EP1951955A1 - A paper substrate having enhanced print density - Google Patents

A paper substrate having enhanced print density

Info

Publication number
EP1951955A1
EP1951955A1 EP06827277A EP06827277A EP1951955A1 EP 1951955 A1 EP1951955 A1 EP 1951955A1 EP 06827277 A EP06827277 A EP 06827277A EP 06827277 A EP06827277 A EP 06827277A EP 1951955 A1 EP1951955 A1 EP 1951955A1
Authority
EP
European Patent Office
Prior art keywords
paper
sizing composition
substrate
paper substrate
sizing
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
EP06827277A
Other languages
German (de)
French (fr)
Other versions
EP1951955B1 (en
Inventor
Jay C. Song
Sen Yang
Yan C. Huang
Kapil M. Singh
Michael F. Koenig
David B. Shelmidine
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
International Paper Co
Original Assignee
International Paper Co
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by International Paper Co filed Critical International Paper Co
Priority to PL12002601T priority Critical patent/PL2511419T3/en
Priority to PL06827277T priority patent/PL1951955T3/en
Priority to EP12002601.8A priority patent/EP2511419B1/en
Publication of EP1951955A1 publication Critical patent/EP1951955A1/en
Application granted granted Critical
Publication of EP1951955B1 publication Critical patent/EP1951955B1/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H21/00—Non-fibrous material added to the pulp, characterised by its function, form or properties; Paper-impregnating or coating material, characterised by its function, form or properties
    • D21H21/14—Non-fibrous material added to the pulp, characterised by its function, form or properties; Paper-impregnating or coating material, characterised by its function, form or properties characterised by function or properties in or on the paper
    • D21H21/16—Sizing or water-repelling agents
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H21/00—Non-fibrous material added to the pulp, characterised by its function, form or properties; Paper-impregnating or coating material, characterised by its function, form or properties
    • D21H21/14—Non-fibrous material added to the pulp, characterised by its function, form or properties; Paper-impregnating or coating material, characterised by its function, form or properties characterised by function or properties in or on the paper
    • D21H21/18—Reinforcing agents
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H17/00—Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
    • D21H17/03—Non-macromolecular organic compounds
    • D21H17/05—Non-macromolecular organic compounds containing elements other than carbon and hydrogen only
    • D21H17/07—Nitrogen-containing compounds
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H17/00—Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
    • D21H17/20—Macromolecular organic compounds
    • D21H17/21—Macromolecular organic compounds of natural origin; Derivatives thereof
    • D21H17/24—Polysaccharides
    • D21H17/28—Starch
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H17/00—Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
    • D21H17/20—Macromolecular organic compounds
    • D21H17/33—Synthetic macromolecular compounds
    • D21H17/34—Synthetic macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • D21H17/36—Polyalkenyalcohols; Polyalkenylethers; Polyalkenylesters
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H17/00—Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
    • D21H17/20—Macromolecular organic compounds
    • D21H17/33—Synthetic macromolecular compounds
    • D21H17/34—Synthetic macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • D21H17/41—Synthetic macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds containing ionic groups
    • D21H17/44—Synthetic macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds containing ionic groups cationic
    • D21H17/45—Nitrogen-containing groups
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H19/00—Coated paper; Coating material
    • D21H19/36—Coatings with pigments
    • D21H19/44—Coatings with pigments characterised by the other ingredients, e.g. the binder or dispersing agent
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H21/00—Non-fibrous material added to the pulp, characterised by its function, form or properties; Paper-impregnating or coating material, characterised by its function, form or properties
    • D21H21/14—Non-fibrous material added to the pulp, characterised by its function, form or properties; Paper-impregnating or coating material, characterised by its function, form or properties characterised by function or properties in or on the paper
    • D21H21/30—Luminescent or fluorescent substances, e.g. for optical bleaching

