EP0656971B1 - Process for applying chemical papermaking additives from a thin film to tissue paper - Google Patents

Process for applying chemical papermaking additives from a thin film to tissue paper Download PDF

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Publication number
EP0656971B1
EP0656971B1 EP93920248A EP93920248A EP0656971B1 EP 0656971 B1 EP0656971 B1 EP 0656971B1 EP 93920248 A EP93920248 A EP 93920248A EP 93920248 A EP93920248 A EP 93920248A EP 0656971 B1 EP0656971 B1 EP 0656971B1
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EP
European Patent Office
Prior art keywords
web
additive
tissue
tissue paper
paper
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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.)
Expired - Lifetime
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EP93920248A
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German (de)
English (en)
French (fr)
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EP0656971A1 (en
Inventor
Robert Stanley Ampulski
Paul Dennis Trokhan
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Procter and Gamble Co
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Procter and Gamble Co
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Publication date
Priority claimed from US07/936,439 external-priority patent/US5246546A/en
Priority claimed from US07/936,161 external-priority patent/US5246545A/en
Application filed by Procter and Gamble Co filed Critical Procter and Gamble Co
Publication of EP0656971A1 publication Critical patent/EP0656971A1/en
Application granted granted Critical
Publication of EP0656971B1 publication Critical patent/EP0656971B1/en
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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
    • D21H19/00—Coated paper; Coating material
    • D21H19/10—Coatings without pigments
    • D21H19/14—Coatings without pigments applied in a form other than the aqueous solution defined in group D21H19/12
    • 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
    • D21H21/22—Agents rendering paper porous, absorbent or bulky
    • 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
    • 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
    • D21H19/10—Coatings without pigments
    • D21H19/14—Coatings without pigments applied in a form other than the aqueous solution defined in group D21H19/12
    • D21H19/24—Coatings without pigments applied in a form other than the aqueous solution defined in group D21H19/12 comprising macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • D21H19/32—Coatings without pigments applied in a form other than the aqueous solution defined in group D21H19/12 comprising macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds obtained by reactions forming a linkage containing silicon in the main chain of the macromolecule
    • 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
    • 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
    • D21H21/20—Wet strength 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
    • D21H23/00—Processes or apparatus for adding material to the pulp or to the paper
    • D21H23/02—Processes or apparatus for adding material to the pulp or to the paper characterised by the manner in which substances are added
    • D21H23/22—Addition to the formed paper
    • D21H23/52—Addition to the formed paper by contacting paper with a device carrying the material
    • D21H23/56—Rolls
    • 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
    • D21H25/00—After-treatment of paper not provided for in groups D21H17/00 - D21H23/00
    • D21H25/02—Chemical or biochemical treatment

Definitions

  • This invention relates to a process for applying low levels of chemical papermaking additives to the surface of tissue paper for enhancing the properties of the paper. e.g., strength, softness, absorbency, and/or aesthetics.
  • Consumer products such as toilet tissue, toweling and facial tissue made from cellulosic webs are a pervasive part of modern society. In general, these products need to possess certain key physical properties to be considered acceptable to consumers. While the exact mix of key properties and the absolute value of the individual properties will vary depending on the nature of the product, nonetheless, softness, wet and dry strength, absorbency, and pleasing aesthetic nature are universally desirable properties. Softness is that aspect of the fibrous web that elicits a pleasing tactile response and insures that the product is not harsh or abrasive when it contacts human skin or other fragile surfaces. Strength is the ability of the structure to retain its physical integrity during use. Absorbency is the property of the fibrous structure which allows it to acquire and retain contacted fluids in an acceptable time. Aesthetic nature refers to the psycho-visual response that occurs when the consumer views the product either alone or in the context of the product's surroundings.
  • tissue products The most common method for the manufacture of tissue products is the wet laid papermaking process.
  • individual fibers are first suspended in a dilute slurry with water.
  • This slurry is then laid on a foraminous screen to remove a large portion of the water and to form a thin, relatively uniform-weight embryonic web.
  • This embryonic web is then molded and/or dried in a variety of ways to form the final tissue web.
  • the molded and/or dried web is usually glued to a drying drum and subsequently creped from the surface of the dryer to impart desirable properties.
  • the dense areas can be either discrete or continuous. These dense areas result from localized compaction of the web during papermaking by raised areas of an imprinting carrier fabric or belt.
  • EP-A-0 253 596 issued March 11, 1987 to B.G. Stokes discloses a flexible, durable, stretchable paper web which is particularly suited for applications such as label stock for flexible containers.
