Note : Les descriptions sont présentées dans la langue officielle dans laquelle elles ont été soumises.
CA 02394799 2002-08-23
WO 96/29369 PCTIUS96/03546
INK JET RECORDINC3 PAPER INCORPORaITIN(~
NOVEL PRECIPITATED CALCIDM CARBONATE PI~1T
This is a divisional application of Canadian Patent
Application Serial No. 2,215,500 filed on March 14, 1996.
The subject matter of this divisional application is
directed to an ink jet recording paper described more in detail
hereinunder. The subject matter of the parent application was
restricted to a process for preparing precipitated calcium
carbonate particles. However, it should be understood that the
expression "the invention" and the like encompasses the subject
matter of both the parent and the divisional application.
Field of the Invention
The present invention relates to novel heat
aged and milled precipitated calcium carbonate pigments
for use in ink jet recording papers. More
particularly, the present invention relates to an ink
jet recording paper which incorporates Buch pigments
and at least one water soluble binder to impart
enhanced print quality. The invention also relates to
ZO methods of applying these components to paper, and to
methods of producing the novel pigments.
Backarouad of the Invention
The thermal ink jet process applies a dilute
aqueous iuk onto the surface of a paper by heating a
sill volume of the ink is a small chamber with an
orifice that is directed at the recording paper. The
small volume of ink that is heated rapidly reaches its
boiling point, sad the steam bubble formed propels a
tiny drop of liquid ink at the paper, where the drop
Produces a single dot is a dot matrix that forms a
character or image on the sheet. This process requires
an ink that is law in solids and high boiling
components so that it is capable of boiling rapidly
without leaving a residue that can foul the heating
element, sad clog the orifice. Therefore, up to 96
percent of ink jet printer ink is a mixture of water
and low molecular weight glycols. Although such an ink
boils quickly when heated to ensure rapid printing, and
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is not prone to clog, it results is as applied ink that
is very mobile and slow to dry. Therefore, good print
quality can be obtained only if the ink colorant or dye
remains on or near the outer surface of the paper, and
does not spread or move from the point at which it was
applied_
It is also important that drying occurs
rapidly to prevent smearing of the colorant. In
printers that are not equipped with heating elements,
the water and glycol comoponents of the ink must
penetrate into the body of the paper for proper drying
of the colorant on the surface. If the colored phase
is carried into the paper with the liquid phase as it
penetrates into the paper, or if the colorant migrates
across the surface of the paper, the quality of the
resulting priest or image will be poor. Also, dry ink
colorant that is not permanently fixed on the paper
will blot or run if the printed surface becomes wet or
is marked with a highlighter. Therefore, the dry ink
should have excellent water sad highlighter fastness
properties for optimum perforrmaace.
Ia moat applications, multipurpose office
papers provide inadequate or poor thermal ink jet print
quality. This is particularly true where multicolor
printing with concomitant superimposed ink applications
is utilised. The poor print quality is compounded in
printers that apply the colors in one order when the
print head moves to the right sad the reverse order
when the print head moves to the left. Multipurpose
office papers often allow the colorant to penetrate
into the paper, which results in reduced optical
density of the printed image, and increased ahowthrough
on the reverse side of the paper. Multipurpose office
papers that are highly sized prevent liquid
penetration. leading to higher ink optical density,
but, also. excessive feathering and spreading.
One method of improving thermal ink jet print
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quality is to apply a material to the paper surface
that binds the ink colorant to the surface, but allows
the water/glycoi liquid phase to pass into the body of
the paper, which speeds drying. However, the ink
colorant often is an unsaturated or aromatic organic
compound, sad if the surface material interacts too
strongly with the colorant the color of the ink can
change. Therefore, a surface material must be obtained
that prevents the ink colorant from penetrating the
paper, but does not interact so strongly as to effect
the colorant, sad cause a color change.
Oshima et al., U.S. Patent No. 4,478,910,
discloses a paper base stock that is coated with a high
specific surface area colloidal silica pigment and a
polyvinyl alcohol binder, where the specific surface
area of the colloidal silica is greater than 200 mZ/g.