Definitions

  • the present invention relates to a sizing composition that, when applied to paper
  • substrate creates a substrate, preferably suitable for inkjet printing, having increased
  • the substrate print density, print sharpness, low HST, and/or image dry time, the substrate
  • the present invention relates to a method of reducing the HST of a paper
  • FIG. 2 A second schematic cross section of just one exemplified embodiment of the
  • the present inventors have discovered a sizing composition that, when
  • substrate preferably has a high brightness.
  • the sizing composition may contain a pigment.
  • pigments are examples of pigments.
  • the pigment when it is a calcium carbonate, it may be in any form. Examples include
  • Omya Inc and OmyaJet B5260, C4440 and 6606 from Omya Inc.
  • the pigment may have any surface area. Those pigments having a high
  • surface area are included, including those having a surface area of greater than 20
  • square meters/gram preferably greater than 30 square meters/gram, more preferably
  • the sizing composition may contain a pigment at any amount.
  • composition may include from 0 to 99wt% based upon the total weight of the solids
  • the composition preferably at least 15wt%, more preferably at least 30wt%, most
  • composition This range may include 0, 1, 5, 10, 15, 20, 25, 30, 35, 40, 45, 50, 55,
  • the sizing composition may contain a binder.
  • binders include,
  • polychloride emulsion modified starch such as hydroxyethyl starch, starch or
  • potato for example, poly aery lamide, modified polyacrylamide, polyol, polyol
  • glyoxal glyoxal urea, ethanedial, aliphatic polyisocyanate, isocyanate, 1 ,6
  • one embodiment includes a sizing composition
  • one embodiment relates to a
  • system including at least starch and deriviates thereof with polyvinyl alcohol.
  • the sizing composition may be any ratio so long as both are present in the composition.
  • the sizing composition may contain a ratio of starcli/PVOH wt%
  • polyvinyl alcohol is produced by hydrolyzing polyvinyl acetate (PVA).
  • the PVOH are less viscous and more water soluble.
  • the PVOH may have a
  • %hydrolysis ranging from 100% to 75%.
  • the % hydrolysis may be 75, 76, 78, 80,
  • the % hydrolysis of the PVOH is
  • the sizing composition may contain a binder at any amount.
  • composition may contain at least one binder from 0 to 99wt%, preferably at least 10wt%, more preferably at least 20wt%, most preferably at least 30 wt% based on
  • the total weight of the solids in the composition may include 0, 1, 5, 10,
  • the sizing composition when the sizing composition contains a binder and a
  • the weight ratio of the binder/pigment may be any ratio.
  • pigment weight ratio may be from 99/1 to 1/99, preferably from 50/1 to 1/10, more
  • the sizing composition may contain at least one nitrogen containing organic compound
  • Exemplified nitrogen containing organic species are compounds,
  • oligomers and polymers are those containing one or more quaternary ammonium
  • DEAMEMA diethylaminoethylmethacrylate
  • polyamides polyamides
  • glycigyl addition polymers poly[oxyethylene (dimethyliminio) ethylene
  • containing species are polymers and copolymers of diallyldimethyl ammonium
  • the sizing composition may contain at least one nitrogen containing organic compound
  • the composition based on the total weight of the solids in the composition, including any and all ranges and subranges contained therein.
  • the total weight of the solids in the composition including any and all ranges and subranges contained therein.
  • inorganic salts may be monovalent and/or divalent and/or trivalent and may contain
  • Exemplified inorganic salts are those
  • the cationic metal may be sodium, calcium, magnesium, and aluminum
  • the anionic counterion to the cationic metal of the inorganic salt may be
  • any halogen such as chloride, boride, fluoride, etc and/or hydroxyl group(s).
  • most preferred inorganic salt being sodium chloride.
  • the sizing composition may contain at least one inorganic salt at any amount.
  • the sizing composition may contain from 0 to 99wt%, preferably from 0.25 to 25
  • inorganic salt based on the total weight of the solids in the composition. This range
  • inorganic salt based on the total weight of the solids in the composition.
  • the sizing composition may contain at least one optical brightening agent
  • the OBAs may be commercially available from
  • the OBA contained in the sizing composition is cationic.
  • the sizing composition may contain any amount of at least one anionic OBA.
  • the sizing composition may contain anionic OBA at an amount from O to 99wt%,
  • range may include 0, 1, 5, 10, 15, 20, 25, 30, 35, 40, 45, 50, 55, 60, 65, 70, 75, 80,
  • the sizing composition contains about 35wt% of anionic
  • the sizing composition may contain any amount of at least one cationic
  • the sizing composition may contain cationic OBA at an amount from O to
  • composition This range may include 0, 1, 5, 10, 15, 20, 25, 30, 35, 40, 45, 50, 55,
  • the sizing composition contains about 8wt% of
  • the present invention also relates to a paper substrate containing any of the
  • the paper substrate contains a web of cellulose fibers.
  • fibers may be from any fibrous plant.
  • the paper substrate of the present invention is
  • Recycled fibers may contain recycled fibers and/or virgin fibers. Recycled fibers differ from virgin fibers in that the fibers have gone through the drying process at least once.
  • the fiber source may be any, the preferable sources of the cellulose
  • fibers are from softwood and/or hardwood.
  • the paper substrate of the present invention is from softwood and/or hardwood.
  • inventions may contain from 1 to 100 wt%, preferably from 5 to 95 wt%, cellulose
  • This range includes 1, 2, 5, 10, 15, 20, 25, 30, 35, 40,
  • the paper substrate of the present invention may contain from 1 to 100 wt%,
  • cellulose fibers originating from hardwood species preferably from 5 to 95 wt%, cellulose fibers originating from hardwood species
  • This range includes 1, 2, 5, 10, 15, 20, 25, 30, 35, 40, 45, 50, 55, 60, 65, 70, 75, 80, 85, 90, 95,
  • the hardwood/softwood ratio be from 0.001 to 1000. This range may
  • Examples of physical means include, but is not limited to, electromagnetic
  • Means for electrical modification include, but are not
  • optical brighteners i.e. OBAs
  • OBAs optical brighteners
  • One example of a recycled fiber is a "fine”. Sources of "fines" may be found
  • amount of "fines" present in the paper substrate can be modified by tailoring the rate at which such streams are added to the paper making process.
  • the paper substate preferably contains a combination of hardwood fibers
  • Fibers are, as discussed above,
  • Fines may typically be not more that 100 ⁇ m in
  • the fines are preferably not more than 5, 10, 15, 20, 25, 30, 35, 40, 45, 50, 55, 60,
  • the paper substrate may contain fines at any amount.
  • the paper substrate may contain fines at any amount.
  • the paper substrate contains not more than 0.01, 0.05, 0.1 ,
  • the paper substrate may also contain an internal sizing and/or external sizing
  • the internal sizing composition may be applied to the fibers during
  • compositions of the present invention may be the internal and/or external sizing
  • composition contained by the paper substrate of the present invention contains
  • FIGS 1-3 demonstrate different embodiments of the paper substrate 1 in the
  • Figure 1 demonstrates a paper substrate 1
  • composition 2 has minimal interpenetration of the web of cellulose fibers 3.
  • an embodiment may be made, for example, when a sizing composition is coated
  • Figure 2 demonstrates a paper substrate 1 that has a web of cellulose fibers 3
  • the interpenetration layer 4 of the paper substrate 1 defines a
  • the interpenetration layer may be from 1 to 99% of the entire cross
  • section of at least a portion of the paper substrate including I 5 2, 5, 10, 15, 20, 25, 30, 35, 40, 45, 50, 55, 60, 65, 70, 75, 80, 85, 90, 95, and 99% of the paper substrate,
  • Addition points may be at the size press, for example.
  • Figure 3 demonstrates a paper substrate 1 that has a web of cellulose fibers 3
  • Such an embodiment may be
  • the paper substrate may be made by contacting any component of the sizing
  • the contacting may occur at acceptable concentration levels that provide the paper
  • substrate of the present invention to contain any of the above-mentioned amounts of
  • the contacting may occur anytime
  • the components of the sizing solution are preformulated either
  • the paper or paperboard of this invention can be prepared using known
  • the paper substrate may contain the sizing composition at any amount.
  • paper substrate may contain the sizing composition at an amount ranging from 70 to
  • This range includes, 70, 80, 90, 100, 110, 120, 130, 140, 150, 160, 170, 180, 190,
  • the paper substrate contains a size press applied sizing composition at an amount of 150
  • the paper substrate contains 1501bs of
  • the paper substrate contains 50% x 1501bs/ton of
  • the paper substrate contains any amount of at least one pigment.
  • substrate may contain from 0.5 wt % to 10 wt%, preferably from 1 to 8wt%, more
  • the paper substrate contains any amount of at least inorganic salt.
  • inorganic salt based upon the total weight of the substrate, including any and all
  • the OBA may be any organic radical mentioned above and/or within the substrate itself.
  • the OBA may be any organic radical mentioned above and/or within the substrate itself.
  • the OBA may be any organic radical mentioned above and/or within the substrate itself.
  • the OBA may be any organic radical mentioned above and/or within the substrate itself.
  • the OBA may be any organic radical mentioned above and/or within the substrate itself.
  • the OBA may be any organic radical mentioned above and/or within the substrate itself.
  • the OBA may be any organic radicals mentioned above and/or within the substrate itself.
  • the paper substrate contains internal OBA and externally applied OBA.
  • the internal OBA may be cationic or
  • the externally applied OBA may be cationic or
  • the externally applied OBA is preferably
  • the paper substrate of the present invention may have any amount of OBA.
  • the OBA is present in as sufficient amount so that the paper has
  • the GE brightness is preferably at least 80, 85, 90, 91,
  • OBA effective amount of OBA is such that the GE brightness is at least 90, preferably at
  • inventions preferably have a final caliper, after calendering of the paper, and any
  • the caliper is from about 4 mils to about 20 mils, and most
  • the final density of the papers may be calculated by any of the above-
  • the web density is from about 7 lb/3000ft 2 /mil to about
  • the web may also include other conventional additives such as, for example,
  • starch expandable microspheres, mineral fillers, bulking agents, sizing agents,
  • wet strength resins internal sizes, dry strength resins, alum, fillers,
  • the internal sizing agents encompass any of those commonly used at
  • Ketene dimers are commercially available, as Aquapel.RTM. and Precis.RTM.
  • the paper substrate may be made by contacting further optional substances
  • cellulose fibers may occur anytime in the papermaking process including, but not
  • the paper substrate may be pressed in a press section containing one or more
  • nips any pressing means commonly known in the art of papermaking may be utilized.
  • the nips may be, but is not limited to, single felted, double felted,
  • the paper substrate may be dried in a drying section. Any drying means
  • the substrate is
  • the paper substrate may be passed through a size press, where any sizing
  • metered size press e.g. blade metered, rod metered. At the size press, sizing
  • the sizing apparatus is a puddle size press.
  • the paper substrate may be calendered by any commonly known calendaring
  • composition and/or particle of the present invention may reduce and alleviate
  • Microfinishing is a means commonly known in the art of papermaking. Microfinishing is a means
  • substrate may be microfmished with or without a calendering means applied thereto
  • microfinishing means can be any suitable microfinishing means.
  • HST Hercules Sizing Test Value
  • the HST is measured using the
  • the paper substrate of the present invention may
  • the HST may be as much as 400, 300, 200,
  • the HST may be is as low as 0.1, 1, 5 and 10 seconds.
  • the HST may be 0.001, 0.01, 0.05, 0.1 ,
  • the HST will vary directly with the basic weight of the
  • the paper substrate of the present invention may have any black optical
  • the black optical density may be 0.5, 0..6, 0.7, 0.8, 0.9, 1.0, 1.05, 1.06, 1.07, 1.08, 1.09, 1.10, 1.11, 1.12,
  • the paper substrate of the present invention may have any waterfastness.
  • the paper substrate of the present invention may have any waterfastness.
  • substrate may have a waterfastness of at least 90%, preferably at least 95%, more
  • the paper substrate may contain
  • An effective amount of pigment and binder An effective amount of pigment and
  • binder is that which bestows on the paper a black optical density that is at least 1.0
  • the present invention relates to a method of decreasing the HST of a paper
  • the above-mentioned sizing composition is contacted with a
  • substrate having a first HST and containing a web of cellulose fibers and optional
  • the sizing composition the web of cellulose fibers, and optional substance.
  • the present invention preferably reduces
  • the first HST by at least 10%, more preferably by at least 25%, most preferably by
  • This reduction range may be at least 10, 15, 20, 25, 30, 35, 40, 45, 50,
  • the p i gmented size press formulations were applied to an unsurface sized 90 gsm base paper using a rod mete ⁇ ng size press
  • the target coat weight or pick up is 6 gsm Calendering was done on a steel -to- steel lab calender at room temperature with a nip p ressure of 90 psi
  • the smoothness target is 125 Sheffield smoothness
  • Paper substrates having a basis weight of 24 lb/1300 square feet were made and a
  • the sizing compositions applied to the paper substrate are those according to
  • Mowiol 28-99 (Clariant) is a version of PVOH, which is 99% hydrolyzed and is of
  • the paper after size press was dried to 4.2 to 5.0% moisture.
  • the two numbers before and after the slash sign represent readings from the two
  • InkJet print densities are measured by means of optical densities with an X-
  • Densitometer manufactured by X-Rite Inc. Density is a function of the percentage

Abstract

The present invention relates to a sizing composition that, when applied to paper substrate, creates a substrate, preferably suitable for inkjet printing, having increased print density, print sharpness, low HST, and/or image dry time, the substrate preferably having high brightness and reduced color-to-color bleed as well. In addition, the present invention relates to a method of reducing the HST of a paper substate by applying the sizing composition to at least one surface thereof. Further, the application relates to methods of making and using the sizing composition, as well as methods of making and using the paper containing the sizing composition.

