to
demonstrate the
adverse effect on high speed converting performance that results with the use
of such a surface
size. The internally sized alkaline paper in Control 1C was surface treated
with an alkenyl
ketene dimer reactive size made from a mixture of unsaturated/branched fatty
acids (the same
size used to internally size the paper), applied at the size press at an
addition rate of 2.5 kglmetric
to tonne. Evaluation of the high speed converting performance on the IBM 3800
high speed laser
printer gave a billowing maximum height after 10 minutes that was in excess of
6 inches (in
excess of 15 cm), indicating unacceptable high speed converting performance
for this surface
sized alkaline fine paper.
The results of the evaluations of Control IA, Control 1B and Control 1C, as
well as of
t5 the other examples carried out in this Example 1, are summarized below in
Table 1. In the high
speed converting evaluation of Controls 1A and 1B on the IBM 3800 laser
printer, paper
runnability was excellent and no stacker or registration errors were
encountered. By contrast,
Control 1 C surface treated with an alkenyl k:etene dimer surface size gave
unacceptable high
speed converting performance when evaluated on the IBM 3800 laser printer,
since maximum
2o billowing height increased to more than 6 inches (more than 15 cm) after 5-
6 minutes of running
time, and frequent stacker and registration errors were also observed.
Several examples were carried out using the internally sized alkaline paper
used in
Control 1B, but surface treated with a combination of the alkenyl ketene dimer
with an inorganic
filler to demonstrate the beneficial results in. high speed converting
performance for such surface
?5 treated alkaline fine paper. The surface size applied in each of these
examples was the same as
that used in Control IC, namely, an alkenyl ketene dimer that was applied at
the size press at a
rate of 2.5 kglmetric tonne, the same addition rate as used in Control IC.
However, each of
these examples differed from Control 1 C in that an inorganic filler was also
applied at the size
press in combination with the alkenyl ketene dimer surface size treatment.
SUBSTITUTE SHEET (RULE 26)
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In Example I-1, the inorganic filler was kaolin clay, HYDRAFINE~ 90 kaolin,
available
from J.M. Huber Corp., Edison, New Jersey, applied at an addition rate of 10
kglmetric tonne.
The weight ratio of inorganic filler to surface size in this Example I-1 was
4:1. Evaluation of
high speed converting performance on the IBM 3800 laser printer gave a
billowing maximum
height after 10 minutes of 2.75 - 3.0 inches .(7.0 - 7.6 cm).
In Example 1-2, the inorganic filler was silicon dioxide, OPTISIL~ 3265
silicon dioxide,
a precipitated amorphous silica, available from J.M. Huber Corp., that was
applied at an addition
rate of 2.5 kg/metric tonne of paper. The weight ratio of filler to surface
size was 1:1 in this
Example 1-?. Evaluation of high speed converting performance gave a billowing
maximum
1o height after 10 minutes of 2.75 - 3.0 inches (7.0 - 7.6 cm).
In Example 1-3, the inorganic filler was titanium dioxide, TI-PUREE R-941
rutile
titanium dioxide, available from E.I, duPonvt de Nemours & Company,
Wilmington, Delaware,
applied at a filler addition rate of 2.5 kg/metric tonne of paper. The weight
ratio of filler to
surface size in this Example 1-3 was 1: I . Evaluation of high speed
converting performance
~ 5 gave a billowing maximum height after 10 minutes of 3.0 inches (7.6 cm).
In Example 1-4, the inorganic filler was bentonite, AQUAGEL GOLD SEAL~
bentonite,
i.e., sodium montmorillonite, available from Baroid Corporation, Houston,
Texas, applied at an
addition rate of 1.0 kglmetric tonne. The weight ratio of filler to surface
size in this Example 1-4
was 0.4:1. Evaluation of high speed converting performance gave a billowing
maximum height
20 after 10 minutes of 2.75 - 3.0 inches (7.0 - 7.6 cm).
The surface treatments for each of these Examples 1-1 to 1-4, using preferred
inorganic
fillers of this invention that were surface-applied in combination with an
alkenyl ketene dimer
surface size, demonstrated excellent high speed converting performance that
was very similar to
that obtained with Control 1 B, which used the same alkaline fine paper but
without any surface
?5 treatment. In the evaluation of high speed converting performance for
Examples I-1 to 1-4 on
the IBM 3800 laser printer, billowing maximum height was significantly
reduced, to a maximum
of 3 inches (7.6 cm), and the number of starker and registration errors was
greatly reduced or
eliminated, as compared with the unsatisfactory converting results for Control
I C. This
improvement in high speed converting performance far Examples 1-1 to 1-4 is
remarkable, being
o both surprising and unexpected, when contrasted with the poor converting
performance
SUBSTITUTE SHEFf (RULE 26)
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WO 99141452 PCT/US99/01436
encountered with Control 1C, in which the alkaline paper was surface treated
with~the same
reactive surface size and amount as in Examples 1- I to 1--1 but without the
presence of a surface-
applied inorganic filler.