  • Tissue paper has also been treated with cationic surfactants, as well as noncationic surfactants to enhance softness. See, for example, U. S.-A- 4,959,125 which issued September 25, 1990, to Spendel; and U. S.-A- 4,940,513 which issued July 10, 1990, to Spendel, that disclose processes for enhancing the softness of tissue paper by treating it with noncationic, preferably nonionic, surfactants.
  • tissue paper in particular, high-bulk pattern densified tissue papers
  • various agents such as vegetable, animal or synthetic oils, and especially polysiloxane materials typically referred to as silicone oils.
  • silicone oils typically referred to as silicone oils.
  • U. S.-A-5,059,282 which issued October 22, 1991, to Ampulski et al.
  • the Ampulski patent discloses a process for adding a polysiloxane compound to a wet tissue web (preferably at a fiber consistency of between about 20% and about 35%).
  • These polysiloxane compounds impart a silky, soft feeling to the tissue paper.
  • the majority of the existing tissue manufacturing processes glue the web to the surface of a drying drum and subsequently crepe the web from the dryer surface. Creping generally produces a web with improved softness and importantly improves the extensibility of the web. For proper creping to occur, it is imperative that the web be securely attached to the surface of the drum. Many of the chemicals added to the wet end of the machine, to ostensibly improve key properties, end up interfering with the adhesion of the web to the drying drum and hence adversely affect the creping process and the quality of the tissue produced.
  • the creping operation runs optimally when the adhesive used to adhere the web to the creping surface is free of interference from non-creping related chemicals such as those added at the wet end of the overall tissue making process
  • Additives introduced in the wet end of the process must be retained by the cellulose fibers if the chemicals are to be functional. This is generally done by using chemicals that possess an ionic charge; most preferably a positive ionic charge which is attracted to the inherent negative ionic charge of cellulose. Many additives which could improve the properties of the web are not charged. Introduction of such chemicals into the dilute fiber slurry at the wet end of the process results in poor retention and exacerbates the interference problems described above.
  • an object of this invention to provide an improved process to incorporate chemical papermaking additives into the tissue web that enhance softness, strength, absorbency, and aesthetics or combinations of these properties.
  • diluted chemical papermaking additives diluted to insure controlled application of small quantities of additive
  • the present invention encompasses a process for making soft, strong, absorbent, and aesthetically pleasing tissue paper.
  • This process includes the steps of providing a dry tissue paper web and then applying a sufficient amount of a chemical papermaking additive to the dry web.
  • the softener application process includes the steps of diluting a chemical papermaking additive compound with a suitable solvent to form a diluted papermaking additive solution; applying the diluted papermaking additive solution to a heated transfer surface by, for example, spraying; and evaporating a portion of the solvent from the heated transfer surface to form a film containing the papermaking additive.
  • solvent is meant a fluid that completely dissolves a chemical papermaking additive, or a fluid that is used to emulsify a chemical papermaking additive, or a fluid that is used to suspend a chemical papermaking additive.
  • the solvent may also be a carrier or delivery vehicle that contains the chemical additive or aids in the delivery of chemical papermaking additive. All references are meant to be interchangeable and not limiting.
  • the solution is the fluid containing the chemical papermaking additive. By solution is meant a true solution, an emulsion, and/or suspension.
  • the solvent is water then, preferably, the hot web is dried to a moisture level below its equilibrium moisture content (at standard conditions) before being contacted with the papermaking additive film, however this process is also applicable to tissue paper at its equilibrium moisture as well, if most of the water is evaporated from the transfer surface.
  • the amount of papermaking additive retained by the tissue paper is preferably, between 0.01% to about 1.0%, based on the dry fiber weight of the tissue paper.
  • the resulting tissue paper preferably has a basis weight of from about 10 to about 80 g/m 2 and a fiber density of less than about 0.6 g/cc.
  • the papermaking additive is applied to the web , after the web has been dried and creped.
  • the papermaking additive By adding the papermaking additive to the web after drying and creping, there is no interference with the glue on the Yankee dryer, which can cause skip crepe and/or loss in sheet control.
  • papermaking additives applied by means of the process described in this invention do not interfere with the papermaking water system, since they are not added in the wet end of the paper machine.
  • a further advantage of this process is that the additives do not need to be substantive to the paper. That is, they do not need to contain a cationic charge for bonding with the anionic charge on the cellulosic papermaking fibers.
  • the papermaking additive is applied to a hot, creped web after it leaves the doctor blade and before it is wound on the parent roll.