Description

A PAPER SUBSTRATE HAVING ENHANCED PRINT DENSITY
The present application claims the benefit of priority under 35 USC § 119(e)
to United States Provisional Patent Application 60/732,828 , filed November 1,
2005, which is hereby incorporated, in its entirety, herein by reference.
Field of the Invention
The present invention relates to a sizing composition that, when applied to paper
substrate, creates a substrate, preferably suitable for inkjet printing, having increased
print density, print sharpness, low HST, and/or image dry time, the substrate
preferably having high brightness and reduced color-to-color bleed as well. In
addition, the present invention relates to a method of reducing the HST of a paper
substate by applying the sizing composition to at least one surface thereof. Further, the
application relates to methods of making and using the sizing composition, as well as
methods of making and using the paper containing the sizing composition.
Background of the Invention
InkJet recording systems using aqueous inks are now well known. These
systems usually generate almost no noise and can easily perform multicolor
recordings for business, home and commercial printing applications. Recording sheets for ink jet recordings are known. See for example U.S. Pat. Nos. 5,270,103;
5,657,064; 5,760,809; 5,729,266; 4,792,487; 5,405,678; 4,636,409; 4,481,244;
4,496,629; 4,517,244; 5,190,805; 5,320,902; 4,425,405; 4,503,118; 5,163,973;
4,425,405; 5,013,603; 5,397,619; 4,478,910; 5,429,860; 5,457,486; 5,537,137;
5,314,747; 5,474,843; 4,908,240; 5,320,902; 4,740,420; 4,576,867; 4,446,174;
4,830,911; 4,554,181; 6,764,726 and 4,877,680, which are hereby incorporated, in
their entirety, herein by reference.
However, conventional paper substrates, such as those above remain poor in
balancing good print density, HST, color-to-color bleed, print sharpness, and/or
image dry time. Accordingly, there is a need to provide such high-performance
functionality to paper substrates useful in inkjet printing, especially those substrates
preferably having high brightness.
BRIEF DESCRIPTION OF THE DRAWINGS
Figure 1: A first schematic cross section of just one exemplified embodiment of the
paper substrate that is included in the paper substrate of the present invention. Figure 2: A second schematic cross section of just one exemplified embodiment of the
paper substrate that is included in the paper substrate of the present invention.
Figure 3: A third schematic cross section of just one exemplified embodiment of the
paper substrate that is included in the paper substrate of the present invention.
DETAILED DESCRIPTION OF THE INVENTION
The present inventors have discovered a sizing composition that, when
applied to paper or paperboard substrates, improves the substrate's print density,
color-to-color bleed, print sharpness, and/or image dry time. Further, the paper
substrate preferably has a high brightness.
The sizing composition may contain a pigment. Examples of pigments are
clay, calcium carbonate, calcium sulfate hemihydrate, and calcium sulfate
dehydrate, calcium carbonate, preferably precipitated calcium carbonate, in any
form including ground calcium carbonate and silica-treated calcium carbonate.
When the pigment is a calcium carbonate, it may be in any form. Examples include
ground calcium carbonate and/or precipitated calcium carbonate. Commercially available products that are preferred are those offered as Jetcoat 30 from Specialty
Minerals Inc., Jetcoat MD 1093 from Specialty Minerals Inc., XC3310-1 from
Omya Inc, and OmyaJet B5260, C4440 and 6606 from Omya Inc.
The pigment may have any surface area. Those pigments having a high
surface area are included, including those having a surface area of greater than 20
square meters/gram, preferably greater than 30 square meters/gram, more preferably
greater than 50 square meters/gram, most preferably greater than 100 square
meters/gram. This range includes greater than or equal to 1, 5, 10, 15, 20, 25, 30,
35, 40, 45, 50, 55, 60, 65, 70, 75, 80, 85, 90, 100 square meters/gram, including any
and all ranges and subranges contained therein.
The sizing composition may contain a pigment at any amount. The
composition may include from 0 to 99wt% based upon the total weight of the solids
in the composition, preferably at least 15wt%, more preferably at least 30wt%, most
preferably at least 45wt% pigment based upon the total weight of the solids in the
composition. This range may include 0, 1, 5, 10, 15, 20, 25, 30, 35, 40, 45, 50, 55,
60, 65, 70, 75, 80, 85, 90, 100wt% of pigment based upon the total weight of the
solids in the composition, including any and all ranges and subranges contained therein. The most preferred amount being about 52 wt% pigment based upon the
total weight of the solids in the composition.
The sizing composition may contain a binder. Examples of binders include,
but are not limited to, polyvinyl alcohol, Amres (a Kymene type), Bayer Parez,
polychloride emulsion, modified starch such as hydroxyethyl starch, starch or
derivatives thereof including cationic and oxidized forms and from corn and/or
potato for example, poly aery lamide, modified polyacrylamide, polyol, polyol
carbonyl adduct, ethanedial/polyol condensate, polyamide, epichlorohydrin,
glyoxal, glyoxal urea, ethanedial, aliphatic polyisocyanate, isocyanate, 1 ,6
hexamethylene diisocyanate, diisocyanate, polyisocyanate, polyester, polyester
resin, polyacrylate, polyacrylate resin, acrylate, and methacrylate. While any
combination of binders may be used, one embodiment includes a sizing composition
containing starch or modifications thereof combined with polyvinyl alcohol as
multi-component binder.
When there is a multicomponent binder system, one embodiment relates to a
system including at least starch and deriviates thereof with polyvinyl alcohol. In this
embodiment, the ratio of starch/PVOH solids based on the total weight of the solids
in the sizing composition may be any ratio so long as both are present in the composition. The sizing composition may contain a ratio of starcli/PVOH wt%
solids based on the total weight of the solids in the composition of from 99/1 to
1/99, preferably from 50/1 to 1/5, more preferably at most 10/1 to 1 :2, most
preferably at most 8/1 to 1/1. This range includes 99/1, 50/1, 25/1, 15/1., 10/1, 9/1,
8/1, 7/1, 6/1, 5/1, 4/1, 3/1, 2/1, 1/1, 2/3, 1/2, 1/10, 1/25, 1/50, 1/99, including any
and all ranges and subranges therein. The most preferred starch/PVOH ratio being
6/1.
When polyvinyl alcohol is utilized in the sizing solution and/or in the paper,
polyvinyl alcohol (PVOH) is produced by hydrolyzing polyvinyl acetate (PVA).
The acetate groups are replaced with alcohol groups and the higher the hydrolysis
indicates that more acetate groups have been replaced. Lower hydrolysis/molecular
weight PVOH are less viscous and more water soluble. The PVOH may have a
%hydrolysis ranging from 100% to 75%. The % hydrolysis may be 75, 76, 78, 80,
82, 84, 85, 86, 88, 90, 92, 94, 95, 96, 98, and 100%hdrolysis, %, including any and
all ranges and subranges therein. Preferably, the % hydrolysis of the PVOH is
greater than 90%.
The sizing composition may contain a binder at any amount. The sizing
composition may contain at least one binder from 0 to 99wt%, preferably at least 10wt%, more preferably at least 20wt%, most preferably at least 30 wt% based on
the total weight of the solids in the composition. This range may include 0, 1, 5, 10,
15, 20, 25, 30, 35, 40, 45, 50, 55, 60, 65, 70, 75, 80, 85, 90, 100wt% based on the
total weight of the solids in the composition, including any and all ranges and
subranges contained therein. The most preferred being about 37wt% binder based
on the total weight of the solids in the composition.
In one embodiment, when the sizing composition contains a binder and a
pigment, the weight ratio of the binder/pigment may be any ratio. The binder
pigment weight ratio may be from 99/1 to 1/99, preferably from 50/1 to 1/10, more
preferably from 25/1 to 1/5, most preferably from 10/1 to 1/3. This range includes
99/1, 50/1, 25/1, 10/1, 5/1, 2/1, 1/1, 1/2, 2/3, 1/3, 1/4, 1/5, 10/1, 25/1, 50/1, and
99/1, including any and all ranges and subranges therein. The most preferred
binder/pigment weight ratio is 7/10.
The sizing composition may contain at least one nitrogen containing organic
species. Exemplified nitrogen containing organic species are compounds,
oligomers and polymers are those containing one or more quaternary ammonium
functional groups. Such functional groups may vary widely and include substituted and unsubstituted amines, imines, amides, urethanes, quaternary ammonium groups,
dicyandiamides and the like. Illustrative of such materials are polyamines,
polyethyleneimines, polymers and copolymers of diallyldimethyl ammonium
chloride (DADMAC), copolymers of vinyl pyrrolidone (VP) with quaternized
diethylaminoethylmethacrylate (DEAMEMA), polyamides, cationic polyurethane
latex, cationic polyvinyl alcohol, polyalkylamines dicyandiamid copolymers, amine
glycigyl addition polymers, poly[oxyethylene (dimethyliminio) ethylene
(dimethyliminio) ethylene] dichlorides. Examples of nitrogen containing species
include those mentioned in US Patent Number 6,764,726, which is hereby
incorporated, in its entirety, herein by reference. The most preferred nitrogen
containing species are polymers and copolymers of diallyldimethyl ammonium
chloride (DADMAC).
The sizing composition may contain at least one nitrogen containing organic
species at any amount. The sizing composition may contain the nitrogen containing
species at an amount ranging from 0 to 99wt%, preferably from 0.5 to 50wt%, more
preferably from 1 to 20 wt %, most preferably from 2 to 10 wt% based on the total
weight of the solids in the composition. This range may include 0, 0.5, 1, 2, 3, 4, 5,
6, 7, 8, 9, 10, 15, 20, 25, 30, 35, 40, 45, 50, 55, 60, 65, 70, 75, 80, 85, 90, 100wt%
based on the total weight of the solids in the composition, including any and all ranges and subranges contained therein. In a preferred embodiment, the
composition contains about 8wt% of the nitrogen containing species based on the
total weight of the solids in the composition.
The sizing composition may contain at least one inorganic salt. Suitable
inorganic salts may be monovalent and/or divalent and/or trivalent and may contain
any level of hydration complexes thereof. Exemplified inorganic salts are those
from Groups 1 , 2 and 13 from the Periodic Table of Elements and hydrated
complexes thereof, including monohydrates, dihydrates, trihydrates, tetrahydrates,
etc. The cationic metal may be sodium, calcium, magnesium, and aluminum
preferably. The anionic counterion to the cationic metal of the inorganic salt may be
any halogen such as chloride, boride, fluoride, etc and/or hydroxyl group(s). The
most preferred inorganic salt being sodium chloride.
The sizing composition may contain at least one inorganic salt at any amount.