Migamoto, ~.S. Patent No. 4,576,867, sad
Rojima et al., tl.S. Patent No. 4,830,911, teach that
application of a cationic quaternary aamaonium polymer
to a paper stock will improve the water fastness of the
resulting paper. Application of such a quaternary
animoafum polymer is a size press is also disclosed by
Malhotra, tl.S. Patent No. 5,223,338. However, high
quality, cammnercial thermal ink jot recording paper is
produced with off machine Boaters, i.e., the paper is
not treated in the size press of the paper making
machine, but moat be removed sad coated in as
additional step using a ~eparata coating process.
Precipitated calcium carbonate ("PCC") has
been disclosed as a useful pigment or filler is ink jet
paper, but is typically included in a long list of
compounds that also includes natural ground calcium
carbonate, a form of the compound that differs greatly
- from PCC is its physical sad chemical properties; e.g.,
natural ground calcium carbonate particles are far
larger than those found is PCC, sad are normally
anionic, whereas PCC is naturally cationic.
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Koado et al., U.S. Patent No. 5,320,897,
describes coating ink jet recording paper with off-the-
shelf pigments sad a water soluble binder. The
pigments which are disclosed as being useful have an
apparent specific gravity is the range of 0.10 to 0.50
g/em3. and produce a paper with a water contact angle
of 45° to I00°.
Tbukisaka et al., U.S. Patent No. 5,007,964,
disclose a generic precipitation method incorporating a
chelatiag agent to obtain a porous agglomeration of
chain like PCC particles with a HET specific surface
area is the range of 25 to 55 mZ/g for use is a
recording paper. Particles with a BST specific surface
area of greater than 55 m2/g, are disclosed as being
I5 undesirable because they have a higher density, are not
porous, sad exhibit a low ability to absorb oil sad
water. It is further disclosed that PCC can be used as
a paste, or as a powder obtained by pulverizing the
dried paste, which is disclosed as not affecting the
agglomeration of the particles.
Ruaesh et al., U.S. Pataat No. 5,215,734,
disclose an accelerated heat aging process for PCC that
produces crystals with a specific surface area of about
3 to about 15 mZ/g and an average discrete particle
size of about 0.2 to about 0.9 ~. The PCC is used to
improve the optical properties of paper.
In view of the above, there is nothing in the
prior art to suggest how to improve the print quality
of ink jet recording paper. The present invention
provides one such solution to this probla~m.
Summary of the Invention
The present invention relates to as ink jet
recording paper with anhaaced properties that
incorporates novel heat aged and/or milled precipitated
calcium carbonate pigments sad a binder. The heat aged
PCC is prepared by carbonating a slurry of calcium
hydroxide to form a slurry of precipitated calcium
CA 02394799 2002-08-23
carbonate, screening the slurry to remove impurities,
adding an organophosphonate compound, such as ethanolamine
bis-(methylenephosphonic acid), to the slurry, and heat
aging the PCC slurry in the presence of the
5 organophosphonate to produce an improved pigment for ink
jet recording paper.
The ink jet recording paper of the present invention
is produced by coating at least one side of a paper base
stock with a coating comprising heat aged and/or milled PCC
and a binder to form the ink jet recording paper. The heat
aged and/or milled precipitated calcium carbonate is made
by carbonating a slurry of calcium carbonate, heat aging
the PCC in the presence of an organophosphonate compound
and/or milling the PCC to produce discrete particles of PCC
with a surface morphology and chemistry that enhances the
ability of the PCC to bind to the ink jet printer ink
colorant.
The present invention also provides an ink jet
recording paper comprising a paper base stock, having
thereon a coating comprising a heat aged precipitated
calcium carbonate pigment, and a binder, the pigment
produced by heat aging a slurry of precipitated calcium
carbonate particles in the presence of an effective amount
of an organophosphonate compound to control the extent or
degree of heat aging.
The present invention also provides a process for
making an ink jet recording paper comprising:
a) precipitating calcium carbonate particles from a
slurry of calcium hydroxide by introducing carbon dioxide;
b) heat aging the precipitated calcium carbonate
particles in the presence of an organophosphonate compound
CA 02394799 2002-08-23
Sa
to produce particles having a BET specific surface area of
at least about 60 m2/g; and
c) coating at least one side of a paper base stock with a
coating comprising heat aged calcium carbonate particles
and binder to form the ink jet recording paper.