  • tissue softening, strength, absorbency, and/or aesthetic benefits can be achieved by low levels of a chemical papermaking additive when the papermaking additive is diluted with a solvent, applied to a heated transfer surface which evaporates the carrier solvent and then transfers the papermaking additive to a hot web before the converting operation.
  • An advantage of the process disclosed herein is that the amount of residual solvent transferred to the paper web is sufficiently low that it does not degrade other product properties.
  • the quantity of papermaking additive used is low enough to be economical.
  • tissue paper treated with low levels of chemical softeners, such as polysiloxanes retain a high level of wettability, an important feature for a tissue product.
  • Preferred softener additives for use in the process of the present invention include an amino-functional polydimethylpolysiloxane wherein less than about 10 mole percent of the side chains on the polymer contain an amino-functional group.
  • effective substitution may be made with carboxyl, hydroxyl, ether, polyether, aldehyde, ketone, amide, ester, and thiol groups.
  • the family of groups comprising amino, carboxyl, and hydroxyl groups are more preferred than the others; and amino-functional groups are most preferred.
  • Exemplary commercially available polysiloxanes include DOW 8075 and DOW 200 which are available from Dow Corning; and Silwet L720 and Ucarsil EPS which are available from Union Carbide.
  • Nonionic surfactants selected from sorbitan esters, ethoxylated sorbitan esters, propoxylated sorbitan esters, mixed ethoxylated/propoxylated sorbitan esters, and mixtures thereof.
  • the process for preparing tissue paper treated with a chemical softener additive such as the polysiloxane and/or nonionic surfactants discussed above may further comprise the step of adding an effective amount of an absorbency additive to enhance the tactile perceivable surface smoothness of the tissue paper and/or to at least partially offset any reduction of wettability the tissue paper which would otherwise result from the incorporation of the polysiloxane or other chemical softener.
  • an absorbency additive to enhance the tactile perceivable surface smoothness of the tissue paper and/or to at least partially offset any reduction of wettability the tissue paper which would otherwise result from the incorporation of the polysiloxane or other chemical softener.
  • a suitable absorbency additive such as a surfactant.
  • the effective amount of surfactant is such that, preferably, from about 0.01 to about 2 percent on a dry fiber weight of the tissue paper; and, more preferably, from about 0.05 to about 1.0 percent is retained by the tissue paper.
  • the surfactant is noncationic; and is substantially nonmigratory in situ after the tissue paper has been manufactured in order to substantially obviate post-manufacturing changes in the tissue paper's properties which might otherwise result from the inclusion of surfactant. This may be achieved, for instance, through the use of surfactants having melt temperatures greater than the temperatures commonly encountered during storage, shipping, merchandising, and use of tissue paper product embodiments of the invention: for example, melt temperatures of about 50°C or higher.
  • the process for preparing tissue paper in accordance with the present invention may further comprise the step of adding an effective amount of a strength additive such as a starch-based material to at least partially offset any reduction of tensile strength and/or increase in linting propensity which would otherwise result from the incorporation of the chemical softener additive and, if present, absorbency additive.
  • the effective amount of strength additive is such that, preferably, from about 0.01 to about 2 percent on a dry fiber weight basis of the tissue paper, is retained by the tissue paper.
  • Figure 1 is a schematic representation illustrating a preferred embodiment of the process of the present invention of adding chemical papermaking additive compounds to a tissue web.
  • the present invention provides tissue paper having enhanced tactile perceivable softness through the addition of a chemical softener additive, improved strength through the addition of a strength additive, enhanced absorbency through the addition of an absorbency additive, and/ or enhanced aesthetics by incorporating an aesthetic additive such as inks, dyes, and perfumes to a dry tissue web.
  • tissue paper having enhanced tactile perceivable softness through the addition of a chemical softener additive, improved strength through the addition of a strength additive, enhanced absorbency through the addition of an absorbency additive, and/ or enhanced aesthetics by incorporating an aesthetic additive such as inks, dyes, and perfumes to a dry tissue web.
  • an aesthetic additive such as inks, dyes, and perfumes
  • tissue softening effect when applied to dry tissue webs in accordance with the present invention.
  • levels of softener additives used to soften the tissue paper are low enough that the tissue paper retains high wettability.
  • the tissue web is preferably overdried and at an elevated temperature when the papermaking additive is applied and because carrier water is depleted on the hot transfer surface, further drying is not required.
  • hot tissue web refers to a tissue web which is at an elevated temperature that is higher than room temperature.
  • the elevated temperature of the web is at least 43°C, and more preferably at least 65°C.
  • the moisture content of a tissue web is related to the temperature of the web and the relative humidity of the environment in which the web is placed.
