WO2004027145A2 - Compositions de papier, procedes de formation d'images et procedes de fabrication de papier - Google Patents

Compositions de papier, procedes de formation d'images et procedes de fabrication de papier Download PDF

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Publication number
WO2004027145A2
WO2004027145A2 PCT/US2003/029358 US0329358W WO2004027145A2 WO 2004027145 A2 WO2004027145 A2 WO 2004027145A2 US 0329358 W US0329358 W US 0329358W WO 2004027145 A2 WO2004027145 A2 WO 2004027145A2
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WO
WIPO (PCT)
Prior art keywords
paper
anionic
acid
polymeric material
image
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PCT/US2003/029358
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English (en)
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WO2004027145A3 (fr
Inventor
Joseph H. Torras, Sr.
Clifford W. Parker
Satish Agrawal
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Eastern Pulp & Paper Corporation
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Application filed by Eastern Pulp & Paper Corporation filed Critical Eastern Pulp & Paper Corporation
Priority to AU2003267281A priority Critical patent/AU2003267281A1/en
Publication of WO2004027145A2 publication Critical patent/WO2004027145A2/fr
Publication of WO2004027145A3 publication Critical patent/WO2004027145A3/fr

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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
    • 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
    • D21H17/42—Synthetic macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds containing ionic groups anionic
    • D21H17/43—Carboxyl groups or derivatives thereof
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03G—ELECTROGRAPHY; ELECTROPHOTOGRAPHY; MAGNETOGRAPHY
    • G03G7/00—Selection of materials for use in image-receiving members, i.e. for reversal by physical contact; Manufacture thereof
    • G03G7/0006—Cover layers for image-receiving members; Strippable coversheets
    • G03G7/0013—Inorganic components thereof
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03G—ELECTROGRAPHY; ELECTROPHOTOGRAPHY; MAGNETOGRAPHY
    • G03G7/00—Selection of materials for use in image-receiving members, i.e. for reversal by physical contact; Manufacture thereof
    • G03G7/0006—Cover layers for image-receiving members; Strippable coversheets
    • G03G7/002—Organic components thereof
    • G03G7/0026—Organic components thereof being macromolecular
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03G—ELECTROGRAPHY; ELECTROPHOTOGRAPHY; MAGNETOGRAPHY
    • G03G7/00—Selection of materials for use in image-receiving members, i.e. for reversal by physical contact; Manufacture thereof
    • G03G7/0006—Cover layers for image-receiving members; Strippable coversheets
    • G03G7/002—Organic components thereof
    • G03G7/0026—Organic components thereof being macromolecular
    • G03G7/004—Organic components thereof being macromolecular obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03G—ELECTROGRAPHY; ELECTROPHOTOGRAPHY; MAGNETOGRAPHY
    • G03G7/00—Selection of materials for use in image-receiving members, i.e. for reversal by physical contact; Manufacture thereof
    • G03G7/0006—Cover layers for image-receiving members; Strippable coversheets
    • G03G7/002—Organic components thereof
    • G03G7/0026—Organic components thereof being macromolecular
    • G03G7/0046—Organic components thereof being macromolecular obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • 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

Definitions

  • This application relates to a novel paper composition and, more particularly, to paper which is suitable for use in electrophotographic copying and printing methods using dry or liquid toners as well as to methods for forming images on the paper and a method for manufacturing the paper.
  • a latent electrostatic image is initially formed on a photoconductive surface, typically by depositing a substantially uniform electrostatic charge on the photoconductive surface and exposing the charged surface to an imagewise pattern of radiation which corresponds to an image to be reproduced thereby discharging the photoconductive surface in an imagewise pattern.
  • the latent electrostatic image is then developed by applying to it a composition of charged colored particles, which, depending upon the charge on the colored particles, that is, negative or positive, can be arranged to adhere to areas of the photoconductive surface having the higher potential or lower potential, respectively.
  • the image thus formed on the photoconductive surface can then be transferred to a receiver material, typically paper, and adhered thereto so as to provide the desired reproduction.
  • the development of the latent electrostatic image can be either by a "dry” process wherein a dry composition of colored particles is used or by a “wet” process wherein colored particles are dispersed in a liquid vehicle, typically an insulating, nonpolar liquid such as mineral oil or the like.
  • the developer composition which is utilized to form the visible image, includes particles of the image-forming material, commonly referred to as "toner", such as, for example, carbon black, or other colored pigments, or dyes, and a thermoplastic polymeric binder material.
  • the thermoplastic polymeric binder materials together with other charge control agents and the colored pigments, also referred to hereinafter as pigmented polymer particles, are chosen so as to impart the desired charge triboelectrically to the image-forming material, as well as to provide an adequate degree of plasticity either at the temperature of the transferring surface or, where a specific fusing step is used to bind the image to the receiver surface, at the temperatures of the fusing step.
  • the plasticity is necessary to fuse the pigmented toner particles together (cohesive strength), and to the paper (adhesive strength).
  • the visible image formed on the photoconductive surface is transferred to the receiver material. Such transfer can be made directly to a receiver material to form the final hard copy image.
  • electrophotographic imaging methods in which the image formed on a photoconductive surface is first transferred to an intermediate transfer surface, also referred to hereinafter as ITS, and transferred from that surface to a final receiver material. Methods of this type are commonly referred to as "digital offset printing".