The present invention also provides a process for
making an ink jet recording paper comprising:
a) preparing precipitated calcium carbonate particles
having a BET specific surface area of at least 60 m2/g and
b) coating at least one side of a paper base stock with a
coating comprising the precipitated calcium carbonate
particles and a binder to form the ink recording paper.
Detailed Description of the Invention
An ink jet recording paper has been obtained that
provides full color ink jet print quality that approaches
or surpasses that of the best ink jet specialty paper at a
greatly reduced price. The selection of PCC particle size,
surface area, surface chemistry, and degree of aggregation,
and its combination with an appropriate formulation binder
allows each thermal ink jet print characteristic to be
individually adjusted and optimized.
The cationic PCCs of the present invention bind ink
colorants without the use of expensive cationic resins and can
be manufactured on-site at the paper mill, so that, unlike
silica, they do not need to be dried, shipped, and then
rewetted for use. The present formulations are designed for
application in a metering size press, such as those installed
on large, low unit cost paper machines. Therefore, the PCC
compositions of the present invention can be applied as
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part of the paper making operation, rather than as a
separate, additional step after normal papermakiag
operations are co~plsted that increases the cost of the
process and the finished product. As a metered size
press application is typically two sided, both sides of
a paper coated on such a press are available for
printing, rather than the single sided coating that is
found in expensive, high quality comimarcial papers.
Although polyvinyl alcohol is a preferred binder in the
present invention, treating as ink jet recording paper
with heat aged and/or milled PCC provides a significant
improve~meat is print quality with lower cost binders.
Finally, the present formulations provide a paper that
is still suitable for photocopying, which allows
multiple uses of the paper.
PCC is normally produced by bubbling a gas
containing carbon dioxide through as aqueous suspension
of calcium hydroxide. Other inorganic materials, in
particular, inorganic materials coataiaiag aluminum,
such as alum, can bs coprecipitated with PCC, or can be
precipitated onto the surface of the PCC precipitate.
It has been unexpectedly discovered, however, that when
such a PCC ie heat aged and/or milled, trsatad with as
appropriate binder, sad then used in a composition for
treating thezmal ink jet recording paper, a high
quality ink jet recording paper is obtained, which
provides a print quality that eomopares favorably with
that of high coat, cemomareial, silica coated thermal
ink jet papers, but at a greatly reduced cost.
The heat aging and milling processes produce
discrete particles of PCC with a surface morphology sad
chemistry that enhances the :bility of the PCC to bind
to the ink jet ink colorant without binding so strongly
that the color of the ink is changed. Ink jet
recording papers incorporating the PCC sad binders of
the present invention have bean produced that are
superior to multipurpose office papers with reduced
CA 02394799 2005-08-04
feathering, spreading, and penetration or backside
showthrough, as well as improved optical density, dry
time, and water fastness.
The PCCs of the present invention are
produced by the conventional precipitation method of
introducing a gas containing carbon dioxide into a
suspension of calcium hydroxide: The calcium carbonate
precipitate is then~heat aged and/or milled before use.
The print quality of an ink jet recording paper
incorporating such a PCC is controlled by the state of
aggregation of the particles and the surface chemistry
of the pigment and the binder. The chemical nature of
the pigment surface is controlled by the specific
synthetic pathway and post synthesis treatment of the
pigment.
A PCC particularly useful is the present
invention is prepared by a process which comprises
introducing carbon dioxide into an aqueous slurry of
calcium hydroxide at a temperature of from about 7° to
2a about 18°C. The slurry contains from about 0.02 to 1
weight percent, based oa the calcium carbonate
equivalent of the calcium hydroxide in the reaction
slurry, of an anionic organopolyphosphonate
polyelectrolyte (typically, Briquest Z21-50A,
ethanolamfae bis-(methyleaephosphoaic acid), Albright
Wilson Americas, Iac., Richmond, VA) and from 0 to 10
weight percent of aluminum aulfate-octadacahydzate
(A1ZS04-I6H2~?). The introduction of carbon dioxide is
continued until precipitation of the calcium carbonate
ie substantially -complete. This typically occurs when
the conductivity of the carbonated slurry reaches a
minimum at a pH of about 10 to 11.
8xcept for the addition of aluminum sulfate
octadecahydrate; the process to this point is
essentially tbat of U.S. Patent No. 4,367,207.