Several additional Comparative Examples were also carried out in this Example,
using
other inorganic fillers applied at the size press but different from those
used in Examples 1-1 to
1-4, that did not result in satisfactory high speed converting performance for
such surface treated
papers. Although these inorganic fillers provided little or no improvement in
the conversion
performance of the surface sized alkaline fine paper, it is believed that
improvements in paper
runnability could be achieved with either hif;her addition levels of these
same inorganic fillers or
to use of different grades of these inorganic fillers having either a higher
surface area or higher
absorptivity.
Comparative Examples C1-1 to C1-=~ evaluated three types of silicate fillers
at an
addition rate of 2.5 kg/metric tonne of paper; so that the weight ratio of
filler to surface size in
each example was 1:I. In Comparative Examples C1-1 and C1-2, the inorganic
fillers were
15 respectively calcium silicate, HUBERS012P.~ 600 calcium silicate and
HLBERSORB~ 250
calcium silicate, available from J.M. Huber Corp., Edison, New Jersey. The
precipitated
amorphous calcium silicate in Comparative Example C1=1 was finer in average
particle size than
that used in Comparative Example C1-2. In Comparative Example C1-3, the
inorganic filler was
HYDREX" P precipitated~amorphous silicate, available from J. M. Huber Corp.,
Edison, New
1o Jersey. Far each of these Comparative Examples C1-1 to C1-3, evaluation of
high speed
converting performance gave unsatisfactory results since billowing maximum
height after 10
minutes was in excess of 6 inches (in excess of 15 cm).
The unpredictability of using an inorganic filler as a surface treatment in
combination
with a reactive surface size, to provide improved paper convertibility
notwithstanding the
25 presence of the reactive surface size on the paper, is further evidenced by
the following findings
regarding the use of internal fillers. The present inventors have discovered
that HCTBERSORB~
600 calcium silicate, when used as an internal Filler added at a rate of 10
kg/metric tonne at the
wet end of a gapermaking process, improves the convertibility performance of
an alkaline fine
paper that is internally sized with an alkyl 1';etene dimer at an addition
rate of 1.1 k~g/metric
3o tonne, but the comparable use of either OP'CISIL" 3?65 silicon dioxide or
HYDREX~ P
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precipitated amorphous silicate as internal additives does not improve paper
convertibility of
alkaline fine paper containing the identical internal size (alkyl ketene
dimer) at the same addition
rate.
Comparative Examples Cl-4 and CI-S evaluated calcium carbonate as the
inorganic
filler as a surface treatment, applied at a filler addition rate of 10.0
kg/metric tonne paper, so the
weight ratio of filler to surface size was 4:1. In Comparative Example C 1-4,
the inorganic filler
was HYDROCA.RB'~ 90 ground calcium carbonate, available from OMYA, Inc.,
Florence,
Vermont, and in Comparative Example C 1-5, the inorganic filler was ALBACAR~
HO
precipitated calcium carbonate, available from Specialty Minerals Inc., New
York, New York.
1o Evaluation of high speed converting performance gave unsatisfactory
results, with billowing
maximum height being in excess of 6 inchfa (in excess of 15 cm) for both
Comparative
Examples.
Comparative Example CI-6 evaluated alumina as the inorganic filler, applied at
an
addition rate of 2.5 kg/metric tonne paper so that the weight ratio of filler
to surface size was 1:1.
t5 The inorganic filler was HYDRAL~ 710 alumina, available from Alcoa Alumina
and Chemicals,
LLC, Pittsburgh, Pennsylvania. In Comparative Example Cl-7, the inorganic
filler was talc, i.e.,
magnesium silicate, applied at an addition rate of 10.0 kg/metric tonne so
that the weight ratio of
filler to surface size was 4:1. The inorganic filler in this Comparative
Example C1-7 was
VANT.ALC~ 6I-I talc, available from R.T. Vanderbilt Company, Inc., Norwalk,
Connecticut.
2o High speed converting performance for both Comparative Examples C1-6 and Cl-
7 was
unacceptable, the billowing maximum height after l0 minutes being in excess of
6 inches (in
excess of IS cm).
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WO 99/41452 PCT/US99/01436
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Example 2
Example 2 evaluates the effect on high speed converting performance of an
alkaline fine
paper that is surface-treated with various amounts of an alkenyl ketene dimer
reactive surface
size used in combination with kaolin clay as the inorganic filler, both
applied at various addition
rates and weight ratios of filler to surface size. The paper used in this
Example was alkaline
paper that had been internally sized with an alkenyl ketene dimer at an
addition rate of 0.47
kg/metric tonne of paper, the same internally sized alkaline fine paper used
in Control 1 B of
Example 1. The 2-oxetanone reactive size was an alkenyl ketene dimer sizing
agent, and this
reactive size was the same as that used in Example 1. The inorganic filler
used in this Example 2
t0 was HYDRAFINE~ 90 kaolin clay, available from J.M. Huber Corporation,
Edison, New Jersey,
and this kaolin clay is a fine particle size clay having a particle size
distribution in which 90-96
wt% is finer than 2 microns:in size. Although the kaolin clay used in this
Example 2 was a dry
powder, an aqueous slurry of kaolin clay is preferable in commercial practice.