  • the term "overdried tissue web” refers to a tissue web that is dried to a moisture content below its equilibrium moisture content at standard test conditions of 23°C and 50% relative humidity.
  • the equilibrium moisture content of a tissue web placed in standard testing conditions of 23°C and 50% relative humidity is approximately 7%.
  • the tissue web in the present invention can be overdried by raising it to a elevated temperature through use of conventional drying means such as a Yankee dryer.
  • an overdried tissue web will have a moisture content of less than 7%, more preferably from about 0 to about 6%, and most preferably, a moisture content of from about 0 to about 3%, by weight.
  • Paper exposed to the normal environment typically has an equilibrium moisture content in the range of 5 to 8%.
  • the moisture content in the sheet is generally less than 3%.
  • the paper absorbs water from the atmosphere.
  • advantage is taken of the low moisture content in the paper as it leaves the doctor blade.
  • the present invention is applicable to tissue paper in general, including but not limited to conventionally felt-pressed tissue paper; pattern densified tissue paper such as exemplified by Sanford-Sisson and its progeny; and high-bulk, uncompacted tissue paper such as exemplified by Salvucci.
  • the tissue paper may be of a homogenous or multilayered construction; and tissue paper products made therefrom may be of a single-ply or multi-ply construction.
  • the tissue paper preferably has a basis weight of between 10 g/m 2 and about 80 g/m 2 , and density of about 0.60 g/cc or less.
  • basis weight will be below about 35 g/m 2 or less; and density will be about 0.30 g/cc or less.
  • density will be between 0.04 g/cc and about 0.20 g/cc.
  • Such paper is typically made by depositing papermaking furnish on a foraminous forming wire.
  • This forming wire is often referred to in the art as a Fourdrinier wire.
  • the web is dewatered by pressing the web and drying at elevated temperature.
  • the particular techniques and typical equipment for making webs according to the process just described are well known to those skilled in the art.
  • a low consistency pulp furnish is provided in a pressurized headbox.
  • the headbox has an opening for delivering a thin deposit of pulp furnish onto the Fourdrinier wire to form a wet web.
  • the web is then typically dewatered to a fiber consistency of between about 7% and about 45% (total web weight basis) by vacuum dewatering and further dried by pressing operations wherein the web is subjected to pressure developed by opposing mechanical members, for example, cylindrical rolls.
  • the dewatered web is then further pressed and dried by a stream drum apparatus known in the art as a Yankee dryer. Pressure can be developed at the Yankee dryer by mechanical means such as an opposing cylindrical drum pressing against the web. Multiple Yankee dryer drums may be employed, whereby additional pressing is optionally incurred between the drums.
  • the tissue paper structures which are formed are referred to hereinafter as conventional, pressed, tissue paper structures. Such sheets are considered to be compacted, since the web is subjected to substantial overall mechanical compressional forces while the fibers are moist and are then dried while in a compressed state.
  • Pattern densified tissue paper is characterized by having a relatively high-bulk field of relatively low fiber density and an array of densified zones of relatively high fiber density.
  • the high-bulk field is alternatively characterized as a field of pillow regions.
  • the densified zones are alternatively referred to as knuckle regions.
  • the densified zones may be discretely spaced within the high-bulk field or may be interconnected, either fully or partially, within the high-bulk field.
  • Preferred processes for making pattern densified tissue webs are disclosed in U.S. Patent No. 3,301,746, issued to Sanford and Sisson on January 31, 1967, U.S. Patent No. 3,974,025, issued to Peter G. Ayers on August 10, 1976, and U.S. Patent No. 4,191,609, issued to Paul D. Trokhan on March 4, 1980, and U.S. Patent 4,637,859, issued to Paul D. Trokhan on January 20, 1987.
  • pattern densified webs are preferably prepared by depositing a papermaking furnish on a foraminous forming wire such as a Fourdrinier wire to form a wet web and then juxtaposing the web against an array of supports. The web is pressed against the array of supports, thereby resulting in densified zones in the web at the locations geographically corresponding to the points of contact between the array of supports and the wet web. The remainder of the web not compressed during this operation is referred to as the high-bulk field.
  • This high-bulk field can be further dedensified by application of fluid pressure, such as with a vacuum type device or a blow-through dryer, or by mechanically pressing the web against the array of supports.
  • the web is dewatered, and optionally predried, in such a manner so as to substantially avoid compression of the high-bulk field. This is preferably accomplished by fluid pressure, such as with a vacuum type device or blow-through dryer, or alternately by mechanically pressing the web against an array of supports wherein the high-bulk field is not compressed.