  • a method of this type, using a modulated laser beam to write the image on the photoconductor is described in U.S. Patent 4,708,460. According to the method described in U.S.
  • Patent 4,708,460 a photoconductive drum is charged electrostatically, exposed imagewise by means of a laser, and the resulting latent image developed by applying pigmented polymer particles in a liquid suspension, or emulsion, to the drum.
  • the image formed on the drum is transferred to an ITS, whereupon the liquid vehicle, typically mineral oil or the like, is heated and a significant amount is driven off and the pigmented polymer particles are caused to melt or soften. Subsequently the image is transferred to a final receiver sheet and adhered thereto.
  • monochrome printing a single color image is formed on the receiver material.
  • multicolor printing two or more separate monochrome images are formed on the drum in registration and transferred to the receiver sheet.
  • the receiver materials which are useful in electrophotographic copying and printing, including digital offset printing, are required to have a number of characteristics.
  • the receiver must be able to rapidly bond-the pigmented polymer particles in the short contact time between the receiver and the transferring surface, or during the short duration of a receiver image fusing step.
  • any reference to dwell time refers to the duration of either the image transfer step or the fusing step.
  • Receiver materials should also have a high surface strength so as to prevent unprinted area ghosting, or spurious images appearing on the receiver surface.
  • material can transfer from the receiver to the transferring surface, and with repeated printing of the same image, a significant deposit can be built up on the transfer surface in non imaged areas. This build up can then create ghost or spurious images upon subsequent printing of a different image.
  • Still another object of the invention is to provide a paper composition which is useful as a receiver material for images formed by electrophotographic imaging methods wherein the image is formed by a liquid developer composition, and the image is either transferred to a receiver and fused thereto or transferred to an intermediate transfer surface prior to being transferred to the receiver.
  • a further object is to provide an imaging method wherein the paper composition of the invention is utilized as the receiver material.
  • Yet another object is to provide electrophotographic printing methods including digital offset printing methods wherein a paper composition according to the invention is utilized as the receiver material.
  • Still another object of the invention is to provide a method for manufacturing the paper of the invention.
  • a paper composition which may be bleached, which comprises at least one anionic polymeric material and at least one binder material and which does not include more than about 20% by weight of mechamcal fiber; and preferably not more than about 10%.
  • the paper includes from about 0.1 to about 18.0 lbs/3300 ft 2 of finished paper of at least one anionic polymeric material and from about 0.25 to about 10.0 lbs/3300 ft 2 of finished paper of at least one binder material and particularly preferably, from about 0.20 to about 5.0 lbs/3300 ft 2 of finished paper of at least one anionic polymeric material and from about 1.0 to about 5.0 lbs/3300 ft 2 of finished paper of at least one binder material.
  • “mechanical fiber” refers to groundwood pulp and thermomechanical pulp. Groundwood pulp is defined as a mechanical wood pulp produced by pressing a barked log against a pulpstone and reducing the wood to a mass of relatively short fibers.
  • Thermomechanical pulp is defined as a high-yield pulp produced by a thermomechanical process in which wood particles are softened by pre-heating under pressure prior to a pressurized primary refining stage. This type of pulp replaces or reduces the chemical pulp component in newsprint or groundwood papers. See The Dictionary Of Paper, Fourth Ed., American Paper Institute, Inc., New York, N.Y. 1980, pages 205 and 416.
  • the paper composition of the invention may be of any type, including paper typically used in dry and wet electrophotographic copying and printing methods, paperboard, or poster board, and packaging paper upon which images may be formed by various image-forming techniques.
  • imaging methods including electrophotographic imaging methods, including dry and wet methods, and including both direct and indirect methods (offset) of image transfer, which utilize, as the receiver for the images formed, paper comprising at least one anionic polymeric material and at least one binder material
  • a method for manufacturing paper of the invention which comprises adding the anionic polymeric material and the binder material, individually or in combination, at any point during the paper manufacturing method or at any point up to the formation of an image on the paper.
  • the anionic polymeric materials utilized according to the invention contain repeat functional units capable of forming anionic salts such as, for example, various polymeric carboxylic acids, sulfonic acids and phosphonic acids, which on reacting with bases can form the corresponding salts.
  • the anionic polymeric materials can be either homopolymers or copolymers.
  • the copolymers may be of any type including graft and block copolymers.
  • binder materials may be utilized according to the invention including for example, starches such as non-ionic starches, latexes, proteins, alginates, vegetable gums and cellulose derivatives such as, for example, carboxymethylcellulose, hydroxymethylcellulose and the like.
  • the anionic polymeric and binder materials can be applied to one or both sides of the paper and can be applied either in the form of solutions, emulsions or dispersions of the polymers or copolymers or as combinations thereof.
  • solutions emulsions or dispersions of the polymers or copolymers or as combinations thereof.
  • any such form is included.
  • the anionic polymeric materials and the binder materials may be applied in combination or separately.
  • Typical suitable anionic polymeric materials which are useful in accordance with the invention include, for example, homopolymers of acrylic acid, methacrylic acid, maleic acid, phosphonic acid, sulfonic acid and copolymers thereof with monomers such as ethylene, styrene, acrylamide, and acrylonitrile, including anionic polyacrylamide, that is, polyacrylamide containing carboxylic acid functionality from either acrylic acid or methacrylic acid. Further, copolymers of maleic anhydride with ethylene or styrene can also be used.