Results of all
evaluations described in this Example 2 arc; summarized in Table 2 below.
t5 Two controls, Control 2A and Control 2B, were carried out using a surface
treatment of
alkenyl ketene dimer alone, applied at the size press at an addition rate of
1.75 kg/metric tonne
of paper without any inorganic filler being surface applied. Evaluation of
high speed converting
performance on the IBM 3800 laser printer resulted in billowing maximum height
after 10 .
minutes being 4.0 - 6.0 inches (10.1 - 15.2 cm) for Control 2A and 3.0 inches
(7.6 cm) far
Control 2B.
Examples 2-1 to 2-3 were carried out using the same reactive surface size and
addition
rate but with the concurrent surface treatment at the size press of the kaolin
filler at three
different addition rates: 2.5, 5 and 10 kg/metric tonne paper, such that the
weight ratio of filler
to surface size was respectively 1.4:1, 2.8:1, and 5.7:1. Evaluation of the
high speed converting
?5 performance for each of these three Examples showed that the surface
treated paper gave
excellent performance, in which billowing maximum height after 10 minutes in
alt cases was
only 2.75 inches (7.0 cm).
In the next set of evaluations in this Example 2, the addition rate of alkenyl
ketene dimer
surface size was increased to 2.5 kg/metric, tonne paper (as compared with
1.7S kglmetric tonne
o in the first group described above). Three controls, Controls 2C, 2D and 2E,
were carried out
using the alkenyl ketene dimer applied at the size press at the specified 2.5
kg/metric tonne
addition rate but without any concurrent surface treatment with an inorganic
filler. Evaluation of
suesrrru~ sHF~- ~RU~ 2s~
CA 02319104 2000-07-19
WD 99141452 PCTIUS99/01436
-?3-
high speed converting performance showed that the reactive size surface-
treated alkaline paper
for Controls 2C, 2D and 2E gave generally poor results, with billowing maximum
height after 10
minutes being 5.0 inches (12.7 cm) for Control 2C, 4.0 - 6.0 inches (10.1 -
15.2 crn) for Control
2D and in excess of 6 inches (in excess of 15 cm) for Control 2E.
In Examples 2-4 and 2-5, surface treatment of the alkaline paper with the
alkenyl ketene
dimer sizing agent at a rate of 2.5 kg/metric tonne also included the
concurrent surface
application at the size press of HYDR.AFINE~ 90 kaolin clay at two different
addition rates:
3.75 kg/metric tonne in Example 2-4, giving a weight ratio of filler to
surface size of 1.5: l, and 5
kg/metric tonne in Example 2-S, giving a weight ratio of filler to surface
size of 2:1. High speed
o converting performance was generally satisfactory for Example 2-4, in which
billowing
maximum height after 10 minutes was 3.0 - 3.25 inches (7.6 - 8.2 cm), and
significantly
improved for Example 2-5 in which the kaolin filler addition rate was 5
kg/metric tonne instead
of 3.75 kglmetric tonne . Billowing maximm" hP;ehr mA~m".ea F .. ~..___,_ ., ~
., ~,.
inches (7.0 cm), indicating excellent high speed converting performance.
15 In the next evaluation grouping in Example 2, the addition rate of the
alkenyl ketene
dimer surface size was increased still further, to 3.75 kg/metric tonne paper.
In Control 2-F, the
alkenyl ketene dimer was surface applied ai: an addition rate of 3.75
kg/metric tonne without the
concurrent surface application of an inorganic filler. Evaluation of the high
speed converting
performance for this Control 2F gave a billowing maximum height that was in
excess of 6 inches
o (in excess of 1 S cm), indicating unacceptable paper runnability. In Example
2-G, the alkenyl
ketene dimer surface size and kaolin clay filler were each surface-applied at
the size press at
identical respective rates of 3.75 kg/metric tonne, giving a weight ratio of
filler to surface size of
1:1. High speed converting performance for this surface treated alkaline paper
was marginally
improved over that of Control 2F, with billowing maximum height after 10
minutes being 4.5 - 6
25 inches (11.4 - 15.2 cm). In Example 2-7, the addition rate of kaolin clay
filler was increased
from 3.75 kg/rnetric tonne (used in Example 2-6) to ~ kglmetric tonne so that
the weight ration
of filler to surface size was I .3:1 in this Example 2-7. The high speed
converting performance
measured for this Example 2-7 was inexplicably unsatisfactory, being in excess
of 6 inches (in
excess of 1 S cm) maximum billowing height after 10 minutes.