The addition of aluminum sulfate
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octadecahydrate is disclosed in U.S. Patent No.
4,892,590,
Once a PCC of the desired particle size and
specific surface area is obtained, the PCC ie heat-aged
or milled to obtain the PCC characteristics required-
for a high-quality.~low cost ink jet recording paper.
Milling breaks pigment aggregates into
individual particles, which expoeeB PCC surfaces that
were joined, and are chemically different from the
aggregate surface. Milling is typically performed on a
PCC with a ecalenohedral, acicular, prismatic, or
rhombohedral morphology. Heat aging is normally
performed on a rhombohedral oz prismatic PCC, and not
only separates aggregates, but also involves further
precipitation on the particle surface. It is believed
that the newly precipitated material may be chemically
different from the original surface material; e.g., the
surface of a heat aged or milled PCC may have a higher
calcium-magnesium ratio.
Conventional heat aging, also known as
Oatwald ripnaiag, is a process whereby crystals such as
calcium carbonate, initially at a higher internal
energy state, and having relatively high phase
solubilities, undergo a phase transformation by
dissolving and redepositing on crystals at a lower
internal energy state. The process results in a final
crystal product characterized by greater perfection of
the crystal lattice structure, a narrower particle size
distribution, a greater degree of particle
discreteness, and a lower surface energy.
In the present invention, heat aging of PCC
starts by ending the reaction of carbon dioxide and
calcium hydroxide when the conductivity of the Blurry
reaches a minimum, which is typically at a pH of about
10-11. The PCC is then screened to remove impurities,
and up to about 1 percent by weight of an
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_ g
orgaaophoephonate, based oa the weight of PCC, is added
to control the extent or degree of heat aging. Other
chemical agents that are surface active with regard to
calcium carbonate will also serve as well as
orgaaophosphoaates to control the extent or degree of
heat aging. Such agents include, but are not limited
to the following, sodium polyphosphates, sodium
silicates, sodium polyacrylatss, various carboxylic
acids, such as mono, di, tri, and polycarboxylic acids,
and their salts, various polysaccharides, and various
gums with repeating carboxylic acid funetioaalities.
The slurry is then heated to a temperature of at least
about 75°C. and preferably about 80°C. or higher to
heat age the PCC particles. The heat aging step is
conducted for up to about 10 hours or more, depending
upon the temperature. At temperatures of about 80 to
85°C., the heating is conducted for about 2 to 5 hours.
The pH of the slurry rises to approximately 10.5 due to
the presence of uareacted calcium hydroxide. The aging
reaction is then monitored by measuring the surface
area of the PCC at hourly intervals. The heat aged PCC
that ie recovered as the final product of the process
has a rhomobohedral or prismatic morphology and a
specific surface area of about 60 to about 100 m2/g,
preferably about 65 to about 95 mZ/g, and most
preferably from about 80 to 90 mZ/g.
The organophosphonates employed is the
present invention are organopolyphosphonates of varying
molecular weights commonly used as scale inhibitors,
ssquesteraats, dsflocculants, and detergent proaroters.
Such orgsnophosphonates include, but are not limited
to, aitrilo tris (methyleae phosphonic acid),
ethyleaediaminetetra (methylane phosphoaic acid),
diethylenetriaminepaata (methyleae phosphoaic acid),
hydroxy ethane-l, 1-dipbosphonic acid, ethaaolamine,
ethanolamine bis-(methylaaephosphonic acid), N,N-
dimethyleae phosphoaic acid, and hexamethyleae-
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diamiaetetra (methyleae phosphoaic acid). The
preferred organophosphonate is ethsaolamine bis-
(methylenephosphoaic acid).
The milling of a calcium carbonate may be
carried out in either a wet or dry milling process in,
for example. a coavaatioaal ball mill, jet mill, micro
mill,. or media mill. The preferred milling is carried
out by introducing an aqueous slurry of PCC into a
media mill contaiaiag glass media of a size from about
0.7 to 0.9 mm. The media mill is equipped with
mechanical agitation, and the preferred weight percent
solids of the PCC slurry is frown about 10 to 30
percent, based on the total weight of the PCC and the
water. When media milling is typically performed on
PCC with a scalanohedral morphology, a PCC with a
specific surface area of frown about 10 to about 40
m2/g, preferably from about 15 to about 30 m2/g, and a
less elongated crystal shape is produced.