  • Salts of the homopolymeric and copolymeric anionic materials may also be used including monovalent and polyvalent salts.
  • Typical suitable monovalent salts include ammonium salts and salts of alkali metals such as sodium salts.
  • Typical suitable polyvalent salts include salts of metals such as zinc and aluminum If the anionic polymeric material is to be added during the papermaking process, then selection of the metal cation should be made to avoid undesirable interactions with other paper making materials. Further, the anionic polymeric materials may be at least partially esterified, that is, some or all of the repeating functional units can be ester groups.
  • the effectiveness of the paper in strongly adhering the pigmented polymer particles to the paper surface is a function of a number of factors including the plasticity, or mobility, of the anionic polymeric material, that is, its ability to rapidly come in contact with the pigmented polymeric toner particles at the receiver temperature during image transfer or fusing.
  • the plasticity, or mobility, of the anionic polymeric material is a function of the softening temperature of the material. This property of the anionic polymeric materials will be discussed in relation to their Vicat softening temperature. (See ASTM Test D 1525-00 Standard Test Method For Vicat Softening Temperature of Plastics).
  • the Vicat softening temperature of the anionic polymeric material should be less than the receiver surface temperature during image transfer or fusing step. Further, the shorter the dwell time of the image transfer or fusing step, it is preferred that the Vicat softening temperature should be lower than the receiver surface temperature by a greater extent.
  • the anionic polymeric material should have a Vicat softening temperature of from about 10°C to about 100°C below the receiver surface temperature for dwell times in the range of 1500 to 250 milliseconds.
  • the receiver surface temperature when in contact with an intermediate transfer surface at a temperature in the vicinity of 125°C (low end of ITS surface temperature range) for dwell times of 1000 milliseconds, may be in the vicinity of about 90 C.
  • Vicat softening temperatures equal to, or less than about 90°C are preferred.
  • the receiver surface temperature during an image fusing step which can be practiced in dry or wet electrophotographic methods, and which is generally present in dry electrophotographic methods, can be higher. Fusing temperatures deployed typically range from about 100°C to about 250°C. In these embodiments of the image- forming methods of the invention, the Vicat softening temperature of the anionic polymeric material could be up to about 180°C.
  • the Vicat softening temperature of the anionic polymeric materials is dependent upon a number of factors. Such factors include the type of anionic polymeric material, i.e., whether a homopolymer or a copolymer, and the particular chemical type of the repeat functional units. For example, homopolymers of polyacrylic acids or polymethacrylic acids typically have lower Vicat softening temperatures than styrenesulfonic acids. Polymaleic acids, being dicarboxyliic acids, typically have a much higher softening point than either polyacrylic acid or polymethacrylic acid. The copolymer type and ratio also typically have a significant effect on Vicat softening temperatures.
  • Copolymers with ethylene or styrene typically have higher Vicat softening temperatures than the comparable anionic homopolymers.
  • the salts of these acids typically have higher Vicat softening temperatures compared to the acid form.
  • Image adhesion is also a strong function of the retention of the anionic polymer at or near the paper surface, which is dependent, in part, on the viscosity of the anionic polymer mixture and the method by which it is applied to the paper. In general, the higher the viscosity, with the upper limit being dependent on the application method selected, the lower will be the penetration of the anionic polymer into the paper, and the higher the concentration of the anionic polymer at or near the paper surface. Other factors which influence the viscosity of the mixture and hence the retention of the anionic polymer material at or near the paper surface include the molecular weight of the polymer, the degree of salt formation, the type of counter ion, and the pH of the mixture.
  • the anionic polymer material should be compatible with the pigmented polymer materials so as to ensure rapid bonding.
  • the anionic polymeric material should also be compatible with the pigmented polymer carrier fluid, so as to ensure absorption of the carrier fluid into the paper for both good cohesive and adhesive strength of the image.
  • the paper of the invention provides very good surface adhesion to pigmented polymer particles thus providing complete or at least substantially complete transfer of pigmented polymer particles used to form images in various electrophotographic imaging methods. Substantial transfer of the pigmented polymer particles to the paper surface significantly reduces or essentially eliminates any "ghost" images that can resuhvfrom any image residue remaining on the transfer surface.
  • the paper also rapidly absorbs liquids, typically used as the vehicle for liquid developers, such as, for example, insulating non-polar fluids such as aliphatic hydrocarbons used in certain electrophotographic imaging methods, to provide good cohesive strength of the receiver image.
  • the paper of the invention also has a hard surface with strongly adhered filler materials and paper fibers which is particularly advantageous in a preferred digital offset printing method of the invention for the conditions of the image transfer from the intermediate transfer surface to the paper as will be described in detail below herein.
  • the hard surface of the printing paper significantly reduces or substantially eliminates any intermediate transfer surface memory, or ghosting, which can result in undesired "ghost” or spurious images on the receiver from material transferred to the transfer surface in non image areas.
  • Fig. 1 is a diagram showing the paper path in one particular commercial printing machine, the HP/Indigo 1000 TurboStream digital offset printing machine.