The sizing composition may contain from 0 to 99wt%, preferably from 0.25 to 25
wt%, more preferably from 0.5 to 5, most preferably from 1 to 3 wt% of the
inorganic salt based on the total weight of the solids in the composition. This range
may include O5 0.25, 0.5, 1, 2, 3, 4, 5, 10, 15, 20, 25, 30, 35, 40, 45, 50, 55, 60, 65,
70, 75, 80, 85, 90, 100wt% based on the total weight of the solids in the composition, including any and all ranges and subranges contained therein. In a
preferred embodiment, the sizing composition contains about 2.5wt% of the
inorganic salt based on the total weight of the solids in the composition.
The sizing composition may contain at least one optical brightening agent
(OBA). Suitable OBAs may be those mentioned in USSN 60/654,712 filed
February 19, 2005, and USP 6,890,454, which are hereby incorporated, in their
entirety, herein by reference. The OBAs may be commercially available from
Clariant. Further, the OBA may be either cationic and/or anionic. Example OBA is
that commercially available Leucophore BCW and Leucophore FTS from Clariant.
In one embodiment, the OBA contained in the sizing composition is cationic.
The sizing composition may contain any amount of at least one anionic OBA.
The sizing composition may contain anionic OBA at an amount from O to 99wt%,
preferably from 5 to 75wt%, more preferably from 10 to 50 wt%, most preferably
from 20 to 40wt% based on the total weight of the solids in the composition. This
range may include 0, 1, 5, 10, 15, 20, 25, 30, 35, 40, 45, 50, 55, 60, 65, 70, 75, 80,
85, 90, 99wt% anionic OBA based on the total weight of the solids in the
composition, including any and all ranges and subranges contained therein. In a preferred embodiment, the sizing composition contains about 35wt% of anionic
OBA based on the total weight of the solids in the composition.
The sizing composition may contain any amount of at least one cationic
OBA. The sizing composition may contain cationic OBA at an amount from O to
99wt%, preferably from 0.5 to 25wt%, more preferably from 1 to 20 wt%, most
preferably from 5 to 15wt% based on the total weight of the solids in the
composition. This range may include 0, 1, 5, 10, 15, 20, 25, 30, 35, 40, 45, 50, 55,
60, 65, 70, 75, 80, 85, 90, 99wt% anionic OBA based on the total weight of the
solids in the composition, including any and all ranges and subranges contained
therein. In a preferred embodiment, the sizing composition contains about 8wt% of
cationic OBA based on the total weight of the solids in the composition.
The present invention also relates to a paper substrate containing any of the
sizing compositions described above.
The paper substrate contains a web of cellulose fibers. The source of the
fibers may be from any fibrous plant. The paper substrate of the present invention
may contain recycled fibers and/or virgin fibers. Recycled fibers differ from virgin fibers in that the fibers have gone through the drying process at least once.
The paper substrate of the present invention may contain from 1 to 99 wt%,
preferably from 5 to 95 wt%, most preferably from 60 to 80 wt% of cellulose fibers
based upon the total weight of the substrate, including 1, 5, 10, 15, 20, 25, 30, 35,
40, 45, 50, 55, 60, 65, 70, 75, 80, 85, 90, 95 and 99 wt%, and including any and all
ranges and subranges therein.
While the fiber source may be any, the preferable sources of the cellulose
fibers are from softwood and/or hardwood. The paper substrate of the present
invention may contain from 1 to 100 wt%, preferably from 5 to 95 wt%, cellulose
fibers originating from softwood species based upon the total amount of cellulose
fibers in the paper substrate. This range includes 1, 2, 5, 10, 15, 20, 25, 30, 35, 40,
45, 50, 55, 60, 65, 70, 75, 80, 85, 90, 95, and 100wt%, including any and all ranges
and subranges therein, based upon the total amount of cellulose fibers in the paper
substrate.
The paper substrate of the present invention may contain from 1 to 100 wt%,
preferably from 5 to 95 wt%, cellulose fibers originating from hardwood species
based upon the total amount of cellulose fibers in the paper substrate. This range includes 1, 2, 5, 10, 15, 20, 25, 30, 35, 40, 45, 50, 55, 60, 65, 70, 75, 80, 85, 90, 95,
and 100wt%, including any and all ranges and subranges therein, based upon the
total amount of cellulose fibers in the paper substrate.
When the paper substrate contains both hardwood and softwood fibers, it is
preferable that the hardwood/softwood ratio be from 0.001 to 1000. This range may
include 0.001, 0.002, 0.005, 0.01, 0.02, 0.05, 0.1, 0.2, 0.5, 1, 2, 5, 10, 15, 20, 25, 30,
35, 40, 45, 50, 55, 60, 65, 70, 75, 80, 85, 90, 95, 100, 200, 300, 400, 500, 600, 700,
800, 900, and 1000 including any and all ranges and subranges therein and well as
any ranges and subranges therein the inverse of such ratios.
Further, the softwood and/or hardwood fibers contained by the paper
substrate of the present invention may be modified by physical and/or chemical
means. Examples of physical means include, but is not limited to, electromagnetic
and mechanical means. Means for electrical modification include, but are not
limited to, means involving contacting the fibers with an electromagnetic energy
source such as light and/or electrical current. Means for mechanical modification
include, but are not limited to, means involving contacting an inanimate object with
the fibers. Examples of such inanimate objects include those with sharp and/or dull
edges. Such means also involve, for example, cutting, kneading, pounding, impaling, etc means.
Examples of chemical means include, but is not limited to, conventional
chemical fiber modification means including crosslinking and precipitation of
complexes thereon. Examples of such modification of fibers may be, but is not
limited to, those found in the following patents 6,592,717, 6,592,712, 6,582,557,
6,579,415, 6,579,414, 6,506,282, 6,471,824, 6,361,651, 6,146,494, Hl, 704,
5,731,080, 5,698,688, 5,698,074, 5,667,637, 5,662,773, 5,531,728, 5,443,899,
5,360,420, 5,266,250, 5,209,953, 5,160,789, 5,049,235, 4,986,882, 4,496,427,
4,431,481, 4,174,417, 4,166,894, 4,075,136, and 4,022,965, which are hereby
incorporated, in their entirety, herein by reference. Further modification of fibers is
found in United States Patent Applications having Application Number 60/654,712
filed February 19, 2005; 11/358,543 filed February 21, 2006; 11/445,809 filed June
2, 2006; and 11/446,421 filed June 2, 2006, which may include the addition of
optical brighteners (i.e. OBAs) as discussed therein, which are hereby incorporated,
in their entirety, herein by reference.
One example of a recycled fiber is a "fine". Sources of "fines" may be found
in SaveAll fibers, recirculated streams, reject streams, waste fiber streams. The
amount of "fines" present in the paper substrate can be modified by tailoring the rate at which such streams are added to the paper making process.
The paper substate preferably contains a combination of hardwood fibers,
softwood fibers and "fines" fibers. "Fines" fibers are, as discussed above,
recirculated and are any length. Fines may typically be not more that 100 μm in
length on average, preferably not more than 90 μm, more preferably not more than
80 μm in length, and most preferably not more than 75 μm in length. The length of
the fines are preferably not more than 5, 10, 15, 20, 25, 30, 35, 40, 45, 50, 55, 60,
65, 70, 75, 80, 85, 90, 95, and 100 μm in length, including any and all ranges and
subranges therein.
The paper substrate may contain fines at any amount. The paper substrate
may contain from 0.01 to 100 wt% fines, preferably from 0.01 to 50wt%, most
preferably from 0.01 to 15wt% based upon the total weight of the fibers contained
by the paper substrate. The paper substrate contains not more than 0.01, 0.05, 0.1 ,
0.2, 0.5, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 12, 15, 20, 25, 30, 35, 40, 45, 50, 55, 60, 65, 70,
75, 80, 85, 90, 95 and 100wt% fines based upon the total weight of the fibers
contained by the paper substrate, including any and all ranges and subranges
therein. The paper substrate may also contain an internal sizing and/or external sizing
composition. The internal sizing composition may be applied to the fibers during
papermaking at the wet end, while the external sizing composition may be applied
to the fibers via a size press and/or coater. The above mentioned sizing
compositions of the present invention may be the internal and/or external sizing
composition contained by the paper substrate of the present invention.
Figures 1-3 demonstrate different embodiments of the paper substrate 1 in the
paper substrate of the present invention. Figure 1 demonstrates a paper substrate 1
that has a web of cellulose fibers 3 and a sizing composition 2 where the sizing
composition 2 has minimal interpenetration of the web of cellulose fibers 3. Such
an embodiment may be made, for example, when a sizing composition is coated
onto a web of cellulose fibers.
Figure 2 demonstrates a paper substrate 1 that has a web of cellulose fibers 3
and a sizing composition 2 where the sizing composition 2 interpenetrates the web
of cellulose fibers 3. The interpenetration layer 4 of the paper substrate 1 defines a
region in which at least the sizing solution penetrates into and is among the
cellulose fibers. The interpenetration layer may be from 1 to 99% of the entire cross
section of at least a portion of the paper substrate, including I5 2, 5, 10, 15, 20, 25, 30, 35, 40, 45, 50, 55, 60, 65, 70, 75, 80, 85, 90, 95, and 99% of the paper substrate,
including any and all ranges and subranges therein. Such an embodiment may be
made, for example, when a sizing composition is added to the cellulose fibers prior
to a coating method and may be combined with a subsequent coating method if
required. Addition points may be at the size press, for example.
Figure 3 demonstrates a paper substrate 1 that has a web of cellulose fibers 3
and a sizing solution 2 where the sizing composition 2 is approximately evenly
distributed throughout the web of cellulose fibers 3. Such an embodiment may be
made, for example, when a sizing composition is added to the cellulose fibers prior
to a coating method and may be combined with a subsequent coating method if
required. Exemplified addition points may be at the wet end of the paper making
process, the thin stock, and the thick stock.
The paper substrate may be made by contacting any component of the sizing
solution with the cellulose fibers consecutively and/or simultaneously. Still further,
the contacting may occur at acceptable concentration levels that provide the paper
substrate of the present invention to contain any of the above-mentioned amounts of
cellulose and components of the sizing solution. The contacting may occur anytime
in the papermaking process including, but not limited to the thick stock, thin stock, head box, and coater with the preferred addition point being at the thin stock.