  • the operations of dewatering, optional predrying and formation of the densified zones may be integrated or partially integrated to reduce the total number of processing steps performed.
  • the web is dried to completion, preferably still avoiding mechanical pressing.
  • from about 8% to about 65% of the tissue paper surface comprises densified knuckles having a relative density of at least 125% of the density of the high-bulk field.
  • the array of supports is preferably an imprinting carrier fabric having a patterned displacement of knuckles which operate as the array of supports which facilitate the formation of the densified zones upon application of pressure.
  • the pattern of knuckles constitutes the array of supports previously referred to.
  • Imprinting carrier fabrics are disclosed in U.S.-A- 3,301,746, Sanford and Sisson, issued January 31, 1967, U.S.-A- 3,821,068, Salvucci, Jr. et al., issued May 21, 1974, U.S.-A-3,974,025, Ayers, issued August 10, 1976, U.S.-A-3,573,164, Friedberg et al., issued March 30, 1971 U.S. -A-3,473,576, Amneus, issued October 21, 1969, U.S.-A-4,239,065, Trokhan, issued December 16, 1980, and U.S.-A-4,528,239, Trokhan, issued July 9, 1985.
  • the furnish is first formed. into a wet web on a foraminous forming carrier, such as a Fourdrinier wire.
  • the web is dewatered and transferred to an imprinting fabric.
  • the furnish may alternately be initially deposited on a foraminous supporting carrier which also operates as an imprinting fabric.
  • the wet web is dewatered and, preferably, thermally predried to a selected fiber consistency of between about 40% and about 80%.
  • Dewatering is preferably performed with suction boxes or other vacuum devices or with blow-through dryers.
  • the knuckle imprint of the imprinting fabric is impressed in the web as discussed above, prior to drying the web to completion.
  • One method for accomplishing this is through application of mechanical pressure.
  • nip roll which supports the imprinting fabric against the face of a drying drum, such as a Yankee dryer, wherein the web is disposed between the nip roll and drying drum.
  • the web is molded against the imprinting fabric prior to completion of drying by application of fluid pressure with a vacuum device such as a suction box, or with a blow-through dryer. Fluid pressure may be applied to induce impression of densified zones during initial dewatering, in a separate, subsequent process stage, or a combination thereof.
  • uncompacted, nonpattern-densified tissue paper structures are described in U.S.-A-3,812,000 issued to Joseph L. Salvucci, Jr. and Peter N. Yiannos on May 21, 1974, and U.S.-A-4,208,459, issued to Henry E. Becker, Albert L. McConnell, and Richard Schutte on June 17, 1980.
  • uncompacted, nonpattern-densified tissue paper structures are prepared by depositing a papermaking furnish on a foraminous forming wire such as a Fourdrinier wire to form a wet web, draining the web and removing additional water without mechanical compression until the web has a fiber consistency of at least 80%, and creping the web. Water is removed from the web by vacuum dewatering and thermal drying. The resulting structure is a soft but weak high-bulk sheet of relatively uncompacted fibers. Bonding material is preferably applied to portions of the web prior to creping.
  • Compacted non-pattern-densified tissue structures are commonly known in the art as conventional tissue structures.
  • compacted, non-pattern-densified tissue paper structures are prepared by depositing a papermaking furnish on a foraminous wire such as a Fourdrinier wire to form a wet web, draining the web and removing additional water with the aid of a uniform mechanical compaction (pressing) until the web has a consistency of 25-50%, transferring the web to a thermal dryer such as a Yankee and creping the web. Overall, water is removed from the web by vacuum, mechanical pressing and thermal means.
  • the resulting structure is strong and generally of singular density, but very low in bulk, absorbency and in softness.
  • the papermaking fibers utilized for the present invention will normally include fibers derived from wood pulp.
  • Other cellulosic fibrous pulp fibers such as cotton linters, bagasse, etc., can be utilized and are intended to be within the scope of this invention.
  • Synthetic fibers such as rayon, polyethylene and polypropylene fibers, may also be utilized in combination with natural cellulosic fibers.
  • pulpexTM available from Hercules, Inc. (Wilmington, Delaware).
  • Applicable wood pulps include chemical pulps, such as Kraft, sulfite, and sulfate pulps, as well as mechanical pulps including, for example, groundwood, thermomechanical pulp and chemically modified thermomechanical pulp. Chemical pulps, however, are preferred since they impart a superior tactile sense of softness to tissue sheets made therefrom. Pulps derived from both deciduous trees (hereinafter, also referred to as "hardwood”) and coniferous trees (hereinafter, also referred to as "softwood”) may be utilized. Also applicable to the present invention are fibers derived from recycled paper, which may contain any or all of the above categories as well as other non-fibrous materials such as fillers and adhesives used to facilitate the original papermaking.
