U.S. patent application number 16/896328 was filed with the patent office on 2021-12-09 for paper enhancing compositions, uses thereof and enhanced paper.
This patent application is currently assigned to ITI Technologies, Inc.. The applicant listed for this patent is ITI Technologies, Inc.. Invention is credited to David H. Creasey, Samuel Horace McCall, IV.
Application Number | 20210381169 16/896328 |
Document ID | / |
Family ID | 1000004938048 |
Filed Date | 2021-12-09 |
United States Patent
Application |
20210381169 |
Kind Code |
A1 |
Creasey; David H. ; et
al. |
December 9, 2021 |
PAPER ENHANCING COMPOSITIONS, USES THEREOF AND ENHANCED PAPER
Abstract
The present invention provides certain paper enhancing
compositions, typically aqueous compositions, for use in the
manufacture and coating of paper, and paper products. The paper
enhancing compositions provide certain paper processing advantages
and distinct final paper product characteristics. The present
invention further provides carbonate enhancing composition useful
for preparing enhanced carbonate compositions used in the paper
manufacturing processes.
Inventors: |
Creasey; David H.; (Leland,
NC) ; McCall, IV; Samuel Horace; (Leland,
NC) |
|
Applicant: |
Name |
City |
State |
Country |
Type |
ITI Technologies, Inc. |
Leland |
NC |
US |
|
|
Assignee: |
ITI Technologies, Inc.
Leland
NC
|
Family ID: |
1000004938048 |
Appl. No.: |
16/896328 |
Filed: |
June 9, 2020 |
Current U.S.
Class: |
1/1 |
Current CPC
Class: |
D21H 23/04 20130101;
D21H 21/36 20130101; D21H 21/18 20130101; D21H 19/385 20130101;
D21H 19/02 20130101; D21H 21/24 20130101; D21H 17/675 20130101 |
International
Class: |
D21H 21/36 20060101
D21H021/36; D21H 21/18 20060101 D21H021/18; D21H 21/24 20060101
D21H021/24; D21H 19/38 20060101 D21H019/38; D21H 19/02 20060101
D21H019/02; D21H 17/67 20060101 D21H017/67 |
Claims
1. A paper forming mixture comprising a paper making fiber and at
least one carbonate enhanced composition wherein the at least one
carbonate enhanced composition comprises: a carbonate selected from
the group consisting of at least one calcium carbonate, at least
one silver carbonate, at least one organic compound carbonate and
mixtures thereof; and at least one carbonate enhancing composition
wherein the carbonate enhancing composition comprises: a solubility
enhancing aqueous composition comprising an anionic component
consisting essentially of sulfate ions, alone or in combination
with bisulfate ions, having a concentration from about 8.00 moles
per liter to about 13.00 moles per liter of the composition volume;
a cationic component consisting essentially of ammonium ions having
a concentration from about 1.45 moles per liter to about 2.01 moles
per liter of the composition volume; and hydrogen ions in a
concentration from about 17.38 mols per liter to about 21.68 moles
per liter of the composition volume; sodium hydroxide solution
having a concentration of about 5% to about 7.5% volume/volume of
the total aqueous phase volume of the composition; and a sulfate
selected from the group consisting of copper sulfate, silver
sulfate and combinations thereof having a concentration from about
20 percent to about 26 percent mass/volume of the total aqueous
phase volume of the composition.
2. A paper forming mixture of claim 1, wherein the paper making
fiber is pulp wood.
3. A method of increasing at least one of the group consisting of
paper tensile, bond and burst strength of paper comprising the
addition of at least one carbonate enhanced composition to the
wet-end of a paper making process compared to an equal amount of
unenhanced calcium carbonate.
4. Antimicrobial paper comprising paper prepared by the addition of
at least one carbonate enhanced composition to the wet-end of a
paper making process.
5. A paper enhancing composition comprising water, at least one
solubility enhancing aqueous composition, sodium hydroxide, and
copper sulfate
6. A paper enhancing composition of claim 5, further comprising at
least one surfactant selected from the group consisting of at least
one non-ionic surfactants and at least one anionic surfactant.
7. A paper enhancing composition of claim 6, wherein the solubility
enhancing aqueous composition comprises 1 part of a first solution
added to about 15 to about 20 parts of water to form a second
solution; sodium hydroxide solution having a concentration of about
5% to about 7.5% volume/volume of the total aqueous phase volume of
the composition; and copper sulfate having a concentration from
about 20 percent to about 26 percent mass/volume of the total
aqueous phase volume of the composition.
8. A paper enhancing composition of claim 7, further comprising the
addition of an acid or base to adjust the pH to a pH from about 2.5
to about 3.5.
9. Enhanced paper comprising paper having applied during the wet
press stage of paper production at least one aqueous enhancing
paper composition.
10. A method of preparing paper for medical and industrial
protective uses comprising applying at least one aqueous paper
enhancing composition at any stage during the paper making
process.
11. A paper coating comprising at least one aqueous paper enhancing
composition.
12. Paper used for medical and industrial protective purposes
comprising paper coated with at least one paper enhancing
composition.
13. Coated paper having antimicrobial activity comprising paper
coated with at least one paper enhancing composition.
14. Coated paper of claim 13, wherein the antimicrobial activity is
selected from the group consisting of antibacterial, antifungal,
antiviral and anti-mold.
15. A method of extending the shelf-life of perishable foodstuff
comprising placing such foodstuff in contact with coated paper of
claim 11.
16. Antimicrobial paper comprising paper prepared by the addition
of at least one paper enhancing composition added to paper in the
wet-end stage of the paper making process, applied to paper during
the wet press stage of the paper making process or applied to paper
or paper products as a coating.
17-18. (canceled)
19. A paper forming mixture of claim 1, wherein the aqueous
carbonate enhancing composition further comprises at least one
surfactant selected from the group consisting of non-ionic
surfactants and anionic surfactants having a concentration from
about 0.05 percent to about 0.15 percent volume/volume of the total
aqueous phase volume of the composition.
20. A paper forming mixture composition of claim 1, wherein the
aqueous carbonate enhancing composition further comprises at least
one acid or at least one base to adjust the final pH in the range
from about 2.5 to about 3.5.
21. A paper forming mixture of claim 20, wherein the paper making
fiber is pulp wood.
22. A paper forming mixture composition of claim 19, wherein the
aqueous carbonate enhancing composition further comprises at least
one acid or at least one base to adjust the final pH in the range
from about 2.5 to about 3.5.
23. A paper forming mixture consisting essentially of a paper
making fiber and at least one carbonate enhanced composition
wherein the at least one carbonate enhanced composition consisting
essentially of: A carbonate selected from the group consisting of
at least one calcium carbonate, at least one silver carbonate, at
least one organic compound carbonate and mixtures thereof; and at
least one carbonate enhancing composition wherein the carbonate
enhancing composition is consisting essentially of: a solubility
enhancing aqueous composition consisting essentially of an anionic
component consisting essentially of sulfate ions, alone or in
combination with bisulfate ions, having a concentration from about
8.00 moles per liter to about 13.00 moles per liter of the
composition volume; a cationic component consisting essentially of
ammonium ions having a concentration from about 1.45 moles per
liter to about 2.01 moles per liter of the composition volume; and
hydrogen ions in a concentration from about 17.38 mols per liter to
about 21.68 moles per liter of the composition volume; sodium
hydroxide solution having a concentration of about 5% to about 7.5%
volume/volume of the total aqueous phase volume of the composition;
and a sulfate selected from the group consisting of copper sulfate,
silver sulfate and combinations thereof having a concentration from
about 20 percent to about 26 percent mass/volume of the total
aqueous phase volume of the composition.
24. A paper forming mixture of claim 23, wherein the paper making
fiber is pulp wood.
25. A paper forming mixture composition of claim 23, wherein the
aqueous carbonate enhancing composition further consists of at
least one acid or at least one base to adjust the final pH in the
range from about 2.5 to about 3.5.
26. A paper forming mixture of claim 23, wherein the aqueous
carbonate enhancing composition further consists at of at least one
surfactant selected from the group consisting of non-ionic
surfactants and anionic surfactants having a concentration from
about 0.05 percent to about 0.15 percent volume/volume of the total
aqueous phase volume of the composition.
27. A paper forming mixture composition of claim 26, wherein the
aqueous carbonate enhancing composition further consists of at
least one acid or at least one base to adjust the final pH in the
range from about 2.5 to about 3.5.
28. A paper forming mixture of claim 26, wherein the paper making
fiber is pulp wood.
29. A paper forming mixture of claim 22, wherein the carbonate
enhancing composition is substantially free of solids.
30. A paper forming mixture of claim 27, wherein the carbonate
enhancing composition is substantially free of solids.
Description
CROSS-REFERENCE TO RELATED APPLICATIONS
[0001] The presently disclosed subject matter is related to U.S.
patent application Ser. No. 16/745,846 entitled "Plastic Modifying
Compositions and Enhanced Carbonate Compositions" filed on Jan. 17,
2020; the entire disclosure of which is incorporated herein by
reference.
BACKGROUND
[0002] The present invention relates to paper enhancing
compositions useful for the manufacture of paper, paper products,
paperboard and paperboard products, and coated paper and paperboard
and products made therefrom including, for example and without
limitation, cardboard and cardboard products. Also provided are
enhanced carbonate compositions comprising at least one carbonate
and at least one carbonate enhancing composition.
[0003] Although large-scale pulp-based paper processing methods
have been established since the 1840's, a variety of substrates
have been used and continue being used over the millennia
including, for example and without limitation, cotton, silk,
bamboo, Phragmites (e.g., common reeds) and traditional hard and
soft wood sources. The use of such substrates each have particular
challenges and techniques, and each typically use one or more
fillers that extend the use of substrate(s), frequently reducing
cost of the final product, while imparting specific and desired
properties to the final product. Process development, particularly
processes for continued cost reduction while maintaining and
improving desired and/or new qualities to the final paper products
continue. Accordingly, the present disclosure provides certain
aspects relative to such continued development and improvement of a
variety of products and processes for the processing of coated and
uncoated paper and the coating of paper.
[0004] As further reviewed herein, once paper is manufactured,
additional challenges exist when coating paper for a variety of
uses. As such, the present invention also provides various aspects
related to compositions and methods related to the preparation and
processing of paper and paper products post manufacture of paper
including, for example, a variety of coatings for various
purposes.
SUMMARY
[0005] One aspect of the present invention provides a paper forming
mixture comprising a paper making fiber and at least one carbonate
enhanced composition of the present invention. Addition of such
carbonate enhanced mixture is typically, without limitation, added
to the paper making process at the wet-end.
[0006] Further provided is a paper forming mixture comprising a
pulp-based mixture of pulp and at least one carbonate enhanced
composition of the present invention.
[0007] An additional aspect of the present invention provides a
paper forming mixture comprising a pulp-based mixture of pulp and
at least one carbonate enhanced composition of the present
invention, wherein the amount of calcium carbonate filler is at
least five percent (5%) greater than the amount calcium carbonate
fill typically added to a given paper type. For example, and
without limitation, as reviewed in part above, for a paper type
typically using 10-30% fill, the amount of fill that can be added
to the paper forming wet mixture will equal at least 31.5% of the
total wet mixture. This increase in calcium carbonate fill amount
can be used for any paper type well known to the skilled
artisan.
[0008] A further aspect of the present invention provides for a
method of modifying the zeta potential of calcium carbonate used in
a paper making process comprising the addition of at least one
carbonate enhanced composition of the present invention to the
wet-end of a paper making process. As used relative to the zeta
potential, such modification can be an increase or decrease of the
zeta potential, but typically is an increase in the zeta potential
as used herein.
[0009] More particularly, the present invention also provides a
method of modifying the zeta potential of calcium carbonate used in
a pulp-based paper making process comprising the addition of at
least one carbonate enhanced composition of the present invention
to the wet-end of a paper making process.
[0010] An additional aspect of the present invention provides for
antimicrobial paper, having a multitude of uses, comprising paper
prepared by the addition of at least one carbonate enhanced
composition of the present invention to the wet-end of a paper
making process. As used herein, the term "antimicrobial activity"
means the inhibition of microbes.