  • the paper composition of the invention may be of any type including paperboard, or poster board, packaging paper and papers typically used in copying and printing methods and comprises at least one anionic polymeric material and at least one binder material and does not include more than about 20% by weight mechanical fiber and preferably not more than 10% by weight.
  • the paper includes from about 0.1 to about 18.0 lbs/3300 ft 2 of finished paper of at least one anionic polymeric material and from about 0.25 to about 10.0 lbs/3300ft 2 of at least one binder material and particularly preferably from about 0.2 to about 5.0 lbs/3300 ft 2 of finished paper of at least one anionic polymeric material and from about 1.0 to about 5.0 lbs/3300 ft 2 of finished paper of at least one binder material.
  • the paper may have any basis weight.
  • the basis weight suitable for paper used as the receiver in electrophotographic copying and printing is in the range of from about 20 to about 400 pounds based on 500 sheets of 25" by 38".
  • the paper composition may have any desired gurly stiffness, measured according to standard TAPPI specification T - 543 (Bending Resistance of Paper). In a preferred embodiment the paper has gurly stiffness in the machine direction of about 25 to about 6000 grams.
  • the anionic polymeric materials include repeating units, which are capable of forming anionic salts.
  • the anionic polymer- may be a homopolymer or a copolymer.
  • the homopolymer or copolymer can be either in the acid form, or partially, or wholly, in the salt form.
  • the Vicat softening temperature of an anionic polymer is affected by the degree of salt formation, the type of counter ion present, the valence of the counter ion, the molecular weight, copolymer type, copolymer ratio, pH of the polymer mixture from which the material is applied to the paper and the degree of esterification of the repeating functional units of the polymer.
  • the Vicat softening temperature is from about 10°C to about 100°C lower than the receiver surface temperature for dwell times in the range of 1500 to 250 milliseconds. It is also preferred to apply the anionic polymeric material to the paper from a polymer mixture, which has a viscosity sufficiently high to ensure maximum retention of the anionic polymer at or near the surface of the paper.
  • a specific test apparatus is a transfer press such as, for example, an AW-3000 Transfer Press made by Airwave Inc., Cincinnati, Ohio. Similar devices made by other manufacturers are commercially available and may be used for this purpose..
  • the press consists of a heated platen with a lever that can serve as the base for the ITS material. Once the ITS material is affixed to the platen, it can be used to apply pigmented polymer to the paper surface under heat and pressure.
  • the temperature of the platen is regulated to approximately simulate the receiver surface temperatures typically encountered in the HP/Indigo digital offset printing machines mentioned above.
  • the HP/Indigo digital printing machines typically have ITS surface temperatures of from about 125°C to about 180°C, resulting in receiver surface temperatures of about 90°C for the lower end of the ITS range.
  • an identical ITS material that is, HP/Indigo product designation MPS 2177-42 was selected.
  • the surface temperature of the ITS in the test apparatus was set at 105°C for a majority of the testing so as to achieve a paper surface temperature in the vicinity of 90 C for 1000 millisecond dwell time. As stated above, this temperature simulates the lower end of the temperature range of the intermediate transfer surface in the HP/Indigo machines. The lower end of the range was selected so as to increase the sensitivity.
  • the anionic polymer should be compatible with both the pigmented polymer and the carrier fluid in which it is dispersed. Since the composition of the specific pigmented polymer toner particles used in any commercial electrophotographic printing or copying machine is typically not in the public domain, it is preferable to use the pigmented polymer particles actually used in the machine of interest. Thus, the black pigmented polymer available from HP/Indigo having the product designation MPS 2131-42 was used. The same test can be repeated for other color pigmented polymers. Generally, for this practice of liquid electrophotography, it has been found that when the anionic polymer is a good bonding agent for the chosen black pigmented polymer, it will also satisfactorily bond to the pigmented polymers of other colors.
  • the black pigment was diluted with mineral oil, specifically that available from HP/Indigo with a product designation MPS 2017-43, the pigmented polymer dispersant, and applied to the ITS, which was affixed to the platen of the transfer press.
  • mineral oil specifically that available from HP/Indigo with a product designation MPS 2017-43, the pigmented polymer dispersant, and applied to the ITS, which was affixed to the platen of the transfer press.
  • MPS 2017-43 the pigmented polymer dispersant
  • the paper samples with the transferred black-pigmented polymer were then tested for adhesion efficacy via either cellophane tape, that is, Highland ® Clear 6200, or Scotch Drafting Tape ® Brand 230, available commercially from 3M Corporation.
  • the tape was applied uniformly to the printed surface and a 1 Kg weight roller was applied to the paper surface twice to get good tape adhesion to the pigmented polymer on the paper surface. The tape was then pulled away from the printed surface.
  • test sample was scanned with an Expression 1600 scanner (Epson. Corp.), and the scanned sample analyzed for the percentage of the material removed by the tape.
  • test sensitivity is shown as a function of the type of tape used. It can be seen that the cellophane tape gives poorer results and is therefore more discriminating.
  • Table 3 shows the results obtained with commercially available digital offset printing papers. It can be seen that all of the papers that were tested, exhibited very poor adhesion.
  • Table 6 shows adhesion data as a function of molecular weight for polyacrylic acid and polystyrenesulfonic acid homopolymers.