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In Example ?-8, the addition rate of kaolin clay filler was increased further,
as compared
with Examples 2-6 and 2-7, to 7.5 kglmetric: tonne. The weight ratio of filler
to surface size in
this Example 2-8 was therefore 2:1, and this. relative amount of kaolin filler
to surface size
provided excellent high speed converting performance. Billowing maximum height
after 10
minutes measured for this Example 2-8 was 2.75 inches (7.0 cm), indicating
excellent paper
runnability for this surface-treated alkaline ifne paper.
In the last evaluation grouping for E.rample ?, the addition rate at the size
press of
alkenyl ketene dimer surface size was increased to 5 kg/metric tonne of paper,
and two different
addition rates of HYDRAFINE~ 90 kaolin clay were evaluated. In Comparative
Example C2-1,
the kaolin filler addition rate was 3.75 kg/metric tonne, giving a weight
ratio of filler to surface
size of 0.75 :1. High speed converting performance measured for this
Comparative Example C2-
I was unsatisfactory, billowing maximum height after 10 minutes being in
excess of 6 inches (in
excess of 15 crn). In Example 2-9, the addition rate of kaolin filler was
twice that used in
Comparative Example C2-1, being 7.5 kg/metric tonne of paper, which provided
a_weight ratio
of filler to surface size of 1.5:1. High speed. converting performance
measured for this Example
2-9 was good; with billowing maximum height after 10 minutes being 3.0 - 3.25
inches (7.6 - 8.2
cm).
These results, which are summarized in Table 2 shown below, demonstrate that
use of a
surface-applied kaolin filler with the alkenyl ketene dimer reactive surface
size provides
excellent results in high speed converting performance when the weight ratio
of the kaolin clay
filler to alkenyl ketene dimer surface size is in excess of 1:1. The results
in this Example
likewise demonstrate that optimal cost-effective high speed converting
performance is obtained
for alkaline fine paper surface sized with an alkenyl ketene dimer when the
weight ratio of
inorganic kaolin clay filler to surface size is about 1.5 - 3: I . Weight
ratios of the kaolin clay
zs filler to surface size in excess of 3:1 also provide excellent high speed
converting performance
but do not appear to be cost effective since weight ratios in the range of 1.5
- 3:1 would give
similar excellent results.
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SUBST'1~ gH~ ~pULE 26)
CA 02319104 2000-07-19
WO 99141452 PCT/US99101436
-27-
Example 3
Example 3 describes another evaluation of hi~:h speed converting performance
of alkaline
paper made as described above and surface rreated with a ?-oxetanone reactive
size in
combination with various inorganic fillers. Results of all evaluations
described in this Example
3 are summarized in Table 3 below.
Several baseline control examples were carried out. Control 3A was an
evaluation of a
prior art acid fine paper made in a conventional manner with rosin and alum as
the internal size
and with no surface treatment being carried out. Evaluation of high speed
convertibility
performance of the acid fine paper in Control 3A using the IBM high speed
printer gave a
1o billowing maximum height after 10 minutes. of 2.5 - 2.75 inches (6.4 - 7.0
cm), indicating
excellent performance. Control 3B, the second benchmark control, was an
alkaline fine paper
made as described above on the Western Michigan University pilot paper machine
with an
internal size that was an alkenyl ketene dimer added at the wet end at a rate
of 0.47 kgJmetric
tonne of paper. This internally sized alkaline paper was not subjected to a
surface treatment with
IS either a 2-oxetanone reactive surface size or an inorganic filler.
Evaluation of this alkaline fine
paper for converting performance gave excellent results, identical to that
obtained with the acid
fine paper in Control 3A. Without any surface size, both the internally sized
acid fine paper and
the internally sized alkaline fine paper provided excellent high speed
converting performance.
Control 3C was a third control that was carried out using the same internally
sized alkaline
2o fine paper used in Control 3B, but surface sized with a reactive 2-
oxetanone size to demonstrate
the adverse effect on high speed converting performance that results with the
use of such a surface
size. The internally sized alkaline paper used in Control 3C was surface-
treated with the same size
used to internally size the paper, i.e., an alkenyl ketene dimer reactive
size, and that was applied at
the size press at an addition rate of 1.0 kg/metric tonne. In a similar
fashion, Controls 3D and 3E
25 were likewise surface-treated with the same alkenyl ketene dimer reactive
size applied at higher
addition rates, 1.75 and 2.5 kglmetric tonne, respectively. Evaluation of the
high speed converting
performance on the IBM 3$00 high speed laser printer for controls 3C, 3D and
3E gave the
following billowing maximum height after 10 minutes: 2.75 inches (7.0 cm); 4 -
6 inches (10.1 -
15.2 cm); and 5.0 inches ( 12.7 cm). The results of the convertibility
performance evaluations of
30 Control 3C, Control 3D and Control 3E demonstrate that as the surface-
applied concentration of an
alkenyl ketene dimer surface size is increased, high speed converting
performance becomes
progressively worse.