[0011] The present invention further provides a paper enhancing
composition comprising water, at least one solubility enhancing
aqueous composition, sodium hydroxide, copper sulfate and,
optionally, at least one surfactant selected from the group
consisting of non-ionic surfactants and/or anionic surfactants.
[0012] An additional aspect of the present invention provides an
aqueous or, substantially aqueous, paper enhancing composition
(aqueous notwithstanding the potential for copper sulfate to not
have completely dissolved in the paper enhancing composition)
comprising an aqueous phase comprising a solubility enhancing
aqueous composition wherein 1 part of a first solution is added to
about 15 to about 20 parts of water, frequently deionized water, to
form a second solution; sodium hydroxide solution having a
concentration of about 5% to about 7.5% volume/volume of the total
aqueous phase volume of the composition; at least one surfactant
selected from the group consisting of non-ionic surfactants and
anionic surfactants having a concentration from about 0.05 percent
to about 0.15 percent volume/volume of the total aqueous phase
volume of the composition; and copper sulfate having a
concentration from about 20 percent to about 26 percent mass/volume
of the total aqueous phase volume of the composition. As used
herein, the term "aqueous paper enhancing composition" also
includes any such composition that is substantially aqueous as
indicated herein.
[0013] A further aspect of the present invention further comprises
the addition of an acid or base to adjust the pH to a pH from about
2.5 to about 3.5 to a paper enhancing composition of the present
invention.
[0014] The present invention further provides a method of
increasing at least one of paper tensile strength, bond strength
and burst strength compared to paper prepared without the addition
of at least one paper enhancing composition comprising the addition
of at least one paper enhancing composition to the wet-end of the
paper making process.
[0015] Another aspect of the present invention provides a method
for decreasing the interstitial pore size between and among paper
fibers in a wet-end-paper making process compared to paper prepared
without the addition of at least one paper enhancing composition
comprising the addition of at least one paper enhancing composition
to the wet-end of the paper making process.
[0016] An additional aspect of the present invention provides a
method for increasing paper density compared to paper prepared
without the addition of at least one paper enhancing composition
comprising the addition of at least one paper enhancing composition
to the wet-end of the paper making process.
[0017] A further aspect of the present invention provides for paper
having antimicrobial properties comprising paper prepared using at
least one paper enhancing composition during the wet-end process
stage of paper making.
[0018] Also provided herein is a method of modifying the zeta
potential of calcium carbonate when used in the paper making
process comprising applying at least one aqueous paper enhancing
composition during the wet-end stage of paper production.
[0019] Further provided is a method of modifying the zeta potential
of calcium carbonate when used in a pulp-based paper making process
comprising applying at least one aqueous paper enhancing
composition during the wet-end stage of paper production.
[0020] Another aspect of the present invention provides for
enhanced paper comprising paper having applied during the wet press
stage of paper production at least one aqueous enhancing paper
composition.
[0021] Further provided herein are the following methods: [0022] A
method of enhancing paper comprising applying at least one aqueous
paper enhancing composition during the wet press stage of paper
production. [0023] A method of increasing at least one of the group
consisting of tensile strength, bond strength and burst strength in
paper compared to the respective tensile strength, bond strength
and burst strength of paper untreated with an aqueous paper
enhancing composition comprising applying at least one aqueous
paper enhancing composition during the wet press stage of paper
production. [0024] A method of modifying the zeta potential of
calcium carbonate when used in the paper making process comprising
applying at least one aqueous paper enhancing composition during
the wet press stage of paper production. [0025] More particularly,
the present invention also provides a method of modifying the zeta
potential of calcium carbonate used in a pulp-based paper making
process comprising applying at least one aqueous paper enhancing
composition during the wet press stage of paper production. [0026]
A method of increasing at least one of the group consisting of
paper tensile strength, bond strength and burst strength of paper
comprising applying at least one aqueous paper enhancing
composition during the wet press stage of paper production compared
to paper untreated with an aqueous paper enhancing composition
without an increase in caliper pose.
[0027] Further provided is antimicrobial paper, having a multitude
of uses, comprising paper prepared by the application of at least
one aqueous paper enhancing composition of the present invention
during the wet press stage of paper production.
[0028] Another aspect of the present invention provides for a paper
coating comprising at least one aqueous paper enhancing
composition.
[0029] An additional aspect provides for paper coated with at least
one aqueous paper enhancing composition.
[0030] Another aspect of the present invention provides a method of
increasing at least one of the group consisting of paper tensile
strength, bond strength and burst strength of paper comprising the
application of a coating to paper comprising at least one paper
enhancing composition of the present invention.
[0031] An additional aspect of the present invention provides for a
method of providing at least one of protection from fingerprints
and other blemishes, help prevent metallic inks from tarnishing,
and provide paper surfaces that can be written on with multiple
media (including, without limitation, pencil, pen, ink jet
printers, laser jet printers off-set printers and the like)
comprising the application of a coating to paper comprising at
least one paper enhancing composition of the present invention.
[0032] A further aspect of the present invention provides for a
method of providing improvement of at least one of protection from
fingerprints and other blemishes, help prevent metallic inks from
tarnishing, and provide paper surfaces that can be written on with
multiple media (including, without limitation, pencil, pen, ink jet
printers, laser jet printers off-set printers and the like)
compared to paper coatings not including the application of at
least one aqueous paper enhancing composition of the present
invention comprising the application of a coating to paper
comprising at least one paper enhancing composition of the present
invention.
[0033] Accordingly, another aspect of the present invention
provides for coated paper having antimicrobial activity comprising
paper coated with at least one aqueous paper enhancing composition
of the present invention.
[0034] An additional aspect of the present invention provides for
paper having antimicrobial properties comprising paper coated with
at least one aqueous paper enhancing composition of the present
invention.
[0035] Another aspect of the present invention provides for a
method of preparing paper having antimicrobial activity comprising
applying as a coating to paper at least one aqueous paper enhancing
composition of the present invention to said paper.
[0036] Further provided is antimicrobial paper, having a multitude
of uses, comprising paper prepared by the application of a coating
of at least one aqueous paper enhancing composition of the present
invention during the wet press stage of paper production.
[0037] Another aspect of the present invention provides a method of
extending the shelf-life of perishable foodstuff comprising placing
such foodstuff in contact with paper coated with at least one
aqueous paper enhancing composition of the present invention. Such
shelf-life can be extended for at least 24 hours, providing
substantial value to providers of such perishable foodstuff.
[0038] Further provided is a method for preparing paper for medical
and industrial protective uses comprising applying as a coating to
paper at least one aqueous paper enhancing composition.
[0039] An additional aspect provides a method of preparing paper
for use in masks for mammalian, particularly human, use comprising
applying as a coating at least one aqueous paper enhancing
composition.
[0040] An additional aspect of the present invention provides a
carbonate enhanced composition comprising at least one carbonate
and at least one carbonate enhancing composition.
[0041] Other aspects of the present invention provide a variety of
methods of using a carbonate enhanced composition of the present
invention to a variety of intermediate and final products as
further described herein below.
[0042] An additional aspect of the present invention provides a
carbonate enhancing composition comprising an aqueous phase
comprising a solubility enhancing aqueous composition wherein 1
part of a first solution is added to about 15 to about 20 parts of
water to form a second solution; sodium hydroxide solution having a
concentration of about 5% to about 7.5% volume/volume of the total
aqueous phase volume of the composition; at least one surfactant
selected from the group consisting of non-ionic surfactants and
anionic surfactants having a concentration from about 0.05 percent
to about 0.15 percent volume/volume of the total aqueous phase
volume of the composition; and copper sulfate having a
concentration from about 20 percent to about 26 percent mass/volume
of the total aqueous phase volume of the composition; optionally
comprising the addition of at least one acid or at least one base
to adjust the final composition pH to a pH of about 2.5 to about
3.5.
[0043] Another aspect of the present invention provides a carbonate
enhancing composition comprising an aqueous phase comprising a
solubility enhancing aqueous composition wherein 1 part of a first
solution is added to about 15 to about 20 parts of water to form a
second solution and sodium hydroxide solution having a
concentration of about 5% to about 7.5% volume/volume of the total
aqueous phase volume of the composition; and copper sulfate having
a concentration from about 20 percent to about 26 percent
mass/volume of the total aqueous phase volume of the composition,
optionally comprising the addition of at least one acid or at least
one base to adjust the final composition pH to a pH of about 2.5 to
about 3.5.
[0044] An additional aspect of the present invention provides an
antimicrobial composition comprising at least one composition
selected from the group consisting of at least one carbonate
enhanced composition and at least one carbonate enhancing
composition, wherein the carbonate enhancing composition is
optionally aqueous or substantially aqueous.
[0045] A further aspect of the present invention provides a product
requiring at least one carbonate as an element in the manufacture
thereof comprising at least, in part, at least one carbonate
enhanced composition used in the manufacture of such product.
[0046] An additional aspect of the present invention provides an
antimicrobial composition comprising at least one carbonate
enhanced composition.
BRIEF DESCRIPTION OF THE DRAWINGS
[0047] Features of the present invention will be more fully
appreciated by reference to the following detailed description when
taken in conjunction with the following drawings in which:
[0048] FIG. 1. depicts a low resolution spectrogram with 1 part
reaction unit to 5 parts total.
[0049] FIG. 2. depicts a high resolution spectrogram with 1 part
reaction unit to 5 parts total.
[0050] FIG. 3. depicts a low resolution spectrogram with 1 part
reaction unit to 10 parts total.
[0051] FIG. 4. depicts a high resolution spectrogram with 1 part
reaction unit to 10 parts total.
[0052] FIG. 5. depicts a low resolution spectrogram with 1 part
reaction unit to 20 parts total.
[0053] FIG. 6. depicts a high resolution spectrogram with 1 part
reaction unit to 20 parts total.
[0054] Each of the spectrograms was run according to the respective
teachings of Example 6. Each of the spectrograms depicts
compositions that are free of salt crystals or other solids formed
from the ammonium sulfate and sulfuric acid reactants.
[0055] While the aspects of the present disclosure are susceptible
to various modifications and alternative forms, specific
embodiments thereof are shown by way of example in the drawings and
will herein be described in detail. It should be understood,
however, that the drawings and detailed description are not
intended to limit the disclosure to the particular forms
illustrated but, on the contrary, the intention is to cover all
modifications, equivalents and alternatives falling within the
spirit and scope of the present disclosure as defined by the
appended claims. The headings used herein are used for
organizational purposes only and are not meant to limit the scope
of the description. As used throughout this application, the word
"may" is used in a permissive sense, meaning: "having the potential
to"; rather than the mandatory sense meaning: "must". Similarly,
the words "include", "including" and "includes" means including,
without limitation. Additionally, as used in this specification and
the appended claims, the singular forms "a`, "an" and "the" include
singular and plural referents unless the content clearly dictates
otherwise.
[0056] The scope of the present disclosure includes any feature or
combination of features disclosed herein (either explicitly or
implicitly), or any generalization thereof, whether or not it
mitigates any or all of the problems addressed herein. Accordingly,
new claims may be formulated during prosecution of this application
(or an application claiming priority thereto) to any such
combinations of features. In particular, with reference to the
appended claims, features from dependent claims may be combined
with those of independent claims and features from respective
independent claims may be combined in any appropriate manner and
not merely in the specific combinations enumerated in the appended
claims.
DETAILED DESCRIPTION
Definitions
[0057] The term "antimicrobial" means antibacterial, anti-fungal,
antiviral and anti-mold, each individually and collectively.
[0058] The term "alkali and alkaline metal carbonates" have their
traditional meanings in the art.
[0059] The term "calcium carbonate" has its traditionally meaning
and included, for example and without limitation, ground calcium
carbonate, precipitated calcium carbonate and needle calcium
carbonate, each being prepared in a variety of, for example and
without limitation, purities, densities, fineness of grain,
morphologies, surface areas, high oil absorption, bulk densities
from ultra-low to super high powder densities, and the like.
[0060] The term "dilute sodium hydroxide" means sodium hydroxide,
typically but not limited to solid form, diluted with water to a
concentration of not greater than about 20 percent.
[0061] The term "first solution" means a solution of ammonium
sulfate and sulfuric acid as further described herein and used in
preparing a solubility enhancing aqueous composition.