Examples of binders useful for coating
compositions for ink jet recording paper are those
heretofore conveatioaally used in the art, and include
polyvinyl alcohol ("PVOH") and derivatives thereof,
oxidized starch, etherified starch, estarified starch,
dextrin.and like starches, carboxymethylcellulose,
hydroxyethylcellulose and like cellulose derivatives,
cassia, gelatin, soybsaa protein, malefic anhydride
resin, lattices of usual styrenebutadieae copolymer,
methyl methacrylate-butadiene copolymer and like
conjugated diene polymers or copolymers, and latticsa
of acrylate and methacrylate polymers or copolymers and
like acrylic polymers, and latex. When required, the
coating composition may have further incorporated
therein is an amount conventionally used is the art of
conventional pigment dispersaats, tackifiere,
flowability modifiers, defoaming agents, foaming
inhibitors, release agents, coloring agents, and the
like.
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Ink jet recording papers incorporating the
PCC formulations of the present invention have been
prepared and tested. The following is a summary of the
procedures sad testing methods used. Once a PCC is
produced, the entire testing process can be categorized
into four areas; pigment preparation,_formulation with
binder, paper coating sad processing, and testing.
Specific details for each of these procedures are given
below.
Pigment Preparation:
Pigments to be tested are typically in the
form of a slurry or a filter cake. Samples in the form
of a slurry are concentrated to the desired solids by
vacuum filtration. In some instances, such ae with a
media milled PCC with a specific surface area of about
10 to 35 m2/g, the slurry solids are not further
altered is order to duplicate trial conditions. Once
the target formulation solids is set, the pigment is
diluted, if necessary, with water and thoroughly mixed.
The pigment is characterized by particle size
distribution (Sedigraph 5100), specific surface area
(Flowsorb), viscosity (Brookfield), and morphology by
scanning electron microscopy ("SEM°).
The surface area of the product was obtained
using a Micromeritics Flowsorb II 2300, which employs
BET theory with nitrogen as the absorbing gas. The
particle size was determined by a sedimentation
technique using a Micrameritics Sedigraph Model_5100 on
as aqueous dispersion of the product at about 3 percent
and using about 0.1 percent carboxylated
TM
polyelectrolyte (Daxad 30) as a dispersant.
Formulation:
Typical binders are cationic starch
(Filmcote-54~. National Starch), polyvinyl alcohol or
PVOH (Airvol 1074, Air Products Iac.). and latex (Dow
experimental size press latex). When a starch is used
as a binder, the dry starch is dispersed in water at
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about 10-25 percent solids, and then cooked in an
auta~ated laboratory cooker at about 195°C. for 50-190
minutes. The resulting viscous starch slurry is
combined with the pigment, which has been appropriately
prepared to attain the target formulation solids, and
mixed thoroughly oa a Preanier mill with.a Cowles type
open impeller blade. The formulation is mixed for
about 5 minutes until a completely homogenous slurry is
obtained, and the resulting formulation is
characterized by Hrookfield viscosity (10, 20, 50, and
100 r.p.m.) and solids.
Polyvinyl alcohol fs prepared is a manner
similar to that used for starch. The PVOH is hydrated
at about 200°C. in a laboratory cooker for 50-190
minutes at 10 percent solids. For the latex binder (50
percent solids), no preparation is necessary before
testing. The formulation of these binders with the
pigment is the same as with the starch.
Formulation solids for the tests were in the
range of about 20-2B percaat, with a typical coating
formulation having about 20 percent solids.
Pager Coatiac:
C3eaerally, as uasised base stock with an
81.3-83.0 g/st2 basis weight is used is the tests. The
paper is cut into 12x1?" sheets and secured to the CSD
Drawdown Apparatus, which coasirts of a glass plate
(12x1?") mounted oa metal base with spring clip at the
top. A coating formulation is applied with a CSD
drawdowa rod by placing the rod of choice, which
depends on target coat weight, at the top of the paper,
adding a thoroughly mixed 10-15 ml sample of the
fosmulation with a 30 ml syringe is a uniform line
across the top to the paper, below the rod, and coating
the paper by pulling the drawdowu rod from top to
bottom using light pressure and a constant, steady rate
for about 2 seconds.