SUHST1TUTE SHEFt (RULE 2fi)
CA 02319104 2000-07-19
WO 99/41452 PCTIIJS99/01436
-28
Several Examples were carried our using the internally sized alkaline paper
used in
Control 3E, but surface-treated with a combination of alkenyl ketene dimer
with an inorganic
filler to demonstrate the beneficial results in :high speed converting
performance for such
surface-treated alkaline fine paper. The surface size applied in each of these
Examples was the
same as that used in Control 3E, namely, the alkenyl ketene dimer that was
applied at a rate of
2.5 kg/metric tonne. However, each of these Examples differed from Control 3E
in that an
inorganic filler was applied, as described below, in combination with the
alkenyl ketene dimer
that was also applied as a surface treatment at the size press.
In Comparative Example C3-l, the inorganic filler was calcium silicate,
HUBERSORB~
to 600 calcium silicate, available from J.M. Huber Corp., Edison, New Jersey,
applied at an
addition rate of 1.5 kglmetric_tonne. The weight ratio of inorganic filler to
surface size in
comparative Example C-1 was 0.6:1. The evaluation of high speed converting
performance on
the IBM 3800 laser printer gave a billowing maximum height after 10 minutes of
6 inches (.15.2
cm), indicating poor paper runnability.
15 In Example 3-1, the same inorganic filler was used, i.e., HUBERSORB~ 600
calcium
silicate, but the filler addition rate in this surface treatment was increased
to 2.5 kg/metric tonne,
as compared to 1.5 kglmetric tonne in Comparative Example C3-1. The weight
ratio of filler to
surface size in this Example 3-1 was 1:1. Evaluation of high speed converting
performance gave
a billowing maximum height after 10 minutes of 2.75 - 3.0 inches (7.0 - 7.6
cm), indicating
2o excellent paper runnability.
At the addition rate and weight ratio of filler to surface size used in
Example 3-l, the
calcium silicate inorganic filler eliminated the paper billowing and
runnability problems caused
by the presence of the alkenyl ketene dimer ;surface size. The positive effect
and improvement in
paper convertibility at the filler addition rate and weight ratio of filler to
surface size used in this
25 E~cample 3-1 contrast with the results obtained with Comparative Example C3-
1 in which lower
levels of calcium silicate provided little or no beneficial effect on paper
runnability. The poor
paper convertibility results obtained with Comparative Example C1-1 in Example
1, which also
used HUBERSORB~ calcium silicate at similar levels to those used in Example
3-l, indicate that a 1:1 weight ratio of filler ro surface size should be
increased, e.g., to a weight
3o ratio in excess of 1:1, to assure consistent improvement in paper
convertibility from this
SUBSTITUTE SHEF't (RULE 26)
CA 02319104 2000-07-19
WO 99/41452
PCT/US99I01436
-29-
surface-applied inorganic filler at the addition rate of alkenyl ketene dimer
used in these
Examples.
In Examples 3-2 to 3-4, the inorganic: filler was a kaolin clay, HYDR.AFINE~
90 kaolin
clay, available from J.M. Huber Corp., Edison, New Jersey, applied at three
different addition
rates, namely, 2.5, 5.0 and 10.0 kg/metric tonne, respectively. Since the
addition rate of alkenyl
ketene dimer that was likewise applied as a :surface treatment in these three
Examples was 2.5
kg/metric tonne, the respective weight ratios of filler to surface size in
Examples 3-2 to 3-4 were
1:1, 2:1 and 4:1. Evaluations of high speed converting performance on the IBM
3800 Laser
printer demonstrated excellent convertibility performance for Examples 3-3 and
3-4, as
to compared with Example 3-2 which gave only fair convertibility performance.
Billowing
maximum heights measured after 10 minutes for Examples 3-2 to 3-4 were 4
inches ( 10.1 cm); 3
inches (7.6 cm); and 2.5 - 3 inches (7.0 - 7.6 cm), respectively. These
results, all of which are
summarized in Table 3 below, demonstrate that weight ratios of kaolin clay
filler to surface size
above a ratio of about 1:1 provide excellent paper convertibility performance
for an alkenyl
ketene dimer applied as a surface size at an addition rate of 2.5 kglmetric
tonne for the internally
sized alkaline paper used in this Example 3.