[0062] The term "fill material" means at least one of calcium
carbonate, China clay, talc, titanium dioxide and/or one or more
other material that is typically added to a substrate for the
formation of a final paper product which includes in part, calcium
carbonate. The term "fill material", when used more generally in
reference to the enhanced carbonate compositions of the present
invention, has the traditional meaning as used in the art for the
respective product in which the enhanced carbonate composition is
used.
[0063] The term "free of solids" means that the solubility
enhancing aqueous composition do not form salt crystals or other
solids that remain in the composition over time, such salt crystals
or other solids being formed from the reactants of ammonium sulfate
and sulfuric acid.
[0064] The term "inhibition" or "inhibiting" means the act of
prophylaxis, retarding and/or controlling the growth of microbes in
products as described herein.
[0065] The term "microbes" means, individually or collectively,
bacteria, fungi, viruses and/or mold.
[0066] The term "paper" means paper and paperboard (single or
multi-ply), unless otherwise differentiated, as each term is known
in the art.
[0067] The term "paper and paperboard products(s) means, without
limitation, any product that contains or is made from paper and/or
paperboard in part or in whole. One example of such products
includes, without limitation, cardboard.
[0068] The term "pulp" or "paper pulp" (used interchangeably) means
any raw material or combination of raw materials used for paper
manufacture. Paper pulp or pulp can contain, for example and
without limitation, vegetable, cellulosic, mineral and/or man-made
fibers.
[0069] The term "reaction unit" relative to the preparation of a
solubility enhancing aqueous composition means the desired total
volume of a first solution as expressed as a ratio of a range of
ammonium sulfate concentrations to sulfuric acid concentrations
(the reactants).
[0070] The term "second solution" means the first solution as
prepared for a final volume plus the requisite amount of water to
form a composition of the present invention as further described
herein and used in preparing a solubility enhancing aqueous
composition.
[0071] The term "sodium hydroxide solution" means a sodium
hydroxide, typically in a dilute sodium hydroxide solution, wherein
the solution can be any dilution as further set forth herein.
[0072] The term "solubility enhancing aqueous composition" means
the solubility enhancing aqueous compositions as described
herein.
[0073] The term "sulfate anions" encompasses each of sulfate
anions, bisulfate anions and combinations thereof. Combinations of
sulfate anions and bisulfate anions are common in the solubility
enhancing aqueous compositions described herein.
[0074] The term "sulfuric acid" means concentrated sulfuric acid
having a concentration of from about 95% to about 98%.
[0075] The term "substantially free of solids" means that the
solubility enhancing aqueous compositions and/or the enhanced
carbonate compositions described herein are at least 95 percent
aqueous or, alternatively, at least 98 percent aqueous without the
formation of salt crystals or other solids. The addition of
materials not an element of the solubility enhancing aqueous
compositions and/or carbonate enhancing compositions in the
preparation of compositions of the present invention may affect the
amount of salts and/or other solids. As such, the term
"substantially free of solids" pertains only to the preparations of
each of the solubility enhancing aqueous compositions and/or the
carbonate enhancing compositions of the present invention described
herein.
DESCRIPTION
[0076] The following description and examples are included to
demonstrate the embodiments of the present disclosure. It should be
appreciated by those of skill in the art that the compositions,
techniques and methods disclosed in the examples herein function in
the practice of the disclosed embodiments. However, those skilled
in the respective arts should, in light of the present disclosure,
appreciate that changes can be made to the specific embodiments and
still obtain a like or similar result without departing from the
spirit and scope of the disclosed embodiments.
[0077] The present specification includes references to "one
aspect/embodiment" or "an aspect/embodiment". These phrases do not
necessarily refer to the same embodiment although embodiments that
include any combination of the features or elements disclosed
herein are generally contemplated unless expressly disclaimed
herein. Particular features, processes, elements or characteristics
may be combined in any suitable manner consistent with this
disclosure.
[0078] With the pulp-paper industry, at least two well-known
problems exist with the use of calcium carbonate filler (e.g.,
precipitated, ground, needles and, without limitation, the like)
incorporated into the paper web during paper formation on the
papermaking wire, particularly increased use of such filler: i.
filler particles added to fiber suspended in water are not easily
retained in the forming sheet because they are often too small to
be entrapped mechanically and because filler particles are
negatively charged, they repel each other; and ii. filler particles
can interfere with fiber-fiber bonding; therefore, causing tensile
strength of the paper to suffer. Also, the addition of calcium
carbonate beyond a certain level will cause, among other problems,
reduced paper strength and stiffness, increased size demand, and
increased abrasion and dusting.
[0079] Moreover, there are four primary means by which filler,
particularly calcium carbonate, interacts with pulp fiber: i.
calcium carbonate is distributed among the fibers; ii. one end of
calcium carbonate is embedded in one fiber with the other end
embedded in another fiber; iii. one end of calcium carbonate is
embedded in one fiber with the other end being distributed among
the fibers; and iv. calcium carbonate is entirely embedded in a
fiber. The challenge is to provide for an environment for
fiber-filler entanglement and friction while also providing for
enhanced hydrogen bonding. The potential benefits can be an
increase in filler loading, reducing fiber input and reducing paper
costs, while maintaining the positive attributes typical of calcium
carbonate used as a filler in paper, which are many and well known
in the art.
[0080] Although filler particles (type and size) are frequently
designed to accommodate individual paper customer needs, there
exists a wide range of filler introduced during this aspect of the
paper making process. For the sake of clarity, as used herein, the
term "paper" also includes "paper board" products in addition to
products made from such paper and paper board products. For
example, and without limitation, calcium carbonate fill is
generally about 10% to about 30%, typically about 20% for printing
paper. The introduction of calcium carbonate can be added during
the process at the wet-end or as a surface application. Filler
level of up to about 50%, although not common, can be used for
coated papers (e.g., wood-free 135 g/m2) and copy and office paper
(75-80 g/m2 with up to 30% filler used; although 15% filler is
reported to be used in North America for weight levels up to 75
g/m2). In essence, there are a plethora of variables known in the
paper preparation art which are incorporated into a variety of
processes, including numerous forms of filler, particularly calcium
carbonate, used to form a broad range of paper, including paper
board, products. It is not the intent of this disclosure to reteach
paper making processes. Rather, it is the intent to recite a
representative sample of some of the processes, and related
variables, used in an intricate yet well-known art. As such, the
use of calcium carbonate and, more specifically, carbonate enhanced
compositions of the present disclosure, is not to be limited to the
brief review of paper making processes disclosed herein. In fact,
the carbonate enhanced compositions of the present invention can be
used in lieu of straight calcium carbonate regardless of form, as
used in wet-end processing.
[0081] Without being held to a particular theory, it is believed
that the addition of at least one carbonate enhanced composition of
the present invention compared to using straight calcium carbonate
as a filler in pulp-based or other paper making processes modifies
the zeta potential of the calcium carbonate, potentially providing
stronger bonds/interaction between the fiber and calcium carbonate
filler. The end result is a potentially higher percentage of
calcium carbonate in the wet-end without the negative attributes
associated with increased amounts of filler for each particular
paper type. Such use of carbonate enhanced compositions of the
present invention provides, without limitation, excellent
runnability, overall potential cost savings, improved hydrophobic
sizing, opacity, and print characteristics, and improved, or at
least not a loss, of tensile, bond and/or burst strength, while
potentially not affecting paper caliper or caliper pose compared to
the use of non-enhanced calcium carbonate.
[0082] Accordingly, one aspect of the present invention provides a
paper forming mixture comprising a paper making fiber and at least
one carbonate enhanced composition of the present invention.
[0083] Addition of such carbonate enhanced mixture is typically,
without limitation, added to the paper making process at the
wet-end.
[0084] Further provided is a paper forming mixture comprising a
pulp-based mixture of pulp and at least one carbonate enhanced
composition of the present invention.
[0085] Also provided is a paper forming mixture comprising a paper
making fiber and at least one paper enhancing composition of the
present invention. Addition of such paper enhancing composition is
added, among other uses as set forth herein, to the paper making
process at the wet-end.
[0086] Further provided is a paper forming mixture comprising a
pulp-based mixture of pulp and at least one paper enhancing
composition of the present invention.
[0087] An additional aspect of the present invention provides a
paper forming mixture comprising a pulp-based mixture of pulp and
at least one carbonate enhanced composition of the present
invention, wherein the amount of calcium carbonate filler is at
least five percent (5%) greater than the amount calcium carbonate
fill typically added to a given paper type. For example, and
without limitation, as reviewed in part above, for a paper type
typically using 10-30% fill, the amount of fill that can be added
to the paper forming wet mixture will equal at least 31.5% of the
total wet mixture. This increase in calcium carbonate fill amount
can be used for any paper type well known to the skilled
artisan.
[0088] An further aspect of the present invention provides for a
method of modifying the zeta potential of calcium carbonate used in
a paper making process comprising the addition of at least one
carbonate enhanced composition of the present invention to the
wet-end of a paper making process. More particularly, the present
invention also provides a method of modifying the zeta potential of
calcium carbonate used in a pulp-based paper making process
comprising the addition of at least one carbonate enhanced
composition of the present invention to the wet-end of a paper
making process.
[0089] The present invention further provides a method of
increasing at least one of the group consisting of paper tensile,
bond and burst strength of paper comprising the addition of at
least one carbonate enhanced composition of the present invention
to the wet-end of a paper making process compared to an equal
amount of unenhanced calcium carbonate. As used herein, the term
"unenhanced calcium carbonate" means straight calcium carbonate
without the addition of at least one aqueous paper enhancing
composition of the present invention.
[0090] A further aspect of the present invention provides a method
of increasing at least one of the group consisting of paper
tensile, bond and burst strength of paper comprising the addition
of at least one carbonate enhanced composition of the present
invention to the wet-end of a paper making process compared to an
equal amount of unenhanced calcium carbonate without a decrease in
at least one selected from the group consisting of runability,
hydrophobic sizing, opacity and print characteristics.
[0091] An additional aspect of the present invention provides a
method of increasing at least one of the group consisting of paper
tensile strength, bond strength and burst strength of paper
comprising the addition of at least one carbonate enhanced
composition of the present invention to the wet-end of a paper
making process compared to an equal amount of unenhanced calcium
carbonate without an increase in caliper pose.
[0092] Further provided is a method of increasing the amount of
calcium carbonate filler particles retained in a paper forming
sheet to fiber suspended in water during the paper making process
comprising the addition of at least one carbonate enhanced
composition of the present invention to the wet-end of a paper
making process compared to an equal amount of unenhanced calcium
carbonate.
[0093] As taught herein, the addition of a carbonate enhanced
composition of the present invention, through the modification of
carbonate zeta potential and otherwise, has the potential to form
more and tighter bonds among the fiber and fill than is otherwise
typically the case when using only unenhanced calcium carbonate as
a fill rather than at least one carbonate enhanced composition of
the present invention. As such, the pores of the paper can be
reduced with the use of the carbonate enhanced composition
resulting in paper that is less penetrable to dust and other
particulate matter, pollutants and microorganisms. Accordingly,
another aspect of the present invention provides for a method of
decreasing the pore size of paper comprising the addition of at
least one carbonate enhanced composition of the present invention
to the wet-end of a paper making process compared to an equal
amount of unenhanced calcium carbonate. This phenomenon also
provides for a method of preparing paper for medical and industrial
protective uses comprising the addition of at least one carbonate
enhanced composition of the present invention to the wet-end of a
paper making process.
[0094] As further referenced herein, the carbonate enhanced
compositions of the present invention also provide antimicrobial
activity. Accordingly, an additional aspect of the present
invention provides for antimicrobial paper, having a multitude of
uses, comprising paper prepared by the addition of at least one
carbonate enhanced composition of the present invention to the
wet-end of a paper making process; such paper being useful for the
inhibition of microbes.
[0095] A further aspect of the present invention provides a
carbonate enhanced composition comprising silver carbonate and at
least one aqueous carbonate enhancing composition. Also provided is
a method of using at least one such carbonate enhanced composition
in the preparations of at least one product using silver carbonate
in its composition.