  • the papermaking furnish used to make tissue paper structures may have other components or materials added thereto as may be or later become known in the art.
  • the types of additives desirable will be dependent upon the particular end use of the tissue sheet contemplated. For example, in products such as toilet paper, paper towels, facial tissues and other similar products, high wet strength is a desirable attribute. Thus, it is often desirable to add to the papermaking furnish chemical substances known in the art as "wet strength" resins.
  • Polyacrylamide resins have also been found to be of utility as wet strength resins. These resins are described in U.S.-A-3,556,932, issued on January 19, 1971, to Coscia, et al. and US-A-3,556,933, issued on January 19, 1971, to Williams et al.
  • One commercial source of polyacrylamide resins is American Cyanamid Co. of Stanford, Connecticut, which markets one such resin under the mark ParezTM 631 NC.
  • Still other water-soluble cationic resins finding utility in this invention are urea formaldehyde and melamine formaldehyde resins.
  • the more common functional groups of these polyfunctional resins are nitrogen containing groups such as amino groups and methylol groups attached to nitrogen.
  • Polyethylenimine type resins may also find utility in the present invention.
  • temporary wet strength resins such as Caldas (manufactured by Japan Carlit) and CoBond 1000 (manufactured by National Starch and Chemical Company) may be used in the present invention. It is to be understood that the addition of chemical compounds such as the wet strength and temporary wet strength resins discussed above to the pulp furnish is optional and is not necessary for the practice of the present development.
  • the chemical papermaking additives are applied after the tissue web has been dried and creped, and preferably is still at an elevated temperature. It has been found that addition of some chemical papermaking additives to the tissue web before the web is dried and creped can result in interference with the coating on the dryer (i.e., glue coating on Yankee dryer), and also cause skip crepe and a loss in sheet control. These problems are eliminated by the process of the present invention wherein the chemical papermaking additives are applied to the web after the web has been dried and creped.
  • the chemical papermaking additives are applied to the dried and creped tissue web before the web is wound onto the parent roll.
  • the chemical papermaking additives are applied to a hot, overdried tissue web after the web has been creped, but before the web passes through the calender rolls.
  • the chemical papermaking additives are preferably applied to the hot transfer surface from an aqueous solution, emulsion, or suspension.
  • the chemical papermaking additives can also be applied in a solution containing a suitable, nonaqueous solvent, in which the chemical papermaking additive dissolves or with which the chemical papermaking additive is miscible: for example, hexane.
  • the chemical papermaking additive may be supplied in neat form or, more preferably, emulsified with a suitable surfactant emulsifier. Emulsified chemical papermaking additives are preferable for ease of application since a neat chemical papermaking additive aqueous solution must be agitated to inhibit separation into water and chemical papermaking additive phases.
  • the chemical papermaking additive should be applied to the heated transfer surface in a macroscopically uniform fashion for subsequent transfer to the tissue paper web so that substantially the entire sheet benefits from the effect of the chemical papermaking additive.
  • the solvent preferably evaporates leaving a thin film containing the chemical papermaking additive.
  • thin film is meant any thin coating, haze or mist on the transfer surface.
  • This thin film can be microscopically continuous. discrete or patterned, but should be macroscopically uniform.
  • the chemical papermaking additive may be distributed in a uniform, random, discrete, patterned, continuous, or discontinuous fashion. Applying the chemical papermaking additive to the tissue paper web in continuous and patterned distributions are both within the scope of the invention and meet the above criteria.
  • the chemical papermaking additive can be added to either side of the tissue web singularly, or to both sides.
  • Methods of macroscopically uniformly applying the chemical papermaking additive to the hot transfer surface include spraying and gravure printing. Spraying has been found to be economical, and susceptible to accurate control over quantity and distribution of the chemical papermaking additive, so it is most preferred.
  • an aqueous mixture containing an emulsified chemical papermaking additive is applied from the transfer surface onto the dried, creped tissue web after the Yankee dryer and before the parent roll.
  • FIG 1 illustrates a preferred method of applying the chemical papermaking additive to the tissue web.
  • a wet tissue web 1 is on carrier fabric 14 past turning roll 2 and transferred to Yankee dryer 5 by the action of pressure roll 3 while carrier fabric 14 travels past turning roll 16.
  • the paper web is adhesively secured to the cylindrical surface of Yankee dryer 5 by adhesive applied by spray applicator 4. Drying is completed by steam-heated Yankee dryer 5 and by hot air which is heated and circulated through drying hood 6 by means not shown.