  • the adhesion results obtained with the acidic form of polyacrylic acid show that as the molecular weight, and hence the polymer mixture viscosity, is increased from 5,000 to 50,000, the adhesion results improve from about 32% to about 7%, that is, only about 7% of the image-forming particles were removed from the paper which had the highest molecular weight anionic polymer. This was so even though the lowest molecular weight polymer was present at a significantly higher amount of 1.481bs/3300 ft 2 compared to 0.93 lb/ft 2 for the higher molecular weight polymer.
  • the adhesion data are presented as a function of the salt or acid form of the anionic polymer at dwell times of 1000 and 250 milliseconds
  • the Na salt form of the polymer which increases polymer mixture viscosity, at both dwell times exhibited significantly better adhesion performance as seen by the approximately 20% and 18% losses, respectively.
  • anionic polymer of specific molecular weight, degree of neutralization, anionic polymer cation, such as Li + , Na + , K + , N " , valency of the cation and polymer mixture pH can be selected to create the requisite anionic polymer mixture viscosity for maximizing retention at or near the surface, and achieve good adhesion performance, nevertheless the Vicat softening temperature of the anionic polymeric material is also a very important factor in the adhesion performance of the paper of the invention.
  • the Vicat softening temperature be below the paper surface temperature during the transfer or fusing step.
  • the paper surface temperature during transfer of the image from the ITS is estimated to be about 90°C.
  • the Vicat softening temperature of the 400,000 molecular weight polystyrene sulfonate, at about 80°C (Table 6) is higher than that of the polyethyleneacrylic acid, at about 40°C (Table 4), it is nevertheless still below the estimated paper surface temperature of 90°C and its adhesion performance is comparable to that of polyethyleneacrylic acid at approximately similar coverage (See Table 4).
  • the data shown in Table 6 and Table 7 indicate that, in accordance with the preferred embodiment of the invention where the Vicat softening temperature is about 10°C or more below the paper surface temperature during the transfer or fusing steps, the viscosity of the polymer mixture will have a significant effect on adhesion performance, and desirable results can be achieved by selecting a sufficiently high viscosity mixture consistent with the specific application technique selected.
  • the pigmented polymer also contains an adequate percentage of polymeric anionic material
  • hydrogen, or hydrophilic, bonding mechanisms can prevail to not only bind the anionic material to components in the paper but also to the pigmented polymer particles, which form the image transferred to the paper, and be effective in providing good adhesion.
  • the pigmented polymer particles include copolymers, which may be likely, and the copolymer includes a hydrophobic moiety such as ethylene or styrene, employing a copolymer as the anionic polymer may be advantageous.
  • anionic polymeric materials for incorporation in the paper of the invention to be used as the receiver for the liquid electrophotographic methods carried out in the HP/Indigo digital offset printing machines.
  • the preferred anionic polymeric materials for incorporation in paper for use with these printing machines are: polyacrylic acid having a molecular weight of about 50,000; polymethacrylic acid having a molecular weight of about 15,000; polystyrenesulfonate (Na Salt) having a molecular weight of about 400,000; and polyethyleneacrylic acid at either the 10% or the 20% acrylic acid.
  • the data show that some of the lower molecular weight anionic polymers such as polyacrylic acid having a molecular weight of about 10,000 or polystyrenesulfonate (Na Salt) having a molecular weight of about 70,000 could be suitable depending upon the application technique, the composition of the polymeric mixture, that is, the presence of other viscosity building species such as starch or, by increasing anionic polymer solubility and hence viscosity via an increase in polymer mixture pH. Further, the data show that other anionic polymers such as polymaleic acid could be suitable at higher transfer or fusing temperatures.
  • anionic polymers such as polyacrylic acid having a molecular weight of about 10,000 or polystyrenesulfonate (Na Salt) having a molecular weight of about 70,000 could be suitable depending upon the application technique, the composition of the polymeric mixture, that is, the presence of other viscosity building species such as starch or, by increasing anionic polymer solubility and hence viscosity via an increase in polymer
  • anionic polymer Vicat softening temperature which is lower than the paper surface temperature by a larger amount, that is, which is more towards the higher end of the preferred temperature difference range of from about 10°C to about 100°C.
  • the particularly preferred anionic polymeric materials for incorporation in the paper receiver for these applications are the polyacrylic acid having a molecular weight of about 50000, polyethyleneacrylic acid at either the 10% acrylic acid or the 20% acrylic acid levels and the polymethacrylic acid, (salt form).
  • the anionic polymeric material should bond with both the paper materials as well as the pigmented polymer particles so that they are retained on the paper surface.
  • the adhesion of the anionic polymer to the paper is primarily through hydrogen bonding and, as discussed earlier, bonding to the pigmented polymer particles can also be primarily, or partially, through hydrogen bonding.
  • the activity of the anionic polymer to adhere to the paper and in some cases to the pigmented polymer particles is directly related to the degree of the anionic polymer in the acid form.
  • the pH of the anionic polymer mixture from which the polymer is applied to the paper can be used to regulate the amount of polymer in the active, or acid, form and that in the inactive, or dissociated, form. Generally, the higher the pH, the greater is the inactive form. This effect can be seen from the data in Table 12.
  • any reference to the active form of the anionic polymer implies the acidic form of the polymer.
  • the paper receiver material should also have a high surface strength so as to prevent unprinted area ghosting, or spurious images appearing on the receiver surface.