[0096] Further provided is a carbonate enhancing composition and a
carbonate enhanced composition wherein at least silver sulfate is
added to each such composition, either as the sole sulfate or in
combination with copper sulfate. In essence, silver sulfate can be
substituted for copper sulfate or used in combination with copper
sulfate wherein the concentration of copper sulfate and/or silver
sulfate in the present compositions as if copper sulfate alone is
used. The same applies for the use of copper sulfate and/or silver
sulfate in the paper enhancing compositions of the present
invention.
[0097] An additional aspect of the present invention provides a
carbonate enhanced composition comprising at least one organic
compound carbonate and at least one aqueous carbonate enhancing
composition. Also provided is a method of using a composition
comprising at least one organic compound carbonate and at least one
carbonate enhanced composition in the preparations of at least one
product using at least one organic compound carbonate in its
composition.
[0098] To prepare the carbonate enhanced compositions for use in
the paper making process when calcium carbonate is used as at least
one filler, at least 1.5 pounds of at least one carbonate enhancing
composition of the present disclosure is added, typically as a
spray designed to provide thorough coverage of the calcium
carbonate particles, to each ton of one or more selected calcium
carbonate products. Up to ten pounds or greater of carbonate
enhancing composition per ton of calcium carbonate can be used to
prepare a carbonate enhanced compositions for use in paper. More
particularly, any whole or fractional number of the enumerated
range of pounds of carbonate enhancing composition per ton of
calcium carbonate is used to prepare a carbonate enhanced
composition for use in paper. The use of the term "ton" as used
herein refers to the U.S. ton. Slight adjustments of the amount of
addition of a carbonate enhancing composition per ton of calcium
carbonate may have to be made if tonnage is determined as metric
tons or a British (long) ton. Any calcium carbonate product(s) used
as filler for making paper can be used to prepare carbonate
enhanced compositions of the present invention. Selection of the
amount of carbonate enhancing composition added to calcium
carbonate to prepare carbonate enhanced compositions for use in
paper may be judicially selected by the manufacturer of either the
calcium carbonate and/or the paper producer based on the type of
paper (including paper board) and/or the use of the paper
product(s). Furthermore, the use of carbonate enhanced compositions
of the present invention should not be restricted by the use of
other additives typically used in the paper manufacturing
process.
[0099] To impart the antimicrobial properties in paper referenced
herein, typically, at least 5 pounds of carbonate enhancing
composition is used for each ton of calcium carbonate to form
carbonate enhanced compositions although less may be adequate for
certain paper uses. More particularly, the amount of calcium
enhancing composition added to calcium carbonate for such
antimicrobial uses in paper is, for example, 5 pounds, 6 pounds, 7
pounds, 8 pounds, 9 pounds, 10 pounds, 11 pounds and greater than
12 pounds, or any fractional number thereof, per ton of calcium
carbonate.
[0100] For paper pulp, at least one carbonate enhanced composition,
typically using calcium carbonate, can also be used as a
causticizing agent in the pulp sulfate process, to prepare calcium
bisulfate in the pulp sulfite process, used with chlorine in the
bleaching process, in the treatment of pulp and paper mill waste
treatment, a filtration conditioner, a neutralizing agent and to
recover alcohol, calcium lignosulfonate and yeast.
[0101] The present invention further provides a paper enhancing
composition comprising water, at least one solubility enhancing
aqueous composition, sodium hydroxide, copper sulfate and,
optionally, at least one surfactant selected from the group
consisting of non-ionic surfactants and/or anionic surfactants.
[0102] An additional aspect of the present invention provides an
aqueous or, substantially aqueous, paper enhancing composition
(aqueous notwithstanding the potential for copper sulfate to not
have completely dissolved in the paper enhancing composition)
comprising an aqueous phase comprising a solubility enhancing
aqueous composition wherein 1 part of a first solution is added to
about 15 to about 20 parts of water, frequently deionized water, to
form a second solution; sodium hydroxide solution having a
concentration of about 5% to about 7.5% volume/volume of the total
aqueous phase volume of the composition; at least one surfactant
selected from the group consisting of non-ionic surfactants and
anionic surfactants having a concentration from about 0.05 percent
to about 0.15 percent volume/volume of the total aqueous phase
volume of the composition; and copper sulfate having a
concentration from about 20 percent to about 26 percent mass/volume
of the total aqueous phase volume of the composition. The use of
such surfactant in the present composition is optional. As used
herein, the term "aqueous paper enhancing composition" also
includes any such composition that is substantially aqueous as
indicated above.
[0103] A further aspect of the present invention further comprises
the addition of an acid or base to adjust the pH to a pH from about
2.5 to about 3.5 to the immediately preceding composition. There
are multiple potential uses of such paper enhancing compositions
throughout paper making and paper finishing processes. For example,
paper enhancing compositions of the present invention can be added
directly to the wet-end process of paper production for use as, for
example, a paper coagulator and/or to provide microbial
control.
[0104] As a coagulator, the addition of at least one paper
enhancing composition to the wet-end of paper production can
increase the tensile strength, bond strength and/or burst strength
of paper through multiple actions. Without being held to a
particular theory, it is believed that the addition of at least one
paper enhancing composition of the present invention creates an
environment wherein the fiber(s) used in paper making, with or
without the presence of calcium carbonate as a fill material,
enhances the attraction of the fibers, narrowing the interstitial
spaces between and among fibers creating smaller pores while
increasing the tensile, bond and/or burst strength of the resulting
paper. The purpose for using such paper enhancing compositions in
this context is to impart additional paper strength compared to
paper produced without the use of such paper enhancing compositions
without affecting paper caliper or pose or, alternatively,
increased amount of such paper enhancing compositions can be used
to increase the density of the resulting paper for a variety of
uses including, for example and without limitation, preparation of
paper, frequently in the form of masks, used for industrial and/or
medical use wherein the passage of pollutions and/or microorganisms
are retarded or prevented.
[0105] Accordingly, the present invention further provides a method
of increasing at least one of paper tensile strength, bond strength
and burst strength compared to paper prepared without the addition
of at least one paper enhancing composition comprising the addition
of at least one paper enhancing composition to the wet-end of the
paper making process.
[0106] Another aspect of the present invention provides a method
for decreasing the interstitial pore size between and among paper
fibers in a wet-end paper making process compared to paper prepared
without the addition of at least one paper enhancing composition
comprising the addition of at least one paper enhancing composition
to the wet-end of the paper making process.
[0107] An additional aspect of the present invention provides a
method for increasing paper density compared to paper prepared
without the addition of at least one paper enhancing composition
comprising the addition of at least one paper enhancing composition
to the wet-end of the paper making process.
[0108] A further aspect of the present invention provides for paper
having antimicrobial properties comprising paper prepared using at
least one paper enhancing composition during the wet-end process
stage of paper making; such paper being useful for the inhibition
of microbes.
[0109] It is believed that the addition of at least one paper
enhancing composition of the present invention modifies the zeta
potential of the calcium carbonate, when calcium carbonate is used
as a filler material, modifying the charge of the calcium carbonate
and potentially providing stronger bond/interaction between the
fiber and calcium carbonate filler. Such modification of the zeta
potential frequently provides an increase in the zeta potential
although a decrease of zeta potential is possible depending upon
the mixture to which at least one paper enhancing composition is
added.
[0110] Accordingly, also provided herein is a method of modifying
the zeta potential of calcium carbonate when used in the paper
making process comprising applying at least one aqueous paper
enhancing composition during the wet-end stage of paper
production.
[0111] More particularly, the present invention also provides a
method of modifying the zeta potential of calcium carbonate when
used in a pulp-based paper making process comprising applying at
least one aqueous paper enhancing composition during the wet-end
stage of paper production.
[0112] To use the aqueous paper enhancing compositions and impart
the benefits of the use thereof including, for example and without
limitation, paper coagulation and antimicrobial activity, at least
one aqueous paper enhancing compositions is added to the wet-end of
a paper making process at a concentration of about at least 1,500
ppm of the total weight of the wet-end mixture to which the paper
enhancing composition(s) is/are added. More specific amounts of
paper enhancing compositions (aqueous or substantially aqueous) are
added to the wet-end processes at concentrations of about 1,500
ppm, about 2,500 ppm, about 3,500 ppm, about 4,500 ppm, about 5,500
ppm, about 6,500 ppm or greater than about 7,000 ppm of the wet-end
mixture to which the paper enhancing composition(s) is/are added.
Moreover, any whole or fractional number of ppm of the stated range
of paper enhancing composition may be added to the wet-end mixture
to which the paper enhancing composition(s) is/are added. Selection
of the amount of paper enhancing composition added to the wet-end
mixture to which the paper enhancing composition(s) is/are added
may be judicially selected by the paper producer based on the type
of paper (including paper board) and/or the intended use of the
paper product(s). Furthermore, the use of paper enhanced
compositions of the present invention should not be restricted by
the use of other additives typically used in the paper
manufacturing process.
[0113] To impart the antimicrobial properties in paper referenced
herein, typically, at least 2,500 ppm of the at least one paper
enhancing composition is added or applied per ton of the wet-end
mixture to which the paper enhancing composition(s) is/are added.
More particularly, the amount of paper enhancing composition added
or applied to the wet-end mixture to which the paper enhancing
composition(s) is/are added for such antimicrobial uses in paper
is, for example, about 2,500 ppm, about 3,500 ppm, about 4,500 ppm
and greater than about 5,000 ppm, or any whole or fractional number
thereof, per ton of wet-end mixture.
[0114] Notwithstanding the teachings for wet-end use of carbonate
enhancing compositions and paper enhancing compositions of the
present invention, a paper producer may not wish to enhance all of
the paper produced from pulp or another fiber to the final product.
It is beneficial for a paper producers to select which paper
products may be treated to impart additional qualities to the final
paper products. Such additional qualities can be imparted into or
onto paper via the application of a paper enhancing composition of
the present invention via application of such composition onto
paper before, during or after the wet press aspect of paper
production. Typically, after the wet-end step of paper production
is completed, the mix of fiber, filler and any additional
components is fed through a series of high pressure rollers for the
purpose of squeezing out a substantial amount of water from the
wet-end prior to the paper entering dryer and calendar sections.
High pressure roller systems can be fitted with spray nozzles
before, during or after the wet press section. It is throughout
this wet press section of paper processing that one or more paper
enhancing compositions of the present invention is/are sprayed onto
the paper.
[0115] Application, typically as a spray, of at least one paper
enhancing composition onto paper entering, during or following the
wet press section of the paper making process can impart the same
and additional benefits and attributes to paper as with the use of
adding at least one carbonate enhanced composition and/or at least
one paper enhancing composition of the present invention during the
wet-end process as described herein. As such, application of at
least one aqueous paper enhancing composition of the present
invention can provide increased tensile, bond strength and/or burst
strength to the respective paper, modify the zeta potential of
calcium carbonate or at least one enhanced carbonate composition of
the present invention used in the paper making process applied when
the paper carries a substantial amount of water/moisture (e.g., the
earlier to mid stages of the wet press process), improved
hydrophobic sizing, opacity, and print characteristics, while
potentially not affecting paper caliper or caliper pose unless
otherwise intended. When desired, however, the density of paper can
be increased by reducing pore spaces between and among the fiber
and/or fill particles via the application of at least one aqueous
paper enhancing composition of the present invention during the wet
press stage of production. The resulting paper can be used for
medical and industrial applications providing improved safety
compared to products prepared without the benefit of the aqueous
paper enhancing compositions. As further referenced herein, the
aqueous paper enhancing compositions of the present invention also
provide antimicrobial activity into and potentially throughout the
paper onto which the present composition is applied during the wet
press process of paper making. Collectively, the attributes
presented in this paragraph represents, for the purposed herein, as
"enhanced paper", and the process of preparing enhanced paper as
"enhancing paper".
[0116] Accordingly, another aspect of the present invention
provides for enhanced paper comprising paper having applied during
the wet press stage of paper production at least one aqueous
enhancing paper composition.