Further addition points include machine chest, stuff box, and suction of the fan
pump. Preferably, the components of the sizing solution are preformulated either
together and/or in combination within a single and/or separate coating layer(s) and
coated onto the fibrous web via a size press and/or coater.
The paper or paperboard of this invention can be prepared using known
conventional techniques. Methods and apparatuses for forming and making and
applying a coating formulation to a paper substrate are well known in the paper and
paperboard art. See for example, G.A. Smook referenced above and references cited
therein all of which is hereby incorporated by reference. All such known methods
can be used in the practice of this invention and will not be described in detail.
The paper substrate may contain the sizing composition at any amount. The
paper substrate may contain the sizing composition at an amount ranging from 70 to
300 lbs/ton of paper, preferably from 80 to 2501bs/ton of paper, more preferably
from 100 to 200 lbs/ton of paper, most preferably from 125 to 175 lbs/ton of paper.
This range includes, 70, 80, 90, 100, 110, 120, 130, 140, 150, 160, 170, 180, 190,
200, 210, 220, 230, 240, 250, 260, 270 280, 290, and 300 lbs/ton of paper, including
any and all ranges and subranges therein. In a preferred embodiment the paper substrate contains a size press applied sizing composition at an amount of 150
lbs/ton of paper substrate.
Given the above mentioned preferred amounts of sizing composition
contained in the substrate of the present invention, combined with the above-
mentioned amounts of pigment, binder, nitrogen containing compound, and
inorganic salt; the amounts of each of the pigment, binder, nitrogen containing
compound, inorganic salt that are contained in the paper may be easily calculated.
For example, if 50wt% of pigment is present in the sizing solution based upon the
total weight of solids in the composition, and the paper substrate contains 1501bs of
the sizing composition/ton, then the paper substrate contains 50% x 1501bs/ton of
paper= 75 lbs pigment/ton of paper, which is 75 lbs/20001bs x 100= 3.75wt%
pigment based upon the total weight of the paper substrate.
The paper substrate contains any amount of at least one pigment. The paper
substrate may contain from 0.5 wt % to 10 wt%, preferably from 1 to 8wt%, more
preferably from 1.5 to 6wt%, most preferably from 2 to 5wt% of pigment based
upon the total weight of the substrate. This range includes 0.5, 1, 1.5, 2, 2.5, 3, 3.5, 4, 4.5, 5, 5.5, 6, 6.5, 7, 7.5, 8, 8.5, 9, 9.5 and 10wt% of pigment based upon the total
weight of the substrate, including any and all ranges and subranges therein.
The paper substrate contains any amount of at least one binder. The paper
substrate may contain from 0.1 wt % to 7 wt%, preferably from .2 to 5 wt%, more
preferably from 0.3 to 3wt%, most preferably from 1 to 3 wt% of binder based upon
the total weight of the substrate. This range includes 0.1, 0.2, 0.3, 0.4, 0.5, 1, 1.5, 2,
2.5, 3, 3.5, 4, 4.5, 5, 5.5, 6, 6.5, 7, and 7.5wt% of binder based upon the total weight
of the substrate, including any and all ranges and subranges therein.
The paper substrate contains any amount of at least one nitrogen containing
compound. The paper substrate may contain from 0.01 wt % to 5 wt%, preferably
from 0.05 to 2wt%, more preferably from 0.1 to 1.5 wt%, most preferably from 0.25
to 1 wt% of nitrogen containing compound based upon the total weight of the
substrate. This range includes 0.01, 0.02, 0.03, 0.05, 0.07, 0.1, 0.2, 0.3, 0.4, 0.5,
0.6, 0.7, 0.8, 0.9, 1 , 1.2, 1.4, 1.6, 1.8, 2.0, 2.2, 2.4, 2.6, 2.8, and 3wt% of nitrogen
containing compound based upon the total weight of the substrate, including any
and all ranges and subranges therein. The paper substrate contains any amount of at least inorganic salt. The paper
substrate may contain from 0.001 wt % to 3 wt%, preferably from 0.01 to 2.5wt%,
more preferably from 0.02 to 1 wt%5 most preferably from 0.05 to 0.5 wt% of
inorganic salt based upon the total weight of the substrate. This range includes
0.001, 0.002, 0.005, 0.007, 0.01, 0.02, 0.03, 0.05, 0.06, 0.07, 0.08, 0.09, 0.1, 0.2,
0.3, 0.4, 0.5, 0.6, 0.7, 0.8, 0.9, 1, 1.2, 1.4, 1.6, 1.8, 2.0, 2.2, 2.4, 2.6, 2.8, and 3wt%
of inorganic salt based upon the total weight of the substrate, including any and all
ranges and subranges therein.
The paper substrate may contain any amount of OBA. The OBA may be
cationic and/or anionic. The OBA may be supplied by the sizing composition as
mentioned above and/or within the substrate itself. For example, the OBA may be
premixed with the fibers at the wet end of the papermaking and even before the
headbox. Preferred examples of using OBA:fϊber mixes is found in United States
Patent Applications having Application Number 60/654,712 filed February 19,
2005; 11/358,543 filed February 21, 2006; 11/445,809 filed June 2, 2006; and
11/446,421 filed June 2, 2006, which are hereby incorporated, in their entirety,
herein by reference.
In one embodiment of the present invention, the paper substrate contains internal OBA and externally applied OBA. The internal OBA may be cationic or
anionic, but is preferably anionic. The externally applied OBA may be cationic or
anionic, but is preferably cationic. The externally applied OBA is preferably
applied as a member of the sizing composition at the size press as mentioned above
in the above preferred amounts of OBA. However, external OBA may also be
applied at the coating section.
The paper substrate of the present invention may have any amount of OBA.
In one embodiment, the OBA is present in as sufficient amount so that the paper has
at least 80% GE brightness. The GE brightness is preferably at least 80, 85, 90, 91,
92, 93, 94, 95, 96, 97, 98, 99, and 100%, including any and all ranges and subranges
contained therein.
Further, the paper may have a suitable amount of OBA and other additives
(such as dyes) so that the paper preferably has a CIE whiteness of at least 130. The
CIE whiteness may be at least 130, 135, 140, 145, 150, 155, 160, 65, 170, 175, 180,
185, 190, 195, and 200 CIE whiteness points, including any and all ranges and
subranges therein. In one embodiment, the substrate contains an effective amount of OBA. An
effective amount of OBA is such that the GE brightness is at least 90, preferably at
least 92, more preferably at least 94 and most preferably at least 95% brightness.
The OBA may be a mixture of the above-mentioned internal and externally applied
OBA, whether cationic and/or anionic so long as it is an effective amount.
The density, basis weight and caliper of the web of this invention may vary
widely and conventional basis weights, densities and calipers may be employed
depending on the paper-based product formed from the web. Paper or paperboard of
invention preferably have a final caliper, after calendering of the paper, and any
nipping or pressing such as may be associated with subsequent coating of from
about 1 mils to about 35 mils although the caliper can be outside of this range if
desired. More preferably the caliper is from about 4 mils to about 20 mils, and most
preferably from about 7 mils to about 17 mils. The caliper of the paper substrate
with or without any coating may be 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 17,
20, 22, 25, 27, 30, 32, and 35, including any and all ranges and subranges therein.
Paper substrates of the invention preferably exhibit basis weights of from
about 10 lb/3000ft 2 to about 500 lb/3000ft 2, although web basis weight can be
outside of this range if desired. More preferably the basis weight is from about 301b/3000ft 2 to about 200 lb/3000ft 2, and most preferably from about 35 lb/3000ft
2 to about 150 lb/3000ft 2. The basis weight may be 10, 12, 15, 17, 20, 22, 25, 30,
32, 35, 37, 40, 45, 50, 55, 60, 65, 70, 75, 80, 85, 90, 95, 100, 110, 120, 130, 140,
150, 160, 170, 180, 190, 200, 225, 250, 275, 300, 325, 350, 375, 400, 425, 450, 500
lb/3000ft 2, including any and all ranges and subranges therein.
The final density of the papers may be calculated by any of the above-
mentioned basis weights divided by any of the above-mentioned calipers, including
any and all ranges and subranges therein. Preferably, the final density of the papers,
that is, the basis weight divided by the caliper, is preferably from about 6 lb/3000ft
2/mil to about 14 lb/3000ft 2/mil although web densities can be outside of this range
if desired. More preferably the web density is from about 7 lb/3000ft 2/mil to about
13 lb/3000ft 2/mil and most preferably from about 9 lb/3000ft 2/mil to about 12
lb/3000ft 2ImU.
The web may also include other conventional additives such as, for example,
starch, expandable microspheres, mineral fillers, bulking agents, sizing agents,
retention aids, and strengthening polymers. Among the fillers that may be used are
organic and inorganic pigments such as, by way of example, polymeric particles
such as polystyrene latexes and polymethylmethacrylate, and minerals such as calcium carbonate, kaolin, and talc. Other conventional additives include, but are
not restricted to, wet strength resins, internal sizes, dry strength resins, alum, fillers,
pigments and dyes. Internal sizing helps prevent the surface size from soaking into
the sheet, thus allowing it to remain on the surface where it has maximum
effectiveness. The internal sizing agents encompass any of those commonly used at
the wet end of a paper machine. These include rosin sizes, ketene dimers and
multimers, and alkenylsuccinic anhydrides. The internal sizes are generally used at
levels of from about 0.00 wt. % to about 0.25 wt. % based on the weight of the dry
paper sheet. Methods and materials utilized for internal sizing with rosin are
discussed by E. Strazdins in The Sizing of Paper, Second Edition, edited by W. F.
Reynolds, Tappi Press, 1989, pages 1-33. Suitable ketene dimers for internal sizing
are disclosed in U.S. Pat. No. 4,279,794, which is incorporated by reference in its
entirety, and in United Kingdom Patent Nos. 786,543; 903,416; 1,373,788 and
1,533, 434, and in European Patent Application Publication No. 0666368 A3.
Ketene dimers are commercially available, as Aquapel.RTM. and Precis.RTM.
sizing agents from Hercules Incorporated, Wilmington, Del. Ketene multimers for
use in internal sizes are described in: European Patent Application Publication No.
0629741A1 , corresponding to U.S. patent application Ser. No. 08/254,813, filed
Jun. 6, 1994; European Patent Application Publication No. 0666368A3,
corresponding to U.S. patent application Ser. No. 08/192,570, filed Feb. 7, 1994; and U.S. patent application Ser. No. 08/601,113, filed Feb. 16, 1996.
Alkenylsuccinic anhydrides for internal sizing are disclosed in U. S. Pat. No.
4,040,900, which in incorporated herein by reference in its entirety, and by C. E.