The coat weight is determine by the stainless
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steel drawdowa rods, which are specifically grooved to
deliver a predetermined coating volume to the paper
surface. Rods with fewer grooves deliver a heavier
coat weight, since the spaces between the grooves are
wider. In tuna, rode with a greater number of more
tightly~spaced grooves produce lighter coat weights.
Typical coat weights are about~2 to 10 g/m2.
Dace a formulation has bean applied, the
paper is immediately dried with a hand held heat gun
for about 30-60 seconds, and then completely dried at
room temperature over a period of about 2-24 hours.
The dried papers are they cut into 8 1/2 x 11" sheets
for testing.
Payer Testing:
Minimum ink jet print quality specifications
have been established by Hewlett Packard Corporation
(wgpwy, ~erefore, most tests utilize HP methods to
determine the following print characteristics.
Optical density is a measure of the
reflection density of as image. A specific test
pattern is printed onto the paper, gad the optical
densities of pure black, composite black, cyan,
magenta, gad yellow are measured using a reflection
deasitometer (Macbeth RD918). The resulting optical
densities are compared to minimum HP specifications.
Ink spreading gad feathering can both
decrease the quality of ink jet print. Ink spreading
is defined as the growth or widening of printed areas.
Feathering is the wicking of ink, which results in
fuzzy images. This is measured by analyzing a specific
portion of the same printed pattern used for optical
- density measurements. The specific portion is
evaluated for ink area, spreading, gad ink perimeter,
- feathering. The resulting, digitized patters is
quaatitated gad co~pared to a commercial premnium ink
jet paper. The HP test method for ink spreading gad
feathering was not used in these tests, since the HP
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test is subjective rather than quantitative.
Ink Dry Time is a measure of the rate of ink
absorption into a sheet of paper. A specific test
pattern is printed, the image is blotted, and the
resulting optical density of the transferred black ink
is measured. The results are fitted to a decaying
exponential model from 8P, and the ink dry time is
calculated. The final dry times are comnpared to
minimum criteria set by 8P.
Waterfastaess is a measure of the amount of
colorant transferred from a printed area to as
unprinted area when water is applied. The
waterfastaess test pattern is printed onto the paper,
2501 of water is applied across the print, and allowed
to run over the printed area and adjacent uaprinted
area. The optical density of the transferred black ink
oa the unprintsd areas is measured. Resulting optical
densities are compared to HP standards.
Highlighter smearfastnsss is the measure of
ZO colorant transferred from a printed area to as
uaprinted area when contacted by two types of
highlighters. The specified test patters is printed
onto the paper sad, using as alkaline highlighter sad
an acid highlighter, a perpendicular line is drawn
Z5 across the test area. The optical density of
tr~sferred black ink oa uaprinted areas is measured
and compared to BP minimum criteria.
1~ color evaluation is performed with a CIBLAH
system, which uses as 8lrephro Dataeolor 2000
30 colorimeter to determine L*, a*, sad b* values to score
color appearance of cyan, green yellow, blue, magenta,
and red printed areas. The results are compared to HP -
diagrams for color quality.
Toner adhesion is a non-ink jet xerographic
35 test, which measures the degree of toner adhesion to
the coating. Toner adhesion is esaeatial for use as a
casmmercial multipurpose paper, which will often be used
CA 02394799 2005-08-04
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as a copier paper. Here, a test pattern ie copied onto
the paper using a Xerox copier, the test areas are
creased with a 5 pound roller, and the resulting toner
loss patterns are compared to a set of standards. The
degree of toner loss is rated from l, best or no toner
loss, to I0, worst or severe toner loss.
In the brightness teat, the coated paper is
tested for TAPPI brightness using the Technidyne S-4
brightness meter. Results are compared to the uncoated
base stock.
EgAMPLSS
The following non-limiting examples are
merely illustrative of the preferred embodiments of the
present invention, and are not to be construed as
limiting the invention, the scope of which is defined
by the appended claims.
B.xample 1
The preparation of a slurry of calcium
hydroxide was carried out by combining 1 part lime with
5 parts water with mechanical agitation at an initial
temperature of 50°C. The slurry was mixed for about 10
minutes, diluted with water to 1 part lime to 15 parts
water, and screened with a 60-mesh screen to remove
grit.