[0117] Further provided herein are the following methods: [0118] A
method of enhancing paper comprising applying at least one aqueous
paper enhancing composition during the wet press stage of paper
production. [0119] A method of increasing at least one of the group
consisting of tensile strength, bond strength and burst strength in
paper compared to the respective tensile strength, bond strength
and burst strength of paper untreated with an aqueous paper
enhancing composition comprising applying at least one aqueous
paper enhancing composition during the wet press stage of paper
production. [0120] A method of modifying the zeta potential of
calcium carbonate when used in the paper making process comprising
applying at least one aqueous paper enhancing composition during
the wet press stage of paper production. [0121] The present
invention also provides a method of modifying the zeta potential of
calcium carbonate used in a pulp-based paper making process
comprising applying at least one aqueous paper enhancing
composition during the wet press stage of paper production. [0122]
A method of increasing at least one of the group consisting of
paper tensile strength, bond strength and burst strength of paper
comprising applying at least one aqueous paper enhancing
composition during the wet press stage of paper production compared
to paper untreated with an aqueous paper enhancing composition
without an increase in caliper pose. [0123] A method of decreasing
the pore size of paper comprising applying at least one aqueous
paper enhancing composition during the wet press stage of paper
production compared to paper untreated with an aqueous paper
enhancing composition. This method typically requires the use of
such compositions at concentrations in the higher end of the stated
ranges. [0124] A method of preparing paper for medical and
industrial protective uses comprising applying at least one aqueous
paper enhancing composition during the wet press stage of paper
production. [0125] A method of preparing paper for use in masks for
mammalian, particularly human, use comprising applying at least one
aqueous paper enhancing composition during the wet press stage of
paper production.
[0126] Further provided is antimicrobial paper, having a multitude
of uses, comprising paper prepared by the application of at least
one aqueous paper enhancing composition of the present invention
during the wet press stage of paper production.
[0127] To use the aqueous paper enhancing compositions and impart
the benefits of the use thereof including, for example and without
limitation, paper strengthening and antimicrobial activity, at
least one aqueous paper enhancing compositions is applied,
typically as a spray, before, during or after the wet press stage
of a paper making at a concentration of about at least 1,500 ppm of
such composition to each ton of wet weight matter entering the wet
press stage. More specifically, amounts of paper enhancing
compositions are applied as a spray during the wet press stage of
paper making at concentrations of about 1,500 ppm, about 2,500 ppm,
about 3,500 ppm, about 4,500 ppm, about 5,500 ppm, about 6,500 ppm
or greater than about 7,000 ppm to each ton of wet weight matter
entering the wet press stage of paper making. Generally,
concentrations of paper enhancing compositions can be reduced at
later stages of the wet press stage if the spray containing paper
enhancing compositions is applied after a substantial amount of
moisture is removed. However, if the spray containing paper
enhancing compositions of the present invention is applied once the
paper is substantially dry but prior to entering the drying
process, it is suggested to use the spray concentrations set forth
below for paper coatings. However, slightly higher concentrations
should be used based on the amount of residual moisture prior to
such drying stage. Moreover, any whole or fractional number of ppm,
within the stated concentration range, of paper enhancing
composition may be applied during the wet press stage. Selection of
the amount of paper enhancing composition applied during the wet
press stage may be judicially selected by the paper producer based
on the type of paper (including paper board) and/or the use of the
paper product(s). Furthermore, the use of paper enhanced
compositions of the present invention should not be restricted by
the use of other additives typically used in the paper
manufacturing process.
[0128] To impart the antimicrobial properties in paper referenced
herein, typically, at least 2,500 ppm of the at least one paper
enhancing composition is applied for each ton of wet weight matter
entering the wet press stage. More particularly, the amount of
paper enhancing composition applied during the wet press stage for
such antimicrobial uses in paper is, for example, about 2,500 ppm,
about 3,500 ppm, about 4,500 ppm and greater than about 5,000 ppm,
or any whole or fractional number thereof, per ton of wet weight
matter entering the wet press stage of paper production. The amount
of paper enhancing composition used can be adjusted pursuant to the
recommendations set forth in the immediately preceding
paragraph.
[0129] Alternatively, at least one of the aqueous paper enhancing
compositions of the present invention can be applied to paper as an
additive to surface sizing, wherever surface sizing is applied
throughout the paper and or paper printing processes. The
concentrations of at least one paper enhancing composition of the
present invention when applied with sizing are the same
concentrations taught herein below for the concentrations used for
paper coatings. The only difference is that the concentrations are
based on the total volume of sizing being surface applied to paper
rather than the total volume of paper coating(s) being applied. As
such, a minimum recommended concentration of at least one paper
enhancing composition of the present invention to be applied with
surface sizing is at least about 1,500 ppm of the total sizing
volume being surface applied for general use and benefit; and at
least about 2,500 ppm of such paper enhancing composition when
antimicrobial activity is desired.
[0130] For each use of an aqueous paper enhancing compositions of
the present invention, application during the paper making process
as described above or when used as paper coatings as described
below, such compositions can be applied individually or in
combination with other additives and/or coating material as such
materials are used in the paper making/processing arts.
[0131] Applications of at least one aqueous paper enhancing
composition of the present invention can also be applied directly
to finished paper at any time following the dryer section of the
paper making process. In other words, such application can be made
from the calender section of paper making through and following
printing thorough a printing press or other printing method; or,
alternatively, to prepare paper products or directly to final paper
products.
[0132] In addition to coatings being applied by the paper
manufacturer, liquid coatings are frequently applied in-line by the
printer as part of the printing process or off-line after the
project leaves the press. Although the paper enhancing compositions
of the present invention can be applied with any liquid coating,
the present paper enhancing compositions are typically applied with
commonly used or specialty aqueous coatings that are usually
flooded across the entire sheet. Different coatings are available
in different finishes, tints, textures and thicknesses, which may
be used to adjust the level of protection or achieve different
visual effects. Areas that are heavily covered with black ink or
other dark colors often receive a protective coating to guard
against fingerprints, which stand out against a dark background.
Coatings are also used on magazine and report covers and on other
publications that are subject to rough or frequent handling.
Moreover, communicable diseases caused by microorganisms,
particularly, without limitation bacteria, including MRSA, and
viruses such as noroviruses and coronaviruses, each of which, along
with other pathogens, have the ability to remain viable and
transmissible on surfaces, including paper, for a period of time.
Accordingly, it is beneficial to have additional materials that can
be added to liquid paper coatings to impart attributes such as
additional tensile strength, bond strength and/or burst strength to
coated paper. Additionally, it is beneficial to provide
antimicrobial attributes to the surface of paper through coatings.
Each of these attributes can be added to paper via the application
of at least one paper enhancing composition of the present
invention as a component in other liquid, commonly aqueous, paper
coatings or at a particular concentration to other acceptable paper
coating media, including water. Coatings including at least one
paper enhancing composition of the present invention can be applied
via any method used in the paper coating industry including, for
example and without limitation, flood coating, blade coating,
premetered film presses and roll metering. Each type of coating has
particular uses, benefits and drawbacks. As such, the applier of
such coatings can select the best coating and type of application
for each such coating application. Accordingly, the application of
at least one paper enhancing composition of the present invention
should not be limited by the type of paper coating or method of
application.
[0133] As such, another aspect of the present invention provides
for a paper coating comprising at least one aqueous paper enhancing
composition.
[0134] An additional aspect provides for paper coated with at least
one aqueous paper enhancing composition.
[0135] Another aspect of the present invention provides a method of
increasing at least one of the group consisting of paper tensile
strength, bond strength and burst strength of paper comprising the
application of a coating to paper comprising at least one paper
enhancing composition of the present invention.
[0136] Paper, including the printing on paper, can also be enhanced
and protected by a variety of well-known liquid additives. The
present aqueous paper enhancing compositions of the present
invention, when applied as paper coatings alone or in combination
with other paper coating materials including, for example and
without limitation, varnish and ultra violet coatings, can also
provide, for example and without limitation: protection from
fingerprints and other blemishes, help prevent metallic inks from
tarnishing, and provide surfaces that can be written on with
pencil, pen, ink jet printers, laser jet printers, off-set printers
and the like. Although the present aqueous paper enhancing
compositions can be applied to paper, in general, it may be best to
use 80# text weight or heavier paper stocks to keep the paper from
becoming curled or wrinkled, particularly when using a flood
coating method.
[0137] An additional aspect of the present invention provides for a
method of providing at least one of protection from fingerprints
and other blemishes, help prevent metallic inks from tarnishing,
and provide paper surfaces that can be written on with multiple
media (including, without limitation, pencil, pen, ink jet
printers, laser jet printers, off-set printers and the like)
comprising the application of a coating to paper comprising at
least one paper enhancing composition of the present invention.
[0138] A further aspect of the present invention provides for a
method of providing improvement of at least one of protection from
fingerprints and other blemishes, help prevent metallic inks from
tarnishing, and provide paper surfaces that can be written on with
multiple media (including, without limitation, pencil, pen, ink jet
printers, laser jet printers, off-set printers and the like)
compared to paper coatings not including the application of at
least one aqueous paper enhancing composition of the present
invention comprising the application of a coating to paper
comprising at least one paper enhancing composition of the present
invention.
[0139] Because of the antimicrobial activity of the present paper
enhancing compositions of the present invention, such compositions
can be used as coatings to paper to provide such antimicrobial
activity. Paper coated with such compositions have almost unlimited
uses including, for example and without limitation, construction of
masks used for industrial pollutants and/or medical masks used by
any individuals including medical and first-responder personnel,
paper used for wrapping food products including produce and/or fish
and/or meat products, paper used as or in diapers, papers used as
diapers, in produce and/or fish and/or meat products (for example,
the absorbent paper underlining packaged poultry products),
packaging, generally, blotters used by children and/or adults,
facial tissues, sanitary napkins, liners for fruit, or any of a
plethora of other paper uses where the inhibition of microorganism
is desired and/or required.
[0140] Accordingly, another aspect of the present invention
provides for coated paper having antimicrobial activity comprising
paper coated with at least one aqueous paper enhancing composition
of the present invention.
[0141] An additional aspect of the present invention provides for
paper having antimicrobial properties comprising paper coated with
at least one aqueous paper enhancing composition of the present
invention.
[0142] Another aspect of the present invention provides for a
method of preparing paper having antimicrobial activity comprising
applying as a coating to paper at least one aqueous paper enhancing
composition of the present invention to said paper.
[0143] Further provided is antimicrobial paper, having a multitude
of uses, comprising paper prepared by the application of a coating
of at least one aqueous paper enhancing composition of the present
invention during the wet press stage of paper production.
[0144] Because of the antimicrobial activity of paper coated with
at least one such aqueous paper enhancing composition, such coated
paper can protect and potentially prolong the shelf-life of
produce, meats and other perishable foodstuff (collectively,
"foodstuff"). As such, another aspect of the present invention
provides a method of extending the shelf-life of perishable
foodstuff comprising placing such foodstuff in contact, in whole or
in part, with paper coated with at least one aqueous paper
enhancing composition of the present invention. Such shelf-life can
be extended for at least 24 hours, providing substantial value to
providers of such perishable foodstuff.
[0145] Another aspect provides a method for preparing paper for
medical and industrial protective uses comprising applying as a
coating to paper at least one aqueous paper enhancing composition
during.
[0146] An additional aspect provides a method of preparing paper
for use in masks for mammalian, particularly human, use comprising
applying as a coating at least one aqueous paper enhancing
composition.
[0147] Aqueous paper enhancing compositions of the present
invention are applied to paper as coatings, either as a single
coating in a liquid-based solution, frequently water, or as at
least one component with other surface-applied paper coating
materials at a concentration of at least about 1,500 ppm of the
total amount of liquid-based solution or coating being applied.
More specifically, amounts of paper enhancing compositions are
applied as a spray coating at concentrations of about 1,500 ppm,
about 2,500 ppm, about 3,500 ppm, about 4,500 ppm, about 5,500 ppm,
about 6,500 ppm or greater than about 7,000 ppm of the total amount
of liquid-based solution or coating being applied. Moreover, any
whole or fractional number of ppm of paper enhancing composition,
within the given concentration range, may be applied during the
coating process. Selection of the amount of paper enhancing
composition applied during the coating process stage may be
judicially selected by the paper producer, printer, or desire of
the end user based on the type of paper (including paper board)
and/or the use of the paper product(s).
[0148] To impart the antimicrobial properties in paper referenced
herein, typically, aqueous paper enhancing compositions of the
present invention are applied to paper as coatings, either as a
single coating in a liquid-based solution, frequently water, or as
at least one component with other surface-applied paper coating
materials at a concentration of at least about 2,500 ppm of the
total amount of liquid-based solution or coating being applied.