SUBST~-E SHEET (RUt.E 26)
CA 02319104 2000-07-19
WO 99/41452 PCT/US99/01436
- 30
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CA 02319104 2000-07-19
WO 99/41452 PCT/US99/01436
-31
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SUBSTITUTE SHEET (RULE 26)
CA 02319104 2000-07-19
WO 99141452 , PCT/US99/01436
-32
Example 4
Example 4 describes the evaluation o E' high speed converting perfornnance of
paper made
as described above and surface treated with a 2-oxetanone reactive size that
was an alkyl ketene
dimer, rather than the alkenyl ketene dimer used in the previous Examples. The
alkyl ketene
dimer was based on C16-Clg saturated fatty acids (palmitic and stearic acids)
that was applied as
a surface treatment to alkaline fne paper at an addition rate of 1.0 kglmetric
tonne.
Two baseline control examples were carried out. Control 4A was an evaluation
of a prior
art acid fine made in a conventional manner with rosin and alum as the
internal size and with no
surface treatment being carried out. Control 4A using this acid fine paper
gave a billowing
1o maximum height after 10 minutes of 2.5 - 2.75 inches (6.4 - 7.0 cm),
indicating generally
excellent paper runnabi~iity for~this prior art fine paper.
Control 4B, the second benchmark control, was an alkaline paper made as
described
above on the Western Michigan University pilot paper machine with an internal
size that was an
alkenyl ketene dimer (not an alkyl ketene dinner) added at the wet end at a
rate of 0.4'7 kglmetric
15 tonne of paper. This internally sized alkalinE: fine paper was also surface
sized with a reactive 2-
oxetanone size, i.e., the above-mentioned alkyl ketene dimer, to demonstrate
the adverse effect
on high speed converting performance that results with the use of such an
alkyl ketene dimer
surface size. The alkyl ketene dimer reactive: size was applied to the paper
surface using the size
press at an addition rate of 1.0 kg/metric tonne. Evaluation of the high speed
converting
2o performance of this surface sized alkaline fine paper on the IBM 3800 high
speed laser printer
gave a billowing maximum height after 10 minutes that was 3.5 inches (8.9 cm)
and also caused
a long loop error.
Example 4-1 was carried out using the internally sized alkaline paper used in
Control 4B,
but surface-treated with a combination of the alkyl ketene dimer with an
inorganic Fller to
25 demonstrate the beneficial results in high speed converting performance for
such surface treated
alkaline fine paper. The inorganic filler was kaolin clay, HYDR.AFINE~ 90
kaolin clay,
available from J.M. Huber Corp., Edison, New Jersey, applied at an addition
rate of 10.0
kg/metric tonne. Since the addition rate of the alkyl ketene dimer at the size
press was 1.0
kg/metric tonne, the weight ratio of filter to surface size was 10:1 in this
Example 4-1.
30 Evaluation of high speed converting performance gave a billowing maximum
height after 10
SUBSTITUTE SHEET (RULE 26)
CA 02319104 2000-07-19
WO 99/41452 PCCIUS99/01436
-33
minutes of 2.75 inches (7.0 cm), indicating excellent paper runnability
similar to that obtained
for the acid fine paper in Control 4A. The results obtained in Example 4-1
demonstrate that the
addition of HYDR.AFINE~ 90 kaolin clay at: a weight ratio of filler to surface
size of 10:1
eliminated the billowing caused by the surface-applied alkyl ketene dimer. The
method of this
invention is thus applicable to alkyl ketene dimers, such as those made from
mixtures of
saturated fatty acids.
For illustrative purposes, Control 4C is included in this Example 4 to
demonstrate that
the presence of moderate-to-heavy amounts of an alkyl ketene dirner as an
internal size in an
alkaline fine paper causes the paper's convertibility performance to
deteriorate. This is shown by
to a billowing maximum height of 3.25 inches ($.2 cm) that resulted with the
internal addition at
the wet end of alkyl ketene dimer, made from a mixture of C16-C 1 g saturated
fatty acids
(palmitic and stearic acids), added at a rate of 1.1 kg/metric tonne. No
surface treatments of
surface size and/or inorganic filler were made to this internally-sized paper.
SU9ST~ SHEET (RULE 26)
CA 02319104 2000-07-19
WO 99141452 ~ PCTIUS99/01436
-34
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SUBSTITUTE SHEET (RULE 25)
CA 02319104 2000-07-19
WO 99/41452 PCT/US99/01436
-35-
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SUBSTi'rUTE SHEET (RULE 2B)
CA 02319104 2000-07-19
WO 99/41452
I'CT/(JS99l01436
-36-
Example 5
Example 5 evaluates the effect on high speed converting performance of an
alkaline fine
paper that is surface-treated with various amounts of an alkenyl ketene dimer
reactive surface size
used in combination with bentonite as the inorganic filler, both applied at
various addition rates
and weight ratios of filler to surface size. The inorganic filler used in this
Example 5 was
VOLCLAY~ HPM 75 bentonite clay, available from Amcol International
Corporation, Arlington
Heights, Illinois. Results of all evaluations described in this Example 5 are
summarized in Table 5
below.