Farley and R. B. Wasser in The Sizing of Paper, Second Edition, edited by W. F.
Reynolds, Tappi Press, 1989, pages 51-62. A variety of alkenylsuccinic anhydrides
are commercially available from Albemarle Corporation, Baton Rouge, La.
The paper substrate may be made by contacting further optional substances
with the cellulose fibers as well. The contacting of the optional substances and the
cellulose fibers may occur anytime in the papermaking process including, but not
limited to the thick stock, thin stock, head box, size press, water box, and coater.
Further addition points include machine chest, stuff box, and suction of the fan
pump. The cellulose fibers, components of the sizing composition, and/or optional
components may be contacted serially, consecutively, and/or simultaneously in any
combination with each other. The cellulose fibers components of the sizing
composition may be pre-mixed in any combination before addition to or during the
paper-making process.
The paper substrate may be pressed in a press section containing one or more
nips. However, any pressing means commonly known in the art of papermaking may be utilized. The nips may be, but is not limited to, single felted, double felted,
roll, and extended nip in the presses. However, any nip commonly known in the art
of papermaking may be utilized.
The paper substrate may be dried in a drying section. Any drying means
commonly known in the art of papermaking may be utilized. The drying section
may include and contain a drying can, cylinder drying, Condebelt drying, IR, or
other drying means and mechanisms known in the art. The paper substrate may be
dried so as to contain any selected amount of water. Preferably, the substrate is
dried to contain less than or equal to 10% water.
The paper substrate may be passed through a size press, where any sizing
means commonly known in the art of papermaking is acceptable. The size press,
for example, may be a puddle mode size press (e.g. inclined, vertical, horizontal) or
metered size press ( e.g. blade metered, rod metered). At the size press, sizing
agents such as binders may be contacted with the substrate. Optionally these same
sizing agents may be added at the wet end of the papermaking process as needed.
After sizing, the paper substrate may or may not be dried again according to the
above-mentioned exemplified means and other commonly known drying means in
the art of papermaking. The paper substrate may be dried so as to contain any selected amount of water. Preferably, the substrate is dried to contain less than or
equal to 10% water. Preferably, the sizing apparatus is a puddle size press.
The paper substrate may be calendered by any commonly known calendaring
means in the art of papermaking. More specifically, one could utilize, for example,
wet stack calendering, dry stack calendering, steel nip calendaring, hot soft
calendaring or extended nip calendering, etc. While not wishing to be bound by
theory, it is thought that the presence of the expandable microspheres and/or
composition and/or particle of the present invention may reduce and alleviate
requirements for harsh calendaring means and environments for certain paper
substrates, dependent on the intended use thereof.
The paper substrate may be microfmished according to any microfinishing
means commonly known in the art of papermaking. Microfinishing is a means
involving frictional processes to finish surfaces of the paper substrate. The paper
substrate may be microfmished with or without a calendering means applied thereto
consecutively and/or simultaneously. Examples of microfinishing means can be
found in United States Published Patent Application 20040123966 and references
cited therein, as well as USSN 60/810181 filed on June 2, 2006, which are all
hereby, in their entirety, herein incorporated by reference. The Hercules Sizing Test Value ("HST") of the substrate is selected to
provide the desired waterfastness characteristics. The HST is measured using the
procedure of TAPPI 530 pm-89. The paper substrate of the present invention may
have any HST. In some embodiments, the HST may be as much as 400, 300, 200,
and 100 seconds. Further, the HST may be is as low as 0.1, 1, 5 and 10 seconds.
However, in a preferred embodiment of this invention, the HST is less than 10
seconds, preferably, less than 5 seconds, more preferably less than 3 seconds HST,
most preferably less than about 1 second. The HST may be 0.001, 0.01, 0.05, 0.1 ,
0.5, 1, 1.5, 2, 2.5, 3, 3.5, 4, 4.5, 5, 5.5, 6, 6.5, 7, 7.5, 8, 8.5, 9, 9.5 and 10 seconds,
including any and all ranges and subranges therein. As it is well known to those of
ordinary skill in the art, the HST will vary directly with the basic weight of the
substrate and other factors known to those of ordinary skill in the art. Based upon
the foregoing information, one of ordinary skill in the art can use conventional
techniques and procedures to calculate, determine and/or estimate a particular HST
for the substrate used to provide the desired image waterfastness characteristics.
The paper substrate of the present invention may have any black optical
density as measured by TAPPI METHOD T 1213 sρ-03. The black optical density
may be from 0.5 to 2.0, more preferably from 1.0 to 1.5. The black optical density may be 0.5, 0..6, 0.7, 0.8, 0.9, 1.0, 1.05, 1.06, 1.07, 1.08, 1.09, 1.10, 1.11, 1.12,
1.13, 1.14, 1.15, 1.16, 1.17, 1.18, 1.19, 1.2, 1.3, 1.4, and 1.5, including any and all
ranges and subranges therein.
From density, one can naturally calculate waterfastness using the following
equation:
(OD of soaked ink area/OD of unsoaked ink area) * 100 = % Waterfastness.
The paper substrate of the present invention may have any waterfastness. The paper
substrate may have a waterfastness of at least 90%, preferably at least 95%, more
preferably greater than 98%, most preferably greater than 100%, including any and
all ranges and subranges therein.
In one embodiment of the present invention, the paper substrate may contain
an effective amount of pigment and binder. An effective amount of pigment and
binder is that which bestows on the paper a black optical density that is at least 1.0,
preferably from 1 to 2, more preferably from 1 to 1.5 and most preferably from 1.1
to 1.3, including any and all ranges and subranges therein. The present invention relates to a method of decreasing the HST of a paper
substrate. Preferably, the above-mentioned sizing composition is contacted with a
substrate having a first HST and containing a web of cellulose fibers and optional
substances mentioned above at a size press or coating section so as to prepare a
paper substrate having a second HST that is less than the first HST and containing
the sizing composition, the web of cellulose fibers, and optional substance. While
the second HST is less than the first HST, the present invention preferably reduces
the first HST by at least 10%, more preferably by at least 25%, most preferably by
at least 50%. This reduction range may be at least 10, 15, 20, 25, 30, 35, 40, 45, 50,
60, 75, 80, 95 and 99% of the first HST, including any and all ranges and subranges
therein.
The present invention is explained in more detail with the aid of the
following embodiment example which is not intended to limit the scope of the
present invention in any manner.
EXAMPLES
Example J-
The following size press formulations were prepared for treating the un-surface sized base paper
The pigmented size press formulations were applied to an unsurface sized 90 gsm base paper using a rod meteπng size press The target coat weight or pick up is 6 gsm Calendering was done on a steel -to- steel lab calender at room temperature with a nip pressure of 90 psi The smoothness target is 125 Sheffield smoothness
J he paper samples from example ] were evaluated forpnnt performance on an Kodak Versamark 5000 digital press ExcelJent pπnt quality were obtained The print density the tnal sam les rovided m example ] are listed m the following table
Example 2:
Paper substrates having a basis weight of 24 lb/1300 square feet were made and a
sizing composition was applied thereto both surfaces of the paper substrate at size
press. The sizing compositions applied to the paper substrate are those according to
the following Table 2.
Table 2
Gen Floe F71 100 (General Chemicals) and Cartafix VXZ (Clariant) are both of the
chemical nature of poly(dadmac) and are nitrogen-containing species.
Amres, a kymene wet-strength resin from Kamira is also nitrogen-containing
species.
Mowiol 28-99 (Clariant) is a version of PVOH, which is 99% hydrolyzed and is of
high molecular weight.
Starch and PVOH were cooked separately and diluted to a solids level of about
15%. Each of the formulation was prepared in accordance with the recipe as
tabulated above and was thoroughly mixed together.
An overall %solids was first arrived at greater than the targeted 15%, because the
rest of the ingredients all have a solids level above 15%.
For each of the formulations, the actual initial %solids was measured and then
diluted, as close as possible, to 15%. Each of the formulations was sent to the 14'
pilot size press, which was pre-configured to C2S puddle operation.
The paper after size press was dried to 4.2 to 5.0% moisture.
The subscript [a] denotes average, which means each of the numbers was averaged
from 4 or even more readings.
The two numbers before and after the slash sign represent readings from the two
sides of the paper, respectively.
InkJet print densities are measured by means of optical densities with an X-
rite densitometer. The density according to TAPPI METHOD T 1213 sp-03 is the
optical -negative logarithm to base 10 of transmittance for transparent material or the reflectance for an opaque material and has the equation Optical Density = log 10
1/R, where R = Reflectance. The following densitometer was used: X-Rite
Densitometer, manufactured by X-Rite Inc. Density is a function of the percentage
of light reflected. From this density procedure, one can easily measure
Waterfastness and % bleed as well using the following equations:
Calculation for % Waterfastness:
(OD of soaked ink area/OD of unsoaked ink area) * 100 = % Waterfastness
Calculation for % Bleed:
[(OD near soaked ink area - OD of paper)/OD unsoaked ink area] * 100 = % Bleed.
Numerous modifications and variations on the present invention are possible
in light of the above teachings. It is, therefore, to be understood that within the
scope of the accompanying claims, the invention may be practiced otherwise than as
specifically described herein.
As used throughout, ranges are used as a short hand for describing each and
every value that is within the range, including all subranges therein.
All of the references, as well as their cited references, cited herein are hereby
incorporated by reference with respect to relative portions related to the subject matter
of the present invention and all of its embodiments