More specifically, to provide antimicrobial properties to paper
coatings, amounts of paper enhancing compositions are applied as a
spray coating at concentrations of about 2,500 ppm, about 3,500
ppm, about 4,500 ppm, about 5,500 ppm, about 6,500 ppm or greater
than about 7,000 ppm of the total amount of liquid-based solution
or coating being applied to the paper. Moreover, any whole or
fractional number of ppm of paper enhancing composition within the
given concentration range, may be applied during the coating
process. Selection of the amount of paper enhancing composition
applied during the coating process stage may be judicially selected
by the paper producer, printer, or desire of the end user based on
the type of paper (including paper board) and/or the use of the
paper product(s).
[0149] For each of the claims set forth herein below, such claims
can be alternatively drafted using "consisting of" and "consisting
essentially of" claim language.
[0150] One element of the present paper enhancing compositions and
carbonate enhancing compositions of the present invention provides
a solubility enhancing aqueous composition comprising a first
solution comprising an anionic component consisting essentially of
sulfate ions, alone or in combination with bisulfate ions, having a
concentration from about 8.00 moles per liter to about 13.00 moles
per liter of the first solution volume, and a cationic component
consisting essentially of ammonium ions having a concentration from
about 1.45 moles per liter to about 2.01 moles per liter of the
first solution volume, combined with a volume of water at least
equal to the volume of the first solution forming a second
solution. Generally, the first solution of this composition will
also comprise hydrogen ions in a concentration from about 17.38 to
about 21.68 moles per liter of the total volume of the first
solution.
[0151] An alternative element of the present paper enhancing
composition provides a solubility enhancing aqueous composition
comprising a first solution comprising an anionic component
comprising sulfate ions, alone or in combination with bisulfate
ions, having a concentration from about 8.00 moles per liter to
about 13.00 moles per liter of the first solution volume, and a
cationic comprising ammonium ions having a concentration from about
1.45 moles per liter to about 2.01 moles per liter of the first
solution volume, combined with a volume of water at least equal to
the volume of the first solution forming a second solution.
Generally, the first solution of this composition will also
comprise hydrogen ions in a concentration from about 17.38 to about
21.68 moles per liter of the total volume of the first
solution.
[0152] It is the intent of the present disclosure to permit the
skilled artisan to prepare a solubility enhancing aqueous
composition element using a range of water in a ratio to the
concentrations of ammonium sulfate and sulfuric acid for each
preparation, with the resultant sulfate anions and ammonium
cations, and the amount of water to be determined by such artisan,
each within the parameters taught herein.
[0153] For the sake of clarity, three solutions are formed in
preparing the second solution which comprise solubility enhancing
aqueous compositions: 1) ammonium sulfate stock solution; 2) a
first solution comprising the ammonium sulfate stock solution in
sulfuric acid; and 3) second solution comprising solubility
enhancing aqueous compositions. Unless context otherwise dictates,
general references to the use of a first solution and a second
solution refers to the preparation of the referenced solubility
enhancing aqueous compositions used in the preparation of paper
enhancing agent compositions of the present invention.
[0154] To prepare the first solution of a composition of the
present disclosure, one needs to first prepare an ammonium sulfate
stock solution. For example and without limitation, an ammonium
sulfate stock solution is prepared to contain 20%, 24%, 30%, 40%,
50% or 60% of ammonium sulfate in water, typically, without
restriction, deionized water. For the sake of clarity, the percent
concentration of ammonium sulfate can be any whole number or
fraction thereof in a range from about 20% to about 60%. The molar
concentration of the stock solution varies by the ammonium sulfate
concentration in a known volume of water.
[0155] By means of exemplification, the following calculations are
used to determine the amount of ammonium sulfate and sulfuric acid
to add to form a first solution.
[0156] Ammonium Sulfate: [0157] Ammonium sulfate equals 132.14
grams per mole. Using, for example, a 24% ammonium sulfate
solution, such solution would have 240 grams of ammonium sulfate
per 1 L of water. Because the ratio of ammonium sulfate to sulfuric
acid in this exemplification is about 48% ammonium sulfate to about
52% sulfuric acid, the first solution would contain 115.20 grams of
ammonium sulfate, equaling 0.872 moles per liter. As such, one mole
of ammonium sulfate provides 2 moles of ammonium and 1 mole of
sulfate. Accordingly, 0.872 moles of ammonium sulfate provides to
the ammonium sulfate stock solution 1.744 moles of ammonium and
0.872 moles of sulfate required per liter of reaction in forming
the first solution.
[0158] Sulfuric Acid (Concentrated): [0159] Sulfuric acid equals
98.079 g/mole as concentrated (95% to 98%) reagent grade sulfuric
acid. Sulfuric acid exists as a liquid and has a density of 1.840
g/mL. For this example, sulfuric acid comprises 52% of a first
solution of 1 liter. As such, 520 mL (0.52 L) of sulfuric acid is
added to the ammonium sulfate stock solution. 520 mL times 1.840
g/mL equals 956.8 grams. 956.8 grams divided by 98.079 grams per
mole provides the target concentration of 9.755 moles of sulfuric
acid per liter of preparation. 9.755 moles of sulfuric acid
provides 9.755 moles of sulfate anion and 2 moles of hydrogen
resulting from each mole of acid, in this example, 19.51 moles of
hydrogen per liter of said first solution.
[0160] Reaction Unit: [0161] Using the values set forth above, in
this instance, there are about 0.872 moles of ammonium sulfate to
about 9.755 moles of sulfuric acid providing: [0162] about 0.872
moles of ammonium sulfate provides about 0.872 moles of sulfate and
about 1.744 moles of ammonium required per reaction unit liter; and
[0163] about 9.755 moles per liter of sulfuric acid provides about
9.755 moles of sulfate anion and about 19.51 moles of hydrogen per
liter of reaction unit. [0164] Using this example, each reaction
unit, forming a first solution, would contain: [0165] about 0.972
moles of sulfate (from ammonium sulfate) plus about 9.755 moles of
sulfate from ammonium sulfate equaling about 10.627 moles of
sulfate anion per liter comprising sulfate anions alone, bisulfate
anions alone or, typically, a mixture of sulfate and bisulfate
anions; [0166] about 1.744 moles of ammonium per liter; and [0167]
about 19.51 moles of hydrogen per liter.
[0168] To accomplish the formation of a solubility enhancing
aqueous composition, a second solution is formed by the addition of
water, a critical component, in an appropriate amount, to provide
solubility enhancing aqueous compositions that are substantially
free, or free, of solids. Alternatively, a first solution can be
added to the appropriate amount of water to form a second solution.
As such, the order of addition of a first solution to water or
water to the first solution to form a second solution is not of
consequence. Use of the solubility enhancing aqueous compositions
may form solids when combined with other chemical or other
materials when using such solubility enhancing aqueous compositions
for its intended purpose: enhancing solubility of such chemical
compounds or other materials.
[0169] Generally, water is at least fifty percent of the second
solution that represents the solubility enhancing aqueous
compositions. Moreover, water can comprise from at least fifty
percent up to ninety-nine percent of the second solution or final
composition. However, the lower concentrations of water, as taught
herein, are typically more useful for further use of the present
compositions used for solubility enhancement. Accordingly, the
amount of water used to form a second solution is at least 50% of
the volume of the first solution or at least 50% of the mass of the
first solution. Alternatively, the mass of the sum of the ammonium
ion concentration plus sulfate ion concentration in a first
solution can also serve as the basis of the amount of water to be
added to form a second solution wherein the amount of water added,
by mass, to form a second solution equals at least 50% of the sum
of the mass of ammonium ions plus sulfate ions. Another means by
which to represent the amount of water added to the first solution
is that the amount of water used to form a second solution is at
least equal to the volume of the first solution or at least equal
to the mass of the first solution. Alternatively, the mass of the
sum of the ammonium ions plus sulfate ions in a first solution can
also serve as the basis of the amount of water to be added to form
a second solution wherein the amount of total water, including the
water used to solubilize the ammonium sulfate and added water, is
at least equal to the sum of the mass of ammonium ions plus sulfate
ions.
[0170] The amount of water used to prepare the second solution,
representing solubility enhancing aqueous compositions, can be
calculated in volume/volume (total volume of the first solution
plus at least the same volume of water). Alternatively, the ratio
of reactants to water (mass/mass) may be used. Using the values for
ammonium sulfate and sulfuric acid from the above example, 115.20
grams of ammonium sulfate and 956.8 grams of sulfuric acid were
used providing a sum of 1072 grams of reactants. Accordingly, for
water to equal at least fifty percent of the final composition, at
least 1072 grams of water are added to the first solution to form
the second solution, a solubility enhancing aqueous composition.
Alternatively, as referenced above, the amount of water used to
form a second solution can be based on the total mass or volume of
the first solution. Accordingly, any method taught herein can be
used for calculating the amount of water required to form a second
solution. As taught above, using the mass of the reactants to
dictate the amount of water required to form a second solution is
the minimum amount of water required to provide an aqueous solution
and to impart the qualities of the compositions of the present
invention as further delineated herein.
[0171] To achieve solubility enhancement, ranges of concentration
of sulfate ions and ammonium ions in the solubility enhancing
aqueous compositions are used while maintaining solubility
enhancing aqueous compositions that are essentially free or are
free of salt crystals or other solids from the reactants that form
a first solution. Accordingly, a first solution comprises an
anionic component consisting essentially of sulfate ions, alone or
in combination with bisulfate ions, has a concentration range from
about 8.00 moles per liter to about 13.00 moles per liter of the
first solution volume. The first solution also comprises a cationic
component consisting essentially of ammonium ions has a
concentration from about 1.45 moles per liter to about 2.01 moles
per liter of the first solution volume. Typically, when the lower
values within the range for sulfate ions are selected for preparing
a first solution, a lower value within the stated range for
ammonium ions is selected and included in the preparation of the
first solution. Similarly, when higher values within the stated
range for sulfate ions are selected for the preparation of a first
solution, higher values of ammonium ions are selected for the
preparation of a first solution. Although not imperative,
typically, the sulfate ion concentration within the given range of
from about 8.00 moles per liter to about 13.00 moles per liter of
first solution volume is proportionally commensurate with the range
of ammonium ion concentration within the given the given range of
from about 1.45 moles per liter to about 2.01 moles per liter of
first solution volume.
[0172] In another embodiment of the solubility enhancing aqueous
compositions, a first solution comprises an anionic component
comprising sulfate ions, alone or in combination with bisulfate
ions, has a concentration range from about 8.00 moles per liter to
about 13.00 moles per liter of the first solution volume. The first
solution also comprises a cationic component comprising ammonium
ions has a concentration from about 1.45 moles per liter to about
2.01 moles per liter of the first solution volume. Typically, when
the lower values within the range for sulfate ions are selected for
preparing a first solution, a lower value within the stated range
for ammonium ions is selected and included in the preparation of
the first solution. Similarly, when higher values within the stated
range for sulfate ions are selected for the preparation of a first
solution, higher values of ammonium ions are selected for the
preparation of a first solution. Although not imperative,
typically, the sulfate ion concentration within the given range of
from about 8.00 moles per liter to about 13.00 moles per liter of
first solution volume is proportionally commensurate with the range
of ammonium ion concentration within the given the given range of
from about 1.45 moles per liter to about 2.01 moles per liter of
first solution volume. When prepared according to the solubility
enhancing aqueous composition embodiments provided herein, the
resulting hydrogen ion concentration will typically fall within the
range from about 17.38 moles per liter to about 21.68 moles per
liter of first solution volume but falling within this hydrogen
range is not necessarily critical to the final first solution but
is beneficial when using the solubility enhancing aqueous
compositions for enhancing solubility of compounds or other
materials depending upon the nature thereof.
[0173] The process for preparing the solubility enhancing aqueous
compositions can be carried out using traditional laboratory and
safety equipment when using concentrated acid and water that could
generate significant heat. Within these considerations, the
selection of laboratory equipment is not critical to the formation
of the solubility enhancing aqueous solutions or compositions. More
particularly, the preparation of the first solution wherein the
reactants ammonium sulfate stock solution is combined with sulfuric
acid requires laboratory apparatuses that are approved for heat
generation, splashing and, potentially, pressure relief.