Three baseline control examples were carried out. Control SA was an evaluation
of a prior
art acid fine paper made.in a conventional manner with rosin and alum as the
internal size and with
to no surface treatment being carried out. Evaluation of the high speed
converting performance far
the acid fine paper of Control SA gave a billowing maximum height after 10
minutes of 2.5 - 2.75
inches (6.4 - 7.0 cm), indicating excellent high speed runnability.
Control SB, the second benchmark control, was an alkaline paper made with an
internal
size that was an alkenyl ketene dimer added at the wet end at a rate of 0.47
kg/metric tonne of
paper, and this alkaline fine paper was essentially the same as that described
in Example 1 as
Control 1B.
The internally sized alkaline paper in this Control.SB was not subjected to a
surface
treatment with either a 2-oxetanone reactive size or an inorganic filler.
Evaluation of this paper on
the IBM 3800 high speed laser printer resulted in a billowing maximum height
after 10 minutes of
2o 2.75 inches (7.0 cm), similar to the results obtained with the acid fine
paper in Control SA.
Without any surface size, both the internally sized acid fine paper and the
internally sized alkaline
fine paper gave excellent high speed converting performance, as noted above.
Control 5C, a third control, was carried out using the same internally sized
alkaline fine
paper used in Control SB but surface sized with a reactive 2-oxetanone size to
demonstrate the
adverse effect on high speed converting performance that results with the use
of such a surface
size. The internally sized alkaline paper in Control SC was surface treated
with the same
aLkenyl ketene dimer reactive size used in Examples 1-3 (and the same size was
used to
internally size the paper), applied at the sizc: press at an addition rate of
2.5 kg/metric tonne.
Evaluation of the high speed converting performance on the iBM 3800 high speed
laser printer
3o gave a billowing maximum height after 10 minutes that was in excess of 6
inches (in excess of
SUBS~'rTUTE SHEET (RULE 25)
CA 02319104 2000-07-19
WO 99/41452
PCTIUS99/01436
37
15 cm), indicating unacceptable high speed converting performance for this
surface sized
alkaline fine paper.
The results of the evaluations of Control 5A, Control SB and Control 5C, as
well as of
the other examples carried out in this Example 5, are summarized below in
Table 5. In the high
speed converting evaluation of Controls 5A. and 5B on the IBM 3800 laser
printer, paper
runnability was excellent and no stacker or registration errors were
encountered. By contrast,
Control SC surface treated with an alkenyl ketene dimer surface size gave
unacceptable high
speed converting performance when evaluated on the IBM 3800 laser printer,
since maximum
billowing height increased to more than 6 inches (more than 15 cm)and frequent
long loop
errors were encountered.
Comparative Example C5-1 and Examples 5-1 and 5-2 were carried out using the
same
reactive surface size and adi~ition rate but with the concurrent surface
treatment at the size press
of the bentonite filler at three different addition rates: 0.25, 0.5 and 1.0
kg/metric tonne paper,
such that the weight ratio of filler to surfacc; size was respectively 0.1:1,
0.2:1, and 0.4:1. High
speed converting performance measured on the IBM 3800 laser printer for
Comparative
Example C5-1 was unsatisfactory, with the billowing maximum height after 10
minutes being in
excess of G inches (in excess of 15 cm). In Example 5-1, the addition rate of
bentonite filler was
twice that used in Comparative Example C.S-1, being 0.5 kg/metric tonne of
paper, which
provided a weight ratio of filler to surface size of 0.2:1. High speed
converting performance
Zo measured for this Example 5-1 was good, with billowing maximum height after
10 minutes
being 3.5 inches (8.9 cm). .In Example 5-2,, the addition rate of bentonite
filler was twice that
used in Example 5-1 (and four times that used in Comparative Example CS-1),
being 1.0
kg/metric tonne of paper, which provided a weight ratio of filler to surface
size of 0.4:1. High
speed converting performance measured for this Example 5-1 was excellent, with
billowing
maximum height after 10 minutes being 2.'15 inches (7.0 cm), equivalent to
that obtained with
benchmark Control 5B which was alkaline paper that contained no surface size
and no surface
filler.
In the next set of evaluations in this Example S, the addition rate of alkenyl
ketene dimer
surface size was increased to 3.75 kg/metric tonne paper (as compared with 2.5
kg/metric tonne
3o in the first group described above). In Comparative Example C5-2, surface
treatment of the
alkaline paper with the alkenyl ketene dimer sizing agent at a rate of 3.75
kg/metric tonne also
included the concurrent surface appticatian. at the size press of VOLCLAY~ 90
bentonite clay at
SU9STffUTE SHEET (RULE 26~
CA 02319104 2000-07-19
WO 99/41452 PCTNS99I01436
38
an addition rate of 0.25 kglmetric tonne, giving a weight ratio of filler to
surface size of 0.07:1.