  • the web is then dry creped from the Yankee dryer 5 by doctor blade 7, after which it is designated creped paper sheet 15.
  • An aqueous mixture containing an emulsified chemical papermaking additive compound is sprayed onto an upper heated transfer surface designated as upper calender roll 10 and/or a lower heated transfer surface designated as lower calender roll 11, by spray applicators 8 and 9 depending on whether the chemical papermaking additive is to be applied to both sides of the tissue web or just to one side.
  • the paper sheet 15 then contacts heated transfer surfaces 10 and 11 after a portion of the solvent has been evaporated.
  • the treated web then travels over a circumferential portion of reel 12, and then is wound onto parent roll 13.
  • Equipment suitable for spraying chemical papermaking additive-containing liquids onto hot transfer surfaces include external mix, air atomizing nozzles, such as the 2 mm nozzle available "from V.I.B. Systems, Inc., Tucker, Georgia.
  • Equipment suitable for printing chemical papermaking additive-containing liquids onto hot transfer surfaces include rotogravure or flexographic printers.
  • the Yankee dryer raises the temperature of the tissue sheet and removes the moisture.
  • the steam pressure in the Yankee is on the order of 750 kPa (110 PSI). This pressure is sufficient to increase the temperature of the cylinder to about 173°C.
  • the temperature of the paper on the cylinder is raised as the water in the sheet is removed.
  • the temperature of the sheet as it leaves the doctor blade can be in excess of 120°C.
  • the sheet travels through space to the calender and the reel and loses some of this heat.
  • the temperature of the paper wound in the reel is measured to be on the order of 65°C.
  • the sheet of paper cools to room temperature. This can take anywhere from hours to days depending on the size of the paper roll. As the paper cools it also absorbs moisture from the atmosphere. As previously mentioned, the moisture content in the sheet is related to the sheet temperature and the relative humidity of the environment in which the paper is placed. For example the equilibrium moisture content of a sheet placed in standard testing conditions of 23°C and 50% RH is approximately 7%. Increasing the moisture content of the sheet above 7% can have a deleterious effect on the tensile strength of the paper. For example, a moisture increase to 9% can cause the tensile strength of the paper to decrease by as much as 15%.
  • One commonly used method for applying low levels of an active material is to first dilute the material with a solvent.
  • the spray systems can then be adjusted to deliver larger particle sizes at high flow rates.
  • the larger particles can penetrate the air boundary layer.
  • volatile organic solvents are not used in papermaking, since they can be fire or environmental hazards.
  • Water can be used as a solvent for water soluble papermaking additives.
  • Water can also be used as a solvent, or more appropriately as a diluent, for the non-water soluble papermaking additives, such as organic oils, polymers, and polysiloxanes, if the non-water soluble papermaking additive, such as a polysiloxane is first emulsified with a suitable surfactant system. While water does not pose the same process risks as an organic solvent, water can degrade the product, causing a loss in crepe and/or tensile strength. Further the water needs to be removed from the paper.
  • the non-water soluble papermaking additives such as organic oils, polymers, and polysiloxanes
  • a further limitation to this process is the limited dilution range and application range of the chemical papermaking additive emulsion imposed by the emulsion properties, (i.e., high concentrations tend to have high viscosities, whereas low concentrations increase the amount of water sprayed on the sheet).
  • the present invention solves the above described problems by first spraying a dilute water soluble chemical papermaking additive or emulsified non-water soluble chemical papermaking additive solution onto a hot transfer surface and evaporating the solvent from the chemical papermaking additive solution before transferring it to the dry web.
  • a typical commercially available silicone emulsion chemical softener is Dow Corning® Q2-7224 Conditioning Agent marketed by the Dow Corning Corporation.
  • This material generally contains about 35% by weight of an amino-functional polysiloxane emulsified in water.
  • This silicone receipt emulsion is diluted with water to less than about 20% concentration, by weight, before being applied to the heated transfer surface.
  • chemical papermaking additive emulsions used in the present invention are first diluted with water to less than about 15% concentration by weight before being applied to the transfer surface.
  • Exemplary materials suitable for the heated transfer surfaces include metal (e.g., steel, stainless steel, and chrome), non-metal (e.g., suitable polymers, ceramic, glass), and rubber.
  • the films of the present invention are preferably less than about 10 x 10 -6 meters (10 microns) in thickness, and more preferably, less than about 1x10 -6 meters (1 micron) in thickness.