Accordingly, the first solution should be prepared in a laboratory
vessel that is not sealed providing for pressure relief, rather
than a potential hazardous situation with pressure build up in an
unrated vessel. The ordinarily skilled artisan should be
knowledgeable in the selection and use of such apparatuses.
[0174] For commercial-scale production of solubility enhancing
aqueous compositions, the ordinarily skilled artisan will recognize
that the reaction between the solubilized ammonium sulfate and
sulfuric acid is typically exothermic. As such, a reaction vessel
appropriate to safely contain and, typically, cool this reaction,
is recommended. Commercial production of a first solution and a
second solution can be accomplished using any of the teachings
herein but on a larger scale than the laboratory scale teachings
and examples disclosed herein. Moreover, such commercial production
can be accomplished, without limitation, as taught herein or with
equipment known to the ordinarily skilled artisan.
[0175] The order of adding the reactants to each other is not
critical in the preparation of a first solution. Either the stock
ammonium sulfate solution can be added to the sulfuric or, more
typically, sulfuric acid is added to the stock ammonium sulfate
stock solution to avoid the splattering typical of adding a
solution containing water to acid. Typically, the heat generating
reaction forming the first solution is permitted to run to
conclusion, with the term "conclusion" having the meaning
understood by the ordinarily skilled artisan, prior to adding the
first solution to the required water or water to the first
solution, without preference to the order of addition. For the sake
of clarity, conclusion of the reaction between the ammonium sulfate
stock solution and sulfuric acid typically occurs when the
reactants no longer produce an exothermic reaction and the
temperature of the solution begins to decrease to ambient
temperature.
[0176] Alternatively, the formation of a first solution is not
required and the ammonium sulfate stock solution and sulfuric acid
can be combined with the final desired volume of a solubility
enhancing aqueous compositions. Accordingly, another aspect of the
solubility enhancing aqueous compositions provides a solubility
enhancing aqueous composition comprising an anionic component
consisting essentially of sulfate anions having a concentration
from about 8.00 moles per liter to about 13.00 moles per liter of
about one-quarter of the final solubility enhancing aqueous
composition volume and a cationic component consisting essentially
of ammonium ions having a concentration from about 1.45 moles per
liter to about 2.01 moles per liter of about one-quarter of the
final solubility enhancing aqueous composition volume or less, and
water comprising at least one-half of the final composition
volume.
[0177] An alternate solubility enhancing aqueous composition
comprises an anionic component comprising sulfate anions having a
concentration from about 8.00 moles per liter to about 13.00 moles
per liter about one-half of the final solubility enhancing aqueous
compositions volume and a cationic component comprising ammonium
ions having a concentration from about 1.45 moles per liter to
about 2.01 moles per liter of about one half of the final
solubility enhancing aqueous composition volume.
[0178] Another alternate solubility enhancing aqueous composition
comprises an anionic component consisting essentially of sulfate
anions having a concentration from about 8.00 moles per liter to
about 13.00 moles per liter and a cationic component consisting
essentially of ammonium ions having a concentration from about 1.45
moles per liter to about 2.01 moles per liter of the final
solubility enhancing aqueous composition volume wherein said liter
volume for calculation for the volume of water comprising the
ammonium ions and sulfate anions comprises at least one percent of
the total volume of the solubility enhancing aqueous
composition.
[0179] A further alternate solubility enhancing aqueous composition
comprises an anionic component consisting essentially of sulfate
anions having a concentration from about 8.00 moles per liter to
about 13.00 moles per liter of not more than about one-half of the
final solubility enhancing aqueous composition volume and a
cationic component consisting essentially of ammonium ions having a
concentration from about 1.45 moles per liter to about 2.01 moles
per liter of not more than about one-half the final solubility
enhancing aqueous composition volume.
[0180] An additional alternate solubility enhancing aqueous
composition comprises an anionic component comprising sulfate
anions having a concentration from about 8.00 moles per liter to
about 13.00 moles per liter of not more than about one-half of the
final solubility enhancing aqueous composition volume and a
cationic component comprising ammonium ions having a concentration
from about 1.45 moles per liter to about 2.01 moles per liter of
not more than about one-half the final solubility enhancing aqueous
composition volume.
[0181] Although certain aspects of the solubility enhancing aqueous
compositions allow for highly dilute concentrations for the
ammonium cations and sulfate anions, specific concentrations of
these ions can be calculated on a basis as if such combination were
prepared on a per liter basis wherein the volume of such
preparation comprises 1%, 10%, 20%, 30%, 40%, 48%, 50% or 60% of
the total volume of the final solubility enhancing aqueous
composition. For the sake of clarity, the volume of water can be
any whole number or fraction thereof in a range from about 1% to
about 60%. In addition, the volume of total water in each of the
solubility enhancing aqueous compositions taught herein can be
calculated by a variety of methods as taught herein and are not
limited by any one teaching. As such, the amount of water used to
form a second solution can be based on weight/weight (first
solution weight to the weight of water added to form a second
solution); mass/mass (first solution mass to the mass of water
added to form a second solution; and mass/mass (the mass of the sum
of ammonium ions and sulfate ions to the mass of total water in the
second solution). Each of these methods can be used in a two-step
process wherein a first solution is formed and water is added to
form a second solution, or a one-step process where the elements of
a second solution of the present invention are pre-calculated and
added accordingly.
[0182] As referenced above, one aspect of the present invention
provides an aqueous paper enhancing composition comprising an
aqueous phase comprising: a solubility enhancing aqueous
composition wherein 1 part of a first solution is added to about 15
to about 20 parts of water to form a second solution; sodium
hydroxide solution having a concentration of about 5% to about 7.5%
volume/volume of the total aqueous phase volume of the composition;
at least one optional surfactant selected from the group consisting
of non-ionic surfactant and anionic surfactant having a
concentration from about 0.05 percent to about 0.15 percent
volume/volume of the total aqueous phase volume of the composition;
and copper sulfate having a concentration from about 20 percent to
about 26 percent mass/volume of the total aqueous phase volume of
the composition. A further aspect of the present invention further
comprises the addition of an acid or base to adjust the pH to a pH
from about 2.5 to about 3.5 to the immediately preceding
composition.
[0183] A further aspect of the present invention further comprises
the addition of an acid or base to adjust the pH to a pH from about
2.5 to about 3.5 to the immediately preceding composition.
[0184] For the preparation of the above-referenced aqueous paper
enhancing composition, a 20 percent to 50 percent dilute sodium
hydroxide solution is prepared using techniques well known to the
skilled artisan. The range of sodium hydroxide concentration in the
present aqueous paper enhancing compositions is based on varied
concentrations of sodium hydroxide. When higher concentration
sodium hydroxide solutions are used, one would typically use the
lower concentration range of about 0.5% volume/volume of the total
aqueous element volume of the composition. Conversely, when lower
concentration sodium hydroxide solutions are used, one would
typically use the higher concentration range of about 0.75%
volume/volume of the total aqueous element volume of the
composition. Total aqueous element volume composition means the sum
volume of the aqueous components of the present composition
including the solubility enhancing aqueous composition, sodium
hydroxide solution and surfactant.
[0185] Various aqueous concentrations of non-ionic and anionic
surfactants are commercially available, frequently found in
concentrations of about 20% to about 80% in water. Such surfactants
can also be prepared by diluting concentrated non-ionic surfactant
and/or anionic surfactants in water to desired concentrations.
Accordingly, such surfactants having a concentration of 20%, 30%,
40%, 50%, 60%, 70% and 80% are useful in the present composition.
Generally, surfactant concentrations of at least 20% in water are
useful. More particularly, a 50% concentration of Glucopon.RTM. 420
in water (available from multiple vendors including, for example,
BASF Corp., Florham Park, N.J., USA) is useful as a nonionic
surfactant in the present aqueous paper enhancing compositions.
When higher concentration surfactant solutions are used, one would
typically use the lower concentration range of about 0.05%
volume/volume of the total aqueous element volume of the
composition. Conversely, when lower concentration surfactant
solutions are used, one would typically use the higher
concentration range of about 0.15% volume/volume of the total
aqueous element volume of the composition.
[0186] Additionally, a solubility enhancing aqueous composition is
prepared wherein 1 part of a first solution, as described above, is
added to about 15 to about 20 parts of water to form a second
solution.
[0187] For preparation of the aqueous paper enhancing composition
of the present invention, to the solubility enhancing aqueous
composition is added dilute sodium hydroxide (about 20% to about
50%) having a concentration of about 5% to about 7.5% volume/volume
of the total aqueous element volume of the composition. The
surfactant element of the present composition can be added to this
aqueous solution or can optionally be added following the addition
of the copper sulfate element. However, the calculation for the
concentration of the surfactant is based on the total aqueous
element volume of the composition as if the copper sulfate had not
yet been added. The at least one surfactant is selected from the
group consisting of non-ionic surfactant and anionic surfactant
having a concentration from about 0.05 percent to about 0.15
percent volume/volume of the total aqueous element volume of the
composition.
[0188] The copper sulfate element of the present aqueous paper
enhancing composition is added to the aqueous solution described
above at a concentration from about 20 percent to about 26%
mass/volume of the total aqueous element volume of the
composition.
[0189] Once the present composition is prepared, the final pH
should be adjusted to a pH of from about 2.5 to about 3.5 with a pH
of about 3.0 being typically used. Any base or acid can be used to
increase or decrease, respectively, the pH of such a composition.
However, it is best to utilize acids and bases already used in the
present compositions; dilute sodium hydroxide to increase the pH
and sulfuric acid to decrease the pH. Alternatively, pH is
controlled throughout the various steps of preparation of an
aqueous paper enhancing composition of the present invention. For
example, pH can be adjusted to the ranges set forth above following
the addition of dilute sodium hydroxide to the previously prepared
solubility enhancing aqueous composition, and then again following
the addition of copper sulfate and, optionally, following the
addition of copper sulfate and the anionic and/or nonionic
surfactant. As such, the pH is adjusted at least one time during
preparation of an aqueous paper enhancing composition, typically
following the addition of the copper sulfate and/or surfactant.
[0190] The process for preparing the carbonate enhancing
compositions, including aqueous carbonate enhancing compositions,
can be carried out using traditional laboratory and safety
equipment when using concentrated acid and water that could
generate significant heat. Within these considerations, the
selection of laboratory equipment is not critical to the formation
of the carbonate enhancing compositions and/or aqueous carbonate
enhancing compositions. The ordinarily skilled artisan should be
knowledgeable in the selection and use of such apparatuses.
[0191] For larger scale production batches of such carbonate
enhancing compositions of the present invention, including aqueous
paper enhancing compositions, such compositions are prepared based
on the percentages taught herein above of the elements required for
preparation of such compositions. As a non-limiting example, such
compositions can be prepared as follows: to produce 330 gallons of
finished product, to an adequate-sized tank having circulation
mixing, is about 2,116 pounds of 17 megohm water, typically,
distilled water, about 183 pounds of a solubility enhancing aqueous
composition, with continued mixing, about 183 pounds of 50% sodium
hydroxide that is slowly added to the prior mixture, with continued
mixing, about 590 pounds copper sulfate, with continued mixing to
maintain the copper sulfate in solution, and about 2 pounds of 50%
Glucopon.RTM. 420 UP, with continued mixing for at least about one
hour. It is beneficial to adjust the pH after addition of each
subsequent element beginning with the addition of the solubility
enhancing aqueous composition. pH should be adjusted to be in the
range from about pH 2.5 to about pH 3.5 with a median of pH 3.0
being a reasonable target. Lowering the pH is accomplished by any
reasonable means known to the skilled artisan but it is recommended
to add an appropriate amount of a solubility enhancing aqueous
composition; and increasing the pH can be accomplished by any means
known to the skilled artisan but is recommended to add an
appropriate amount of sodium hydroxide, particularly 50% sodium
hydroxide.
[0192] The intent and benefit of the present aqueous paper
enhancing composition, and potentially, all aqueous is to provide
an aqueous solution that is substantially free of solids. However,
not all aqueous paper enhancing compositions or carbonate enhancing
compositions will be free or substantially free of solids.