  • a primary-requirement of the binder material then is to strongly bind typical paper additives such as calcium carbonate, clay, titanium dioxide and short, medium and long fibers in order to provide a hard paper surface, which is substantially free from loose particles and fibers.
  • the paper surface should preferably remain hard at the temperatures and pressures encountered during image transfer so as to prevent unprinted area ghosting, or spurious images appearing on the paper surface.
  • the binder material should have sufficient binding strength to the typical paper additives so as to minimize or substantially eliminate abrasion and transfer of such paper additives and fibers during image transfer.
  • the binder material should be substantially unaffected with respect to its binding strength with respect to paper fibers, fillers, etc. at the temperature of the paper during transfer.
  • the binder material also should be compatible with the carrier fluid or dispersant for the pigmented polymer particles.
  • the carrier fluid containing the pigmented polymer particles Upon application of the carrier fluid containing the pigmented polymer particles, the fluid should wet the paper and drain from the surface.
  • the binder materials may be anionic, cationic or neutral.
  • suitable binder materials which are useful in accordance with the invention are starches, such as non-ionic starches, latexes, proteins, alginates, vegetable gums, and cellulose derivatives such as, for example, carboxymethylcellulose, hydroxyethylcellulose and the like.
  • the binder materials may be present in the paper individually or in combination. As stated earlier, for a preferred embodiment, the binder material is present in the paper in an amount of from about 0.25 to about 10.01bs/3300 ft 2 , and particularly preferably from aboutl.O lbs to about 5.0 lbs/3300 ft 2 of finished paper.
  • the starches and other binder materials, and paper fibers have cationic sites, which can preferentially bind to the anionic polymer so as to markedly reduce the amount of anionic polymer available to bind the image-forming pigments.
  • the anionic polymer material may interact with other components such as cationic groups in starches, as is the case with Ko-Film 280 starch.
  • Table 13 illustrate this phenomenon. It should be noted that the higher the percentage of the inactive form of the anionic polymer the lower the interaction with anionically reactive materials such as Ko-Film 280 starch.
  • the anionic polymer material has a high activity
  • the functional anionic units of the anionic polymer can get partially or wholly tied up with the other paper materials including binder, thereby reducing the efficacy of the anionic polymer material to provide the desired adhesion results.
  • the activity of the anionic polymer can be controlled with pH, that is, the higher the pH the more inactive the anionic polymer.
  • a particularly preferred anionic polymer for use in conjunction with Ko-Film 280 starch binder is the salt of polyethyleneacrylic acid with a fugitive ammonium counter ion, commercially available from Michelman Corporation with product designation MP 4990R.
  • ammonium salt form of the anionic polymer depending upon the degree of conversion, which can be determined by the pH of the anionic polymer mixture, can be significantly inactivated at pH 7 and above. It was also shown earlier that the pH of the polymeric mixture could be adjusted upward to achieve a lower degree of activation by the addition of NH 4 OH.
  • the key advantage obtained by reducing the activity of the anionic polymer mixture is that it can minimize the percentage of the anionic polymer interacting with components in the paper as it is being applied to the paper. This in turn will allow more of the anionic polymer to be available to bind the toner particles to the paper surface.
  • Two or more anionic polymeric materials may be used in combination, as can two or more binder materials.
  • the selection criteria for any combination of anionic polymeric material(s) and binder material(s) include the selection of materials which exhibit very good properties for one of the requirements of the respective materials and which also can provide at least some benefit with respect to another requirement. For, example, experiments have shown that when anionic polyacrylamide ? which has carboxylic acid functionality, commercially available from Hercules Corp.
  • the strongly anionic polyacrylamide preferentially binds to the cationic sites of a binder material such as Ko-Film 280 starch thereby preventing such cationic sites from binding to the primary anionic polymer and thereby increasing its efficacy while also providing the additional benefit of substantially reducing ghosting by cross-linking to the binder material.
  • a binder material such as Ko-Film 280 starch
  • anionic polyacrylamide can provide the multiple functions of binding to the cationic sites of a binder material, cross-linking the binder material and binding to the image-forming material.
  • the respective amounts of the anionic polymeric and the binder materials, which are utilized in any specific paper composition are determined in part by the number of functional groups in the molecule in relation to the overall size of the molecule.
  • the amounts of the anionic polymeric material and binder material in the paper composition are also a function of the surface finish of the paper.
  • the optimum amounts of anionic polymer(s) and binder material(s) in any specific paper designed to be used with any specific printing or copying machine can be determined by routine scoping experiments. As discussed previously, for good image quality there must be maximum toner particle transfer to the paper receiver material and maximum toner particle retention by the paper surface. The smoothness of the paper surface has a significant impact on the adhesion of the toner particles to the paper surface.
  • a rougher surface typically has better adhesion to the toner particles.
  • a rougher surface typically is also more susceptible to "ghosting.
  • the Sheffield method described in TAPPI Test T-538, OM-96, which is listed in TAPPI Test Methods (1996-1997), is a commonly accepted technique for measuring the surface smoothness of paper.
  • the paper smoothness is inversely proportional to the Sheffield number, i.e., the higher the Sheffield numbers the rougher the paper surface.
  • the Sheffield smoothness of the paper of the invention is from about 20 to about 400.