High speed converting performance was unacceptable for Comparative Example CS-
2, in which
billowing maximum height after 10 minutes was in excess of 6 inches (in excess
of I5 cm).
In Examples 5-3 and 5-4, surface treatment of the alkaline paper with the
alkenyl ketene
dimer sizing agent was at a rate of 3.75 kglmetric tonne (as in Comparative
Example CS-2) but
with the concurrent surface application at the; size press of VOLCLAY~ 90
bentonite clay at two
higher addition rates: 0.5 kg/metric tonne in Example 5-3, giving a weight
ratio of filler to
surface size of 0.13:1, and 1.0 kg/metric toru~e in Example 5-4, giving a
weight ratio of filler to
surface size of 0.27:1. High speed converting performance was generally
satisfactory for
Example 5-3, in which billowing maximum height after 10 minutes was 3.75
inches (9.5 cm),
and further improved for Example S-4 in which the bentonite filler addition
rate was 1.0
kg/metric tonne instead of 0:5 kglmetric tonne . Billowing maximum height
measured for
Example 5-4 was 3.0 inches (7.6 cm), indicating good high speed converting
performance.
In the Iast set of evaluations in this Example S, the addition rate of alkenyl
ketene dimer
surface size was increased to 5.0 kg/metric tonne paper (as compared with 3.75
kg/metric tonne
in the previous group described above). In (:omparative Examples CS-3 and 5-4,
surface
treatment of the alkaline paper with the alkenyl ketene dimer sizing agent at
a rate of 5.0
kg/metric tonne also included the concurrent: surface application at the size
press of VOLCLAI'~
90 bentonite clay at two different addition rates: 0.25 kg/metric tonne in
Comparative Example
2o CS-3, giving a weight ratio of f ller to surface size of 0.05:1, and 0.5
kg/metric tonne in
Comparative Example CS-4, giving a weight ratio of filler to surface size of
0.1:1. High speed
converting performance was unacceptable for each of Comparative Examples CS-3
and CS-4, in
which billowing maximum height after 10 minutes was in excess of 6 inches (in
excess of 15
cm) for both.
?5 In Examples S-5 and 5-6, surface treatment of the alkaline paper with the
alkenyl ketene
dimer sizing agent was again at a rate of 5.0 kg/metric tonne (as in
Comparative Example C5-3
and CS-4) but with the concurrent surface application at the size press of
VOLCLAY~ 90
bentonite clay at two higher addition rates: 1.0 kg/metric tonne in Example 5-
5, giving a weight
ratio of filler to surface size of 0.2:1, and l .:i kg/metric tonne in Example
5-6, giving a weight
30 ratio of filler to surface size of 0.3:1. High speed converting performance
was generally
satisfactory for Example 5-5, in which billowing maximum height after 10
minutes was 3.5
inches (8.9 cm), and significantly improved for Example 5-6 in which the
bentonite filler
SU6ST1TUTE SHEET (RULE 26)
CA 02319104 2000-07-19
WO 99/41452
PCTIUS99101436
39
addition rate was 1.5 kg/metric tonne instead of 1.0 kglmetric tonne .
Billowing maximum
height measured for Example 5-6 was 2.75 inches (7.U cm), indicating excellent
high speed
converting performance, equivalent to that obtained with benchmark Control SB
which was
alkaline paper that contained no surface size and no surface filler.
The results for this Example 5, which are summarized in Table S shown below,
demonstrate that use of a surface-applied bentonite filler with the alkenyl
ketene dimer reactive
surface size provides satisfactory results in high speed converting
performance when the weight
ratio of the bentonite clay filler to alkenyl ketene dimer surface size is in
excess of 0.1:1. The
results in this Example likewise demonstrate that optimal cost-effective high
speed converting
to performance is obtained for alkaline fine paper surface sized with an
alkenyl ketene dimer when
the weight ratio of inorganic bentonite clay filler to surface size is about
0.2:1 to about 0.4:1.
Weight ratios of the bentonife clay filler to surface size in excess of 0.4:1
would also provide
excellent high speed converting performance; but do not appear to be cost
effective since weight
ratios in the preferred range of about 0.2:1 to about 0.4:1 would give good
results.
IS
SU9STiTUTE SHEET (RULE 26)
CA 02319104 2000-07-19
WO 99141452 PCT/US99101436
x
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PCT/US99101436
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CA 02319104 2000-07-19
WO 99/41452 PCTIUS99/01436
4'2
The preceding specif c embodiments are illustrative of the practice of this
invention. The
present invention may be embodied in other specif c forms without departing
from the spirit or
essential attributes thereof and, accordingly, reference is made to the
appended claims, rather
than the foregoing specification, as indicating the scope of the invention.
StfBST~'UTE SHEET (RULE 25~