Claims

WHAT IS CLAIMED IS:
1) A sizing composition, comprising
at least one pigment
at least one binder;
at least one nitrogen containing organic species; and
at least one inorganic salt.
2) The sizing composition according to Claim 1 , comprising
at least one pigment
at least two binders;
at least one nitrogen containing organic species; and
at least one inorganic salt.
3.) The sizing composition according to Claim 2, wherein the at least two
binders are polyvinyl alcohol and starch.
4.) The sizing composition according to Claim 3, wherein the polyvinyl
alcohol and starch are present at a starch/polyvinyl alcohol weight ratio of
from δ/l to l/1.
5.) The sizing composition according to Claim 4, wherein the total binder is
present at an amount of at least 20wt%, based upon the total weight of the
solids in of the composition.
6.) The sizing composition according to Claim 4, further comprising from 20
to 40wt% based on the total weight of the solids in the composition of an
optical brightening agent.
7.) The sizing composition according to Claim 4, further comprising an
optical brightening agent.
8.) The sizing composition according to Claim 8, wherein the optical
brightening agent is cationic.
9.) The sizing composition according to Claim 1, comprising
at least one pigment at an amount of at least 30wt% based upon the
total weight of the solids in of the composition
at least one binder at an amount of at least 20wt% based upon the total
weight of the solids in of the composition; at least one nitrogen containing organic species at an amount ranging
from 1 to 20wt% based upon the total weight of the solids in of the
composition; and
at least one inorganic salt at an amount ranging from 0.5 to 5wt%
based upon the total weight of the solids in of the composition.
10.) The sizing composition according to Claim 9, comprising
at least two binders wherein the at least two binders are starch and
polyvinyl alcohol at a weight ratio of from 8/1 to 1/1 starch/ polyvinyl
alcohol; and
an optical brightener.
11.) A paper substrate, comprising the sizing composition according to
Claim 1.
12.) The paper substate according to Claim 11, wherein the substrate has a
print density of at least 1.0 and an HST of not more than 10 seconds.
13.) The paper substrate according to Claim 12, wherein the substrate has a waterfastness of at least 95%.
14.) A paper substrate comprising the sizing composition according to
Claim 4.
15.) The paper substate according to Claim 14, wherein the substrate has a
print density of at least 1.0 and an HST of not more than 10 seconds.
16.) The paper substrate according to Claim 15, wherein the substrate has a
waterfastness of at least 95%.
17.) A paper substrate comprising the sizing composition according to
Claim 9.
18.) The paper substate according to Claim 17, wherein the substrate has a
print density of at least 1.0 and an HST of not more than 10 seconds.
19.) The paper substrate according to Claim 18, wherein the substrate has a
waterfastness of at least 95%.
0.) A paper substrate, comprising the sizing composition according to
Claim 10 and having
a print density of at least 1.0;
an HST of not more than 10 seconds; and
a waterfastness of at least 95%.
EP06827277A 2005-11-01 2006-11-01 A paper substrate having enhanced print density Active EP1951955B1 (en)

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Families Citing this family (24)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US7608166B2 (en) * 2003-09-17 2009-10-27 International Paper Company Papers having borate-based complexing and method of making same
US8758886B2 (en) 2005-10-14 2014-06-24 International Paper Company Recording sheet with improved image dry time
US7682438B2 (en) 2005-11-01 2010-03-23 International Paper Company Paper substrate having enhanced print density
US7736466B2 (en) 2006-01-17 2010-06-15 International Paper Company Paper substrates containing high surface sizing and low internal sizing and having high dimensional stability
WO2008144074A1 (en) * 2007-05-21 2008-11-27 International Paper Company Recording sheet with improved image waterfastness, surface strength, and runnability
US8057637B2 (en) 2007-12-26 2011-11-15 International Paper Company Paper substrate containing a wetting agent and having improved print mottle
US8652594B2 (en) 2008-03-31 2014-02-18 International Paper Company Recording sheet with enhanced print quality at low additive levels
US8460511B2 (en) 2008-10-01 2013-06-11 International Paper Company Paper substrate containing a wetting agent and having improved printability
US8678543B2 (en) 2008-10-16 2014-03-25 Hewlett-Packard Development Company, L.P. Composition and print medium
ES2390932T5 (en) 2008-11-27 2020-09-14 Archroma Ip Gmbh Optical Brightening Compositions for High-Quality Inkjet Printing
US20100129553A1 (en) * 2008-11-27 2010-05-27 International Paper Company Optical Brightening Compositions For High Quality Inkjet Printing
CA2744837C (en) * 2008-11-27 2017-06-13 Clariant Finance (Bvi) Limited Improved optical brightening compositions for high quality ink jet printing
EP2192231A1 (en) 2008-11-27 2010-06-02 Clariant International Ltd. Improved optical brightening compositions for high quality inkjet printing
EP2356183B2 (en) 2008-12-08 2021-01-27 Hewlett-Packard Development Company, L.P. Surface coating composition for inkjet media
US8652593B2 (en) 2009-12-17 2014-02-18 International Paper Company Printable substrates with improved brightness from OBAs in presence of multivalent metal salts
US8574690B2 (en) * 2009-12-17 2013-11-05 International Paper Company Printable substrates with improved dry time and acceptable print density by using monovalent salts
US8440053B2 (en) 2010-04-02 2013-05-14 International Paper Company Method and system using surfactants in paper sizing composition to inhibit deposition of multivalent fatty acid salts
US8608908B2 (en) 2010-04-02 2013-12-17 International Paper Company Method and system using low fatty acid starches in paper sizing composition to inhibit deposition of multivalent fatty acid salts
WO2011139481A1 (en) 2010-05-04 2011-11-10 International Paper Company Coated printed substrates resistant to acidic highlighters and printing solutions
US8795796B2 (en) 2010-07-23 2014-08-05 International Paper Company Coated printable substrates providing higher print quality and resolution at lower ink usage
US8697203B2 (en) 2010-11-16 2014-04-15 International Paper Company Paper sizing composition with salt of calcium (II) and organic acid, products made thereby, method of using, and method of making
US9328463B2 (en) 2010-11-17 2016-05-03 Hewlett-Packard Development Company, L.P. Surface sizing composition for print media in digital printing
SG11201501474RA (en) * 2012-09-12 2015-05-28 Yoshino Gypsum Co Gypsum composition, gypsum slurry, gypsum hardened body, gypsum-based building material, gypsum board, and manufacturing method for a gypsum-based building material
US9545810B2 (en) 2013-01-11 2017-01-17 Hewlett-Packard Development Company, L.P. Low grammage recording medium