  • a prefe ⁇ ed printing paper of the invention comprises from about 0.20 to about 5.0 lbs. of an ammonium salt of polyethyleneacrylic acid, (Michelman product designation MP 49990R), about 0.10 to about 1.0 lb of anionic polyacrylamide, (Hercules product designation Ml 343) and about from about 1.0 to about 5.0 lbs of Ko-Film 280 starch, each based on 3300 ft 2 of finished paper.
  • an ammonium salt of polyethyleneacrylic acid Michelman product designation MP 49990R
  • anionic polyacrylamide Hercules product designation Ml 343
  • the electrophotographic printing methods provided according to the invention include those where the pigmented polymer toner particles are applied to the latent electrostatic image in a dry or wet composition with direct or indirect (offset) image transfer to receiver, and wherein an image is formed on a paper receiver material that includes at least one anionic polymeric binder material and at least one binder material.
  • the paper used in these printing methods does not have more than about 20% by weight of mechanical fiber and particularly preferably not more than about 10% by weight.
  • the paper used in these printing methods includes from about 0.1 to about 18.0 lbs/3300 ft 2 of finished paper of at least one anionic polymeric material and from about 0.25 to about 10.0 lbs/3300 ft of finished paper of at least one binder material and particularly preferably from about 0.2 to about 5.0/3300 ft 2 of anionic polymeric material and from about 1.0 to about 5.0 lbs/3300 ft 2 of at least one binder material.
  • Preferred electrophotographic methods are those digital offset printing methods wherein an electrostatic latent image formed on a photoconductive surface, typically by applying a substantially uniform electrostatic charge to the photoconductive surface and irradiating the charged surface with image-modulated laser beam(s), is rendered visible with a liquid toner composition, transferred to a heated intermediate transfer surface and transfe ⁇ ed from the latter to the final paper receiver material.
  • Digital offset printing methods are well known in the art and therefore extensive discussion of such methods is not required here.
  • An imaging method of this type is described in U.S. Patent 4,708,460. There is described in the '460 patent an apparatus wherein an image initially formed on a photoconductive surface by development with a liquid developer composition is transferred to an intermediate member positioned closely to the photoconductive member. The image is subsequently simultaneously transferred and fused to a copy sheet.
  • the printing paper of the invention is useful as the receiver sheet according to this method.
  • the paper of the invention may be used as the receiver for images formed by any suitable electrophotographic printing machine.
  • Fig. 1 shows one particular printing machine, the Indigo TurboStream 1000 digital offset printing machine, having a developer drum that attracts excess non-image ink while repelling image ink, a PIP drum, which carries the image, an ITM drum on which a transfer blank is located, and an impression drum that forms a printing nip with the ITM drum.
  • a PIP drum which carries the image
  • ITM drum on which a transfer blank is located an impression drum that forms a printing nip with the ITM drum.
  • Electrophotographic printing apparatus and methods can be used to form monochromatic and polychromatic images. Polychromatic, or multicolor, images can be formed by two general methods.
  • monochromatic color separation images e.g., magenta, yellow and cyan
  • Digital offset printing machines that carry out this method include the HP/Indigo 1000 and 3000 printing machines in which each individual color separation image is formed, transferred to the intermediate transfer surface and then to the paper receiver in registration.
  • each color separation image is formed, transfe ⁇ ed to an intermediate transfer surface in registration to form the multicolor image on the intermediate transfer surface and the multicolor image is then transferred to the paper receiver.
  • Digital offset printing machines which carry out this method, include the HP/Indigo 2000 and 4000 printing machines.
  • the printing paper of the invention is used as the receiver for multicolor images formed according to the latter method it is prefe ⁇ ed to utilize higher concentrations of the anionic polymeric materials and binders since the contact time of the paper with the heated intermediate transfer surface is less than in the former method where the receiver is brought into contact with the heated intermediate transfer surface more than one time, e.g., three or four times.
  • the paper of the invention may be produced by any conventional method that converts fiber slu ⁇ y into paper, and may be bleached. Further, the anionic polymeric material and the binder material may be applied to the paper of the invention, either individually or in combination, at any point during the paper manufacture or they can be applied to the paper at any point after the paper manufacture process and before the formation of an image on the paper.
  • the anionic polymeric material and the binder material may be mixed with the pulp fiber slu ⁇ y, which is made into a paper sheet.
  • the pulp fiber may be mainly composed of wood pulp and may contain additionally a fibrous material such as a synthetic pulp, synthetic fiber, glass fiber or the like.
  • the anionic polymer and binder materials may be applied to paper by means of an air knife coater, a roll coater, a Champlex coater, a gravure coater, etc to a plain paper sheet or a coated sheet. Further, a plain paper or coated sheet may be immersed in a mixture of the materials, which may be a solution, dispersion, emulsion or combinations thereof, excess fluid removed and the paper dried.
  • both the anionic polymer and the binder are applied to the paper at a size press addition station during manufacture of the paper. Simultaneous addition of these materials at a size press addition station confers significant cost advantages. However, there may be other situations where it is advantageous to apply the anionic polymer and/or the binder to the paper other than at the size press addition station, including addition at any point after the paper manufacturing process and before the formation of the image on the paper.