Calcium carbonate was precipitated from the
slurry in a 30 liter. stainless'steel reactor equipped
with variable speed agitation having two pitched blade
turbine impellers, heating and cooling jackets, a
stainless steel carbonation tube to direct a carbon
dioxide containing gas to the impeller, and a probe for
monitoring the pH of the suspension.
Tweaty-six (26) liters of calcium hydroxide
slurry, prepared ae described above, were added to the
reactor while stirring at 420 r.p.m. To the slurry was
then added 6 grams of organophosphonate (Hriquest 221-
50A, ethaaolamine bi-(methylenephosphonic acid),
Albright & Williams Americas, Iac., Richmond VA),
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corresponding to 0.1 percent by weight of Hriquest M
based on the calcium carbonate equivalent of the
calcium hydroxide slurry. A I liter solution
containing 95.0 g A12S04-168Z0 was then added. The
slurry temperature was adjusted to 9.5°C., and a gas
containing carbon dioxide (28 percent by volume C02 in
air)_was introduced at a rate of 2.3 S.C.F.M. while
stirring at~615 r.p.m. Carbonation of the calcium
hydroxide slurry was continued for 36 minutes with
cooling until a minimum slurry conductivity was
reached, indicating that the calcium carbonate
precipitation was complete. The final temperature of
the slurry was 15.8°C. The specific surface area of
the resulting calcium carbonate was determined to be
115 m2/g.
Example 2
In the same manner as described in Example 1,
calcium carbonate precipitation by carbonation of a
calcium hydroxide slurry with a carboy dioxide
a0 containing gas is the presence of 0.1 percent by weight
Hriquest and 3.15 percent by weight A1ZS04~168Z0 was
carried out with the same equipment. The carbonation
was complete is 35 minutes when a minimum conductivity
was attained. The final temperature of the slurry was
16.7°C.. and the p8 was 11.65. The specific surface
area of the PCC was 102.3 mZ/g. The PCC slurry was
screened with a 325-mash screen, and placed back into
the reactor. While stirring, 45 g of Hriquest 221-50A,
corresponding to 0.7 percent by weight Briquest. based
on the weight of PCC present, was added. The pH was
adjusted to 9.5. the slurry was heated to 80°C., and
the PCC was heat aged at 80°C. for 5 hours. The
specific surface area of the final product was
8Z.4 m2/g.
8xample 3
In the same manner as described in Example 2,
a calcium hydroxide slurry was carbonated in the
CA 02394799 2005-08-04
- 17 -
TM
presence of 0.1 percent by weight Hriquest and 3.15
percent by weight A12S04-16H20, where bath percentages
are based on the calcium carbonate equivalent of the
calcium hydroxide. The carbonation time was 39
minutes, the final pH was,10.9, and a PCC with a
specific surface area of 115.1 m2/g was obtained.
While stirring the mixture, 0.7 percent by weight
TM
Briquest 221-50A, based on the weight of PCC was added.
The slurry Was screened with a 325 mesh screen,
returned to the reactor, and heated to 80°C. for 2
hours. The specific surface area of the final product
was 81.6 m2/g.
Example 4
In the same manner as described in Example 2,
a calcium hydroxide slurry was carbonated in the
TM
presence of 0.? percent by weight Hriquest 221-50A and
3.15 percent by weight A12S04~16H20, both percentages
based on the calcium carbonate equivalent of calcium
hydroxide. The batch time to minimum conductivity was
36 minutes, and the final pH was 11.4. The specific
surface area of the PCC was 99.1 m2/g. The slurry was
passed through a 325 mesh screen, returned to the
reactor, stirred, and 0.15 percent by weight HriquestTM
221-50A, based on the weight of PCC, was added. The pH
of the slurry was adjusted to 9.5, and the slurry was
heated to 80°C. The PCC was heat aged at 80°C. for 2
hours, and a PCC with a specific surface area of 63.8
m2/g was obtained.
Example 5
A calcium carbonate slurry with a volume of
0.6 1 and a solids concentration of 20.2 percent by
weight, based on the total weight of calcium carbonate
and water, where the calcium carbonate was a
scalenohedral PCC with a specific surface area of 11.57
m2/g and an average particle size of 1.35 Ecm was placed
into a 1.5 1 stainless steel media mill containing 1.7
kg of glass beads of 0.7 to 0.9 mm. The media mill was
CA 02394799 2002-08-23
WO 96129369 PCTlUS96l03546
- 18 -
equipped with variable speed mechanical agitation. The
slurry was milled for 10 minutes with as agitation
speed of 2450 rpm. The milled product had a specific
surface area of 15.59 m2/g and as average particle size
of 0.35 microns.