Family Cites Families (79)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB551950A (en) * 1941-09-15 1943-03-17 Du Pont Improvements in or relating to the treatment of paper
US2322888A (en) 1940-11-16 1943-06-29 Du Pont Process for producing high wet strength paper
US2856310A (en) 1955-02-15 1958-10-14 Hercules Powder Co Ltd Stable ketene dimer-emulsifier mixtures and their preparation
NL246493A (en) 1958-12-24
GB1373788A (en) 1971-10-20 1974-11-13 Hercules Powder Co Ltd Sizing method and composition for use therein
DK659674A (en) 1974-01-25 1975-09-29 Calgon Corp
US4166894A (en) 1974-01-25 1979-09-04 Calgon Corporation Functional ionene compositions and their use
US4040900A (en) 1974-05-20 1977-08-09 National Starch And Chemical Corporation Method of sizing paper
US4022965A (en) 1975-01-13 1977-05-10 Crown Zellerbach Corporation Process for producing reactive, homogeneous, self-bondable lignocellulose fibers
US4174417A (en) 1975-10-14 1979-11-13 Kimberly-Clark Corporation Method of forming highly absorbent fibrous webs and resulting products
GB1533434A (en) 1976-03-10 1978-11-22 Hercules Inc Sizing method and a sizing composition for use therein
US4279794A (en) 1979-04-26 1981-07-21 Hercules Incorporated Sizing method and sizing composition for use therein
US4446174A (en) 1979-04-27 1984-05-01 Fuiji Photo Film Company, Ltd. Method of ink-jet recording
US4496427A (en) 1980-01-14 1985-01-29 Hercules Incorporated Preparation of hydrophilic polyolefin fibers for use in papermaking
JPS5738185A (en) 1980-08-20 1982-03-02 Matsushita Electric Ind Co Ltd Ink jet recording paper
US4517244A (en) 1981-08-06 1985-05-14 Canon Kabushiki Kaisha Recording medium and ink jet recording paper
US4496629A (en) 1982-01-12 1985-01-29 Canon Kabushiki Kaisha Material used to bear writing or printing
US4481244A (en) 1982-02-03 1984-11-06 Canon Kabushiki Kaisha Material used to bear writing or printing
US4431481A (en) 1982-03-29 1984-02-14 Scott Paper Co. Modified cellulosic fibers and method for preparation thereof
JPS59185690A (en) 1983-04-07 1984-10-22 Jujo Paper Co Ltd Ink jet recording paper
JPS6011389A (en) 1983-07-01 1985-01-21 Mitsubishi Paper Mills Ltd Ink jet recording paper
US4636409A (en) 1983-09-19 1987-01-13 Canon Kabushiki Kaisha Recording medium
JPS6067190A (en) 1983-09-22 1985-04-17 Ricoh Co Ltd Ink jet recording medium
US4554181A (en) 1984-05-07 1985-11-19 The Mead Corporation Ink jet recording sheet having a bicomponent cationic recording surface
DE3500408A1 (en) * 1985-01-08 1986-07-10 Skw Trostberg Ag, 8223 Trostberg METHOD FOR THE PRODUCTION OF PAPER, CARDBOARD, PAPERBOARDS AND OTHER MATERIALS CONTAINING CELLULOSE UNDER NEUTRAL TO LOW BASIC PH CONDITIONS
JPS62124976A (en) 1985-11-26 1987-06-06 Canon Inc Recording material
US5013603A (en) 1986-06-13 1991-05-07 Mizusawa Industrial Chemicals, Ltd. Ink jet recording paper with amorphous silica filler
JP2667162B2 (en) 1986-11-04 1997-10-27 日本製紙株式会社 Ink jet recording sheet
US4792487A (en) 1987-03-12 1988-12-20 James River Corporation Of Virginia Ink jet recording medium comprising (a) water expansible colloidal clay (b) silica and (c) water insoluble synthetic binder
JPS63314540A (en) * 1987-06-17 1988-12-22 Fuji Photo Film Co Ltd Photosensitive material
DE3730887A1 (en) 1987-09-15 1989-03-23 Basf Ag METHOD FOR IMPROVING THE PRINTABILITY OF PAPER
US4986882A (en) 1989-07-11 1991-01-22 The Proctor & Gamble Company Absorbent paper comprising polymer-modified fibrous pulps and wet-laying process for the production thereof
US5209953A (en) 1989-08-03 1993-05-11 Kimberly-Clark Corporation Overall printing of tissue webs
US5049235A (en) 1989-12-28 1991-09-17 The Procter & Gamble Company Poly(methyl vinyl ether-co-maleate) and polyol modified cellulostic fiber
US5160789A (en) 1989-12-28 1992-11-03 The Procter & Gamble Co. Fibers and pulps for papermaking based on chemical combination of poly(acrylate-co-itaconate), polyol and cellulosic fiber
US5360420A (en) 1990-01-23 1994-11-01 The Procter & Gamble Company Absorbent structures containing stiffened fibers and superabsorbent material
US5163973A (en) 1990-02-14 1992-11-17 Alcan Internatinal Limited Process for producing low soda alumina
US5266250A (en) 1990-05-09 1993-11-30 Kroyer K K K Method of modifying cellulosic wood fibers and using said fibers for producing fibrous products
US5270103A (en) 1990-11-21 1993-12-14 Xerox Corporation Coated receiver sheets
US5190805A (en) 1991-09-20 1993-03-02 Arkwright Incorporated Annotatable ink jet recording media
US5695609A (en) * 1992-01-20 1997-12-09 Kemira Oy Process for producing paper
US5320902A (en) 1992-04-01 1994-06-14 Xerox Corporation Recording sheets containing monoammonium compounds
FR2689530B1 (en) 1992-04-07 1996-12-13 Aussedat Rey NEW COMPLEX PRODUCT BASED ON FIBERS AND FILLERS, AND METHOD FOR MANUFACTURING SUCH A NEW PRODUCT.
JP2927377B2 (en) 1992-08-07 1999-07-28 日本製紙株式会社 Ink jet recording paper and method for manufacturing the same
US5760809A (en) 1993-03-19 1998-06-02 Xerox Corporation Recording sheets containing phosphonium compounds
US6180238B1 (en) 1993-03-19 2001-01-30 Xerox Corporation Recording sheets containing oxazole, isooxazole, oxazolidinone, oxazoline salt, morpholine, thiazole, thiazolidine, thiadiazole, and phenothiazine compounds
US5314747A (en) 1993-03-19 1994-05-24 Xerox Corporation Recording sheets containing cationic sulfur compounds
US6482503B1 (en) 1993-03-19 2002-11-19 Xerox Corporation Recording sheets containing pyrrole, pyrrolidine, pyridine, piperidine, homopiperidine, quinoline, isoquinoline, quinuclidine, indole, and indazole compounds
US5457486A (en) 1993-03-19 1995-10-10 Xerox Corporation Recording sheets containing tetrazolium indolinium, and imidazolinium compounds
US5405678A (en) 1993-05-07 1995-04-11 Otis Specialty Papers Inc. Ink jet recording sheet
GB9311944D0 (en) 1993-06-10 1993-07-28 Hercules Inc Synthesis of alkyl ketene multimers (akm) and application for precision converting grades of fine paper
US5474843A (en) 1993-12-16 1995-12-12 Labelon Corporation Acceptor material for inks
US5685815A (en) 1994-02-07 1997-11-11 Hercules Incorporated Process of using paper containing alkaline sizing agents with improved conversion capability
US5429860A (en) 1994-02-28 1995-07-04 E. I. Du Pont De Nemours And Company Reactive media-ink system for ink jet printing
SG80547A1 (en) * 1994-02-28 2001-05-22 Du Pont Ink jet recording sheet
GB9422280D0 (en) * 1994-11-04 1994-12-21 Ciba Geigy Ag Fluorescent whitening agent formulation
US5662773A (en) 1995-01-19 1997-09-02 Eastman Chemical Company Process for preparation of cellulose acetate filters for use in paper making
DE19534327A1 (en) * 1995-09-15 1996-02-22 Md Papier Gmbh High solids cationic compsn. for coating ink jet printing paper
JPH09119091A (en) * 1995-10-24 1997-05-06 Fuji Xerox Co Ltd Recording paper
US5667637A (en) 1995-11-03 1997-09-16 Weyerhaeuser Company Paper and paper-like products including water insoluble fibrous carboxyalkyl cellulose
US5698688A (en) 1996-03-28 1997-12-16 The Procter & Gamble Company Aldehyde-modified cellulosic fibers for paper products having high initial wet strength
JPH10226154A (en) * 1997-02-18 1998-08-25 Mitsubishi Paper Mills Ltd Ink jet recording sheet
US6146494A (en) 1997-06-12 2000-11-14 The Procter & Gamble Company Modified cellulosic fibers and fibrous webs containing these fibers
JP4034461B2 (en) * 1998-04-21 2008-01-16 三菱製紙株式会社 Inkjet recording paper
US6074057A (en) * 1998-05-22 2000-06-13 Eastman Kodak Company Pigmented ink jet inks and recording elements containing hardening agents
US6471824B1 (en) 1998-12-29 2002-10-29 Weyerhaeuser Company Carboxylated cellulosic fibers
BR9916641A (en) 1998-12-30 2001-09-25 Kimberly Clark Co Steam blast recycling process for fibers and fabrics made from recycled fibers
US6361651B1 (en) 1998-12-30 2002-03-26 Kimberly-Clark Worldwide, Inc. Chemically modified pulp fiber
US6602994B1 (en) * 1999-02-10 2003-08-05 Hercules Incorporated Derivatized microfibrillar polysaccharide
US6030443A (en) * 1999-04-29 2000-02-29 Hercules Incorporated Paper coating composition with improved optical brightener carriers
US6764726B1 (en) 1999-05-12 2004-07-20 Sen Yang Ink jet recording sheet with improved image waterfastness
US6458876B1 (en) * 1999-08-09 2002-10-01 Air Products And Chemicals, Inc. Ink jet paper coatings containing polyvinyl alcohol-alkylated polyamine blends
CA2413709C (en) 2000-06-27 2006-02-07 International Paper Company Method to manufacture paper using fiber filler complexes
JP2002069896A (en) * 2000-08-24 2002-03-08 Oji Paper Co Ltd Paper having excellent opacity
GB0100610D0 (en) 2001-01-10 2001-02-21 Clariant Int Ltd Improvements in or relating to organic compounds
US20040123966A1 (en) 2002-04-11 2004-07-01 Altman Thomas E. Web smoothness improvement process
JP2004050532A (en) * 2002-07-18 2004-02-19 Mitsubishi Paper Mills Ltd Method for manufacturing ink jet recording material
JPWO2004014659A1 (en) * 2002-08-12 2005-12-08 日本製紙株式会社 Inkjet cast coated paper
US20050020448A1 (en) * 2003-07-23 2005-01-27 Fuji Photo Film Co., Ltd. Paper, image-recording material support, and image-recording material

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See references of WO2007053681A1 *

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PT2511419E (en) 2014-04-07
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EP2511419B1 (en) 2014-01-08
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CN101351596A (en) 2009-01-21
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MX358994B (en) 2018-09-11
CA2627050A1 (en) 2007-05-10

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