[0193] Although specific embodiments have been described above,
these embodiments are not intended to limit the scope of the
present disclosure, even where only a single embodiment is
described with respect to a particular feature. Examples of
features provided in this disclosure are intended to be
illustrative rather than restrictive unless stated otherwise. The
present disclosure is intended to cover such alternatives,
modifications and/or equivalents as would be apparent to a person
skilled in the art having the benefit of this disclosure.
[0194] It is to be understood that the present compositions are
limited only to the ranges and or limitation set forth herein and
not to variations within such ranges. It is also to be understood
that the terminology used herein is for the purpose of describing
particular embodiments only, and is not intended to be
limiting.
[0195] Further modifications and alternative embodiments of various
aspects of the embodiments described in this disclosure will be
apparent to the skilled artisan in view of the present disclosure.
Elements and materials may be substituted for those illustrated and
described herein, parts and processes may be reversed, and certain
features of the embodiments may be utilized independently, all as
would be apparent to one skilled in the art after having the
benefit of the description. Changes may be made in the elements
described herein without departing from the spirit and scope of the
appended claims.
EXAMPLES
Example 1
[0196] Preparation of an ammonium sulfate stock solution for a
solubility enhancing aqueous composition: Into a volumetrically
calibrated common 250 mL beaker, 90 mL of deionized H.sub.2O was
added. 20 grams of (NH.sub.4).sub.2SO.sub.4 was completely
dissolved into the deionized water. The total volume was brought to
100 mL using additional deionized water. 20 grams
(NH.sub.4).sub.2SO.sub.4 per 100 mL H.sub.2O is a 20% solution and
is a 1.51 M solution.
Example 2
[0197] Direct preparation of a second solution for the preparation
of a solubility enhancing aqueous composition without the prior
preparation of a first solution wherein the ratio of a first
solution equivalent to water addition in this step is four parts
water to one part first solution equivalent: [0198] 1.15 mL of 20%
(NH.sub.4).sub.2SO.sub.4 was added to a common 10 mL polypropylene
centrifuge tube [0199] 8.0 mL deionized water added to tube [0200]
0.850 mL of concentrated (95-98%) sulfuric acid (H.sub.2SO.sub.4)
added to tube with sufficient force to mix
Example 3
[0201] Direct preparation of a second solution for a solubility
enhancing aqueous composition without the prior preparation of a
first solution wherein the ratio of a first solution equivalent to
water addition in this step is nine parts water to one part first
solution equivalent: [0202] 0.576 mL of 20%
(NH.sub.4).sub.2SO.sub.4 was added to a common 10 mL polypropylene
centrifuge tube [0203] 9.0 mL deionized water added to tube [0204]
0.424 mL of concentrated (95-98%) sulfuric acid (H.sub.2SO.sub.4)
added to tube with sufficient force to mix
Example 4
[0205] Direct preparation of a second solution for a solubility
enhancing aqueous composition without the prior preparation of a
first solution wherein the ratio of a first solution equivalent to
water addition in this step is nineteen parts water to one part
first solution equivalent: [0206] 0.288 mL of 20%
(NH.sub.4).sub.2SO.sub.4 was added to a common 10 mL polypropylene
centrifuge tube [0207] 9.5 mL deionized water added to tube [0208]
0.212 mL of concentrated (95-98%) sulfuric acid (H.sub.2SO.sub.4)
added to tube with sufficient force to mix
Example 5
[0209] Preparation of solubility enhancing aqueous composition
samples for liquid chromatography--mass spectrometry (LC-MS)
analysis: Each of Examples 2, 3 and 4, following addition of the
sulfuric acid: [0210] the centrifugation tubes were briefly capped
and vortexed to mix thoroughly [0211] caps were loosened to vent.
It was observed that the temperatures of the centrifugation tubes
were greater than ambient temperature. Such temperature was not
sufficient to melt the centrifugation tubes. [0212] reactions were
allowed to run for about 60 minutes [0213] after completion of the
reaction time, 1 mL samples of the reacted solutions were filtered
through a 0.44 micro Pall syringe filter and placed into labeled
mass spectrometry vials [0214] vials were loaded into a Thermo Q
Exactive Plus MS system with a Vanquish LC front end [0215] LC
Settings: [0216] 0.25 ml/min [0217] 40% methanol/60% water/0.1%
formic acid [0218] column temp 30.degree. C. [0219] Thermo Accucore
AQ C18 polar end cap column (150 mm.times.3 mm) [0220] Injection
volumes of 20 uL [0221] Low resolution parameters [0222] Full
MS-SIM [0223] 0-10 minutes [0224] Positive polarity [0225]
Resolution: 70,000 [0226] AGC Target: 3.times.10.sup.6 [0227] Max
IT: 200 ms [0228] Scan Range: 50-700 mz [0229] High resolution
parameters [0230] Full MS/dd-MS.sup.2 [0231] 0-7 minutes [0232]
Positive polarity [0233] Full MS: Resolution: 70,500 [0234] AGC
Target: 3.times.10.sup.6 [0235] Max IT: 100 ms [0236] Scan range:
50-700 mz [0237] dd-MS.sup.2: Resolution: 17,500 [0238] AGC target:
2.times.10.sup.6 [0239] Max IT: 50 ms [0240] Scan range: 50-700 mz
[0241] Minimum AGC Target: 2.times.10.sup.3
Example 6: Laboratory Preparations of First Solutions for
Preparation of Solubility Enhancing Aqueous Compositions for Ion
Chromatographic Quantification
[0241] [0242] A 24% solution of ammonium sulfate was created by
adding 96 grams of ammonium sulfate to 400 grams deionized water.
The solution was mixed to completely dissolve the ammonium sulfate.
[0243] Ten (10) identical 20 mL reactions were produced: [0244] 9.6
mL of the preceding 24% ammonium sulfate solution was added to
individually labeled common 50 mL conical tubes by way of
calibrated macropipette [0245] 10.4 mL of concentrated sulfuric
acid (95-98% reagent grade) was added to each tube by way of
calibrated micropipette with sufficient force to thoroughly mix
[0246] Tubes were allowed to stand loosely capped for an hour for
reaction to run to completion.
Example 7: Ion Chromatography (IC) Method
[0247] Samples from Example 6 were transferred to IC vials, diluted
appropriately (1:2500) to bring the ionic concentrations into the
range of testing equipment used, and ion chromatography was
undertaken using the following parameters:
[0248] Ion Chromatography:
[0249] Dual Thermo Dionex Aquion
[0250] Anion Side:
[0251] Column: Dionex IonPac AS22 RFIC 4.times.250 mm
[0252] Mobile phase: carbonate/bicarbonate buffet at 4.8/1.2 mM
[0253] Flow: 1.2 mL/min isocratic
[0254] Suppressor: Dionex ADRS 600 4 mm
[0255] Sup. Voltage: 33 mA
[0256] Standard: IC STD for sulfate, 50-500 ppm
[0257] Anion cell: 35.degree. C.
[0258] Anion column: 30.degree. C.
[0259] 18 minute run time
[0260] Cation Side:
[0261] Column: Dionex IonPac CS16 RFIC 5.times.250 mm
[0262] Mobile phase: 30 mM MSA solution
[0263] Flow: 1 mL/min isocratic
[0264] Suppressor: Dionex CDRS 600 4 mm
[0265] Sup voltage: 89 mA
[0266] Standard: IC STD for ammonium 20-100 ppm
[0267] Cation cell: 40.degree. C.
[0268] Cation column: 35.degree. C.
[0269] 18 minute run time
[0270] All 25 uL injections
Example 8. Ion Chromatography Results
[0271] Using the sample preparations set forth in Example 6 and the
ion chromatography methods set forth in Example 7, the following
results (10 samples; 2 replicates) were obtained:
TABLE-US-00001 Sulfate mol/L Ammonium mol/L 9.1904799 1.6264427
8.00-13.00 1.45-2.01
Example 9: Commercial-Scale Production of a Solubility Enhancing
Composition First Solution
[0272] Into a 500-gallon polyethylene conical-bottom tank was added
160.5 pounds (about 19.2 gallons) of deionized water. Upon addition
of the water, a magnetic-driven shearing pump with an impeller was
engaged, circulating the water in the tank. To the water was slowly
added 50.7 pounds of pre-weighed ammonium sulfate (GAC Chemical
Corp., Searsport Maine, U.S.A.) to enable solubilization of the
ammonium sulfate preparing a 31.6% ammonium sulfate solution. The
recirculating pump was allowed to run for about 20 minutes for this
batch size. Complete solubilization of the ammonium sulfate was
visually confirmed by decanting about 250 mL of solution into a PET
bottle that was allowed to stand undisturbed for about 15 minutes,
confirming complete solubilization.
[0273] A 50-gallon Dietrich (Corpus Christi, Texas, U.S.A.)
closed-loop, stainless steel-jacketed, glass-lined reactor was
pre-cooled using a CTS T-230 cooling tower (Cooling Tower Systems,
Macon, Georgia U.S.A.) circulating a mixture of municipal water and
sufficient sodium hypochlorite to maintain a pH from about 7.5 to
about 7.8. To this reactor was added 400.6 pounds (about 26.1
gallons) of 98% sulfuric acid (Brenntag; Henderson, Kentucky
U.S.A.) while a shaft-driven paddle mixer was engaged at 1700 rpm.
To the sulfuric acid was rapidly added the ammonium sulfate
solution and was mixed for about 20 minutes (until the reaction
mixture cooled to a temperature of about 130 degrees Fahrenheit) at
which time the reaction to form this first solution was
complete.
Example 10: Commercial Production of a Solubility Enhancing
Composition Second Solution
[0274] To a one thousand gallon polyethylene conical-bottom tank is
added deionized water equal to the volume or mass of the first
solution. To this water is added the first solution. The resulting
mixture represents a second solution of the present invention.
Example 11: Ion Chromatography Results
[0275] Using the sample preparations set forth in Example 9 and the
ion chromatography methods set forth in Example 7, the following
results (averages of 3 replicates of 3 samples) were obtained:
TABLE-US-00002 Sulfate mol/L Ammonium mol/L 10.77769681
1.677964718
[0276] Target Ranges:
TABLE-US-00003 Sulfate mol/L Ammonium mol/L 8.00-13.00
1.45-2.01
Example 12. Preparation of an Aqueous Paper Enhancing Composition
(Also Used for the Preparation of an Aqueous Carbonate Enhancing
Composition)
[0277] A 30% sodium hydroxide solution is prepared by dissolving
300 grams of sodium hydroxide per 1000 grams (1.0 L) of water;
[0278] A 50% Glucopon.RTM. 420 solution is prepared by dissolving
500 grams of Glucopon 420 per 1000 grams (1.0 L) of water; [0279]
To an appropriate mixing vessel is added 2700.98 grams of water;
[0280] To the water is added 551.60 grams of a first solution (as
defined above) with slow mixing; [0281] To the previous solution is
added 276.91 grams of a 30% sodium hydroxide solution with slow
mixing; [0282] Mix the previous solution slowly for 30 minutes and,
after which, adjust the pH to 3.0; [0283] To the previous solution,
slowly add 891.74 grams of copper sulfate with mixing until the
copper sulfate is fully dissolved; [0284] To the previous solution,
add 5.80 grams of 50% Glucopon 420 and mix for 1 hour; [0285]
Adjust the final pH to 3.0 with sodium hydroxide.
Example 13. Commercial-Scale Preparation (330 Gallons of Finished
Product) of an Aqueous Paper Enhancing Composition (Also Used for
the Preparation of an Aqueous Carbonate Enhancing Composition)
[0285] [0286] To a 500 gallon polyethylene tank was added 2,116
pounds of 17 megohm water, with mixing via circulation from a
roller pump; [0287] To the water was added 183 pounds of a
solubility enhancing aqueous composition, with continued mixing;
[0288] To the prior solution was slowly added 183 pounds of 50%
sodium hydroxide, with continued mixing; [0289] To the prior
solution was added 590 pounds of copper sulfate, with continued
mixing to maintain the copper sulfate in solution; [0290] To the
prior solution/suspension was added 2 pounds of Glucopon 420.RTM.
with continued mixing for one hour [0291] pH of the final solution
is adjusted to a pH from about 2.5 to about 3.5 using additional
solubility enhancing aqueous composition in the pH needs to be
lowered or add sodium hydroxide if the pH needs to be increased to
the target range.
* * * * *