. 8xample 6
A calcium carbonate slurry having a volume of
0.6 1 and a solids concentration of 18.7 percent by
weight, based oa the total weight of the calcium
carbonate sad the water, where the calcium carbonate
was a scalenohedral PCC with a specific surface area of
26.07 m2/g and an average particle size of 0.88 ~cm, was
placed in a 1.5 1 stainless steel media mill equipped
with variable speed agitation sad 1.7 kg of 0.7 to 0.9
amn glass beads. The slurry was milled for 10 minutes
using a 2450 rpm agitation speed. The milled PCC
product had a specific surface area of 30.11 m2/g sad
an average particle size of 0.26 ~cm.
The heat aged end media milled PCC's of
ales 1 to 6 were formulated with sa appropriate
binder, sad paper test sheets were coated with 6 g/m2
of the formulation in the manner described above.
After drying, the paper hand sheets were tested for
true black optical density. composite optical density,
spreading, penatration, dry time, and water solubility.
The results of these tests are given is Table 1.
CA 02394799 2002-08-23
WO 96/19369 PCTIUS96/03546
-19-
~, M
N
v o w ~n M e
n
o ~ ~ M M o 0
M o N u~
f" N M M
v o ~n ~ w
H
~r1 ,p o r1 . ,.i .-1 0~ d~ o
.
y M o .-t o
d1 ml e-~
d~ If1 N
y -1 N t0 r-1 e1
d~ H O v-~1 ~ 1C N rl O
d M O ri N
y
x" M N CD
a r-1 N e~ o~ o
~
M ,~ o .-i ~ t o ,~ o
y M O N ~i
N
N
p N It1 CD CD O
~
N O e-1 rl O rl !~ O
M O N r1
ri
e~l ~D N
p ri M 1D ~ O
.
~
N If1 v-1 rl ri t~1 O O
r1 O n1
x" N r1 tf1
p N M V~ ~ e-1
w
N ~ O ~-1 ei O CO N O
y M O N
al
r1 N
0t M N ~ O
~
rl O O r-1 O M O O
M O M
ri
'd~ N
01 M M tf1 O
~
ri p If1 O r1 r1 V~ O O
,~
ri O M
O P
V 01 W H M
~i ~ O O a-) ~0 O O O
y M O M
O r~
11 W-i ,'r, rl ,~, 1
rl 11 y ~,i 1 a y ~ y 'd
~1
o ~sm~ o xu..~ xu~ ~a ~..~ N.y
o b ~ a o a ..~ o a -.~ o o o o ~
x ~ ~d a a y ' ..r
~ '~ ~ ~
j' o y ~
~ ~
:~
o i .- .. w m ~ a o
. r ~ a w .
- ~ i
~
a1 3 w V a o4 N a0 m w A 3 on
as ~.1 C7 -.a y N .O
CA 02394799 2002-08-23
WO 96/29369 PCT/US96/03546
- 20 -
These results demonstrate a significant
improvement when compared to a typical uacoated
commercial paper, which, typically, has a composite
black optical density of about 0.9, a true optical
density of about 1.28, spreading of about 108, a
percent. penetration of about 38, a drying time of about
38, sad a water solubility of about 0.17. Hy
comparison, the best high cost, coated commercial paper
has a composite black optical density of about 1.2, a
true black optical density of about 1.56, spreading of
about 98, a percent penetration of about 28, a drying
time of about I2, sad a water solubility of nearly 0.
Therefore, as ink jet recording paper produced
according to the present invention, and, is particular,
a paper that is coated with a formulation based oa the
PCC produced is Example 2, is comparable is ink jet
priest quality to the beat high cost commercial paper
now available.
While it is apparent that the invention
herein disclosed is well calculated to fulfill the
objects above stated, it will be appreciated that
numerous modifications sad embodiments may be devised
by those skilled is the art. It ie intended that the
appended claims cover all such modifications and
embodiments as fall within the true spirit and scope of
the present invention.