  • the rheology of the anionic polymer and binder mixture at the size press addition station should be optimized for the chosen application method. That is, the viscosity of the anionic polymer mixture, under the conditions of being applied to the paper, as discussed earlier, should be sufficiently high so as to maximize retention of the anionic polymer and binder materials at or very near the paper surface. For a specific anionic polymer and binder, maximizing the percent solids of the anionic polymer mixture can also favorably impact the viscosity. It should be further noted that raising the pH to keep the activity of the anionic polymer low would also increase the solubility of the salt, and hence increase the viscosity.
  • the maximum viscosity at the time of application to the paper has to be kept below the allowable maximum for the chosen application method. Additionally, it is also important to keep the temperature of the size solution low so that NH 3 is not prematurely driven off.
  • the temperature of the paper coming in to the size press station will have a large impact on the temperature of the size press polymer mixture.
  • the temperature of the paper at the size press addition station can be maintained at a desired low level by having cooling capability either for the size station polymer mixture, or the incoming paper, or both.
  • the pH of the polymeric mixture is from about 6 to 8
  • Example I This example illustrates the pigment adhesion results obtained from a digital offset printing method utilizing a printing paper according to the invention having a paper surface finish of Sheffield 140 and varying amounts of an anionic polymeric material, namely an ammonium salt of polyethyleneacrylic acid, (Michelman MP
  • the binder material was Ko- Film 280 starch present at about 2.1 lbs.
  • a black pigment was used to form the images on the paper
  • the adhesion values were obtained by applying a piece of Scotch Drafting Tape ® Brand 230 tape to the image areas of the copy sheet fifteen minutes after printing the paper, and then peeling the tape from the paper. The image-forming pigment, which adhered to the tape was then measured using a scanner. The percent adhesion values shown in Table I are the percentages of pigment remaining on the paper.
  • Example II This example illustrates the pigment adhesion results obtained from a digital offset printing method utilizing a printing paper according to the invention having a paper surface finish of Sheffield 140 and varying amounts of the same anionic polymeric material described in Example I, in combination with a second anionic polymeric material, namely, anionic polyacrylamide, (Hercules product designation
  • Ml 343 present in an amount of about 0.33 lb/3300 ft 2 of finished paper.
  • the binder material was Ko- Film 280 starch present at about 2.751bs/3300 ft 2 of finished paper.
  • a cyan pigment was used to form the images on the paper.
  • Example III This example illustrates the "ghosting" results obtained from a digital offset printing method utilizing a printing paper according to the invention having a paper surface finish of Sheffield 140.
  • the severity of the ghosting phenomenon can be judged by the number of cleaning sheets of paper required to remove from the ITS the items which cause the ghost images on the printed paper.
  • This example illustrates the results obtained with varying amounts of binder material.
  • the binder material was Ko-Film 280 starch.
  • the anionic polymeric material comprised a combination of the ammonium salt of polyethyleneacrylic acid described in Example I, present in an amount of from about 0.45 to about 0.501b/3300 ft 2 of finished paper and the anionic polyacrylamide described in Example II, present in the amount of about 0.33 lb/3300 ft 2 of finished paper.
  • 2000 Image cycles, of successive images were printed, that is, successive transfers of 2000 images from the intermediate transfer surface to the paper receiver material.
  • six cleaning sheets were printed.
  • the cleaning sheets were paper sheets according to the invention, which were processed in the digital offset printing machine identified above. The cleaning sheets did not have an image printed on them but rather had a yellow pigment uniformly distributed across their surfaces. The cleaning sheets were examined for the presence of the ghost image or image from the previous cycle. The number of cleaning sheets shown is that required to remove from the intermediate transfer surface the residual material retained thereon after three 2000 image cycles, described above, that is, a cumulative transfer of 6000 images from the intermediate transfer surface to the paper receiver material..
  • ACRYLIC 250 9.09 ACRYLIC ACID o 6200 CLEAR

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Abstract

L'invention concerne une composition de papier qui comprend un matériau polymère anionique et un matériau liant. Les compositions de papier selon l'invention sont particulièrement utiles en tant que matériaux récepteurs d'images formées par des procédés électrophotographiques faisant appel à des révélateurs liquides. L'invention concerne également des procédés de formation d'image qui font appel aux compositions de papier selon l'invention en tant que matériaux récepteurs ainsi que des procédés de fabrication du papier.
PCT/US2003/029358 2002-09-19 2003-09-17 Compositions de papier, procedes de formation d'images et procedes de fabrication de papier WO2004027145A2 (fr)

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US7828935B2 (en) 2003-04-07 2010-11-09 International Paper Company Papers for liquid electrophotographic printing and method for making same
US9981288B2 (en) 2008-09-26 2018-05-29 International Paper Company Process for manufacturing recording sheet

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USRE44070E1 (en) 2005-06-09 2013-03-12 United States Gypsum Company Composite light weight gypsum wallboard
US11306028B2 (en) 2005-06-09 2022-04-19 United States Gypsum Company Light weight gypsum board
US11338548B2 (en) 2005-06-09 2022-05-24 United States Gypsum Company Light weight gypsum board
US7731794B2 (en) 2005-06-09 2010-06-08 United States Gypsum Company High starch light weight gypsum wallboard
US9802866B2 (en) * 2005-06-09 2017-10-31 United States Gypsum Company Light weight gypsum board
JP6830670B2 (ja) 2015-12-18 2021-02-17 マイケルマン，インコーポレーテッド イオノマーベースの印刷可能な被覆

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