  • At least about 50%, more preferably at least about 80%, of the water is evaporated from the dilute chemical papermaking additive solution which is applied to the heated transfer surface before transferring it to the dry tissue web. This leaves a film with a calculated thickness of about 0.075x10 -6 meters (.075 microns). Most preferably greater than about 95% of the water is evaporated from the solution on the heated transfer surface, leaving a calculated film thickness of about 0.05x10 -6 meters (0.05 microns) for transfer to the paper web.
  • the temperature of the heated transfer surface is preferably below the boiling point of the solvent.
  • the temperature of the heated transfer surface should be below 100°C.
  • the temperature is between 50 and 90°C, more preferably between 70 and 90°C when water is used as the solvent.
  • the heat on the transfer surface can also cause a lowering of the viscosity of the chemical papermaking additive, thus increasing its ability to spread into a thin film on the transfer surface.
  • This film is then transferred to the paper web surface by contacting the web with the transfer surface.
  • the chemical papermaking additive transfer efficiency to the web is quite high. Efficiencies on the order of 40 to 80% are typical, based on the flow out of the spray nozzles to the transfer surface and the quantity measured on the paper web.
  • this process is not limited to overdried paper.
  • the process described herein is capable of delivering chemical papermaking additives to equilibrated dry paper as well. However application to a hot overdried web is preferred, to insure that any residual water in the film does not interfere with any paper properties.
  • the chemical papermaking additives for use in the improved process of the present invention are preferably selected from the group consisting of strength additives, absorbency additives, softener additives, aesthetic additives, and mixtures thereof. Each of these types of additives will be discussed below.
  • the strength additive is selected from the group consisting of permanent wet strength resins, temporary wet strength resins, dry strength additives, and mixtures thereof.
  • the chemical papermaking additive can be chosen form the following group of chemicals: polyamid-epichlorohydrin, polyacrylamides, styrene-butadiene latexes; insolubilized polyvinyl alcohol; urea-formaldehyde; polyethyleneimine; and chitosan polymers.
  • Polyamide-epichlorohydrin resins are cationic wet strength resins which have been found to be of particular utility. Suitable types of such resins are described in U.S.-A-3,700,623, issued on October 24, 1972, and US-A-3,772,076, issued on November 13, 1973, both issued to Keim.
  • One commercial source of a useful polyamide-epichlorohydrin resins is Hercules, Inc. of Wilmington, Delaware, which markets such resin under the mark KymemeTM 557H.
  • Polyacrylamide resins have also been found to be of utility as wet strength resins. These resins are described in U.S.-A-3,556,932, issued on January 19, 1971, to Coscia, et al. and US-A-3,556,933, issued on January 19, 1971, to Williams et al.
  • One commercial source of polyacrylamide resins is American Cyanamid Co. of Stanford, Connecticut, which markets one such resin under the mark ParezTM 631 NC.
  • Still other water-soluble cationic resins finding utility in this invention are urea formaldehyde and melamine formaldehyde resins.
  • the more common functional groups of these polyfunctional resins are nitrogen containing groups such as amino groups and methylol groups attached to nitrogen.
  • Polyethylenimine type resins may also find utility in the present invention.
  • the chemical papermaking additive can be chosen form the following group of chemicals.
  • Cationic dialdehyde starch-based resin such as Caldas produced by Japan Carlet or Cobond 1000 produced by National Starch
  • dialdehyde starch and/or the resin described in U.S.-A-4,981,557 issued on January 1, 1991, to Bjorkquist.
  • the chemical papermaking additive can be chosen from the following group of chemicals.
  • Polyacrylamide such as combinations of Cypro 514 and Accostrength 711 produced by American cyanamid of Wayne, N.J.
  • starch such as corn starch or potato starch
  • polyvinyl alcohol such as Airvol 540 produced by Air Products Inc of Allentown, PA
  • guar or locust bean gums such as Airvol 540 produced by Air Products Inc of Allentown, PA
  • polyacrylate latexes such as Aqualon CMC-T from Aqualon Co., Wilmington, DE.
  • suitable starch for practicing the present invention is characterized by water solubility, and hydrophilicity.
  • Exemplary starch materials include corn starch and potato starch, and waxy corn starch that is known industrially as amioca starch is particularly preferred.
  • Amioca starch differs from common corn starch in that it is entirely amylopectin, whereas common corn starch contains both amplopectin and amylose.
  • Various unique characteristics of amioca starch are further described in "Amioca. The Starch From Waxy Corn", H. H. Schopmeyer, Food Industries, December 1945, pp. 106-108 (Vol. pp. 1476-1478).
  • the starch can be in granular or dispersed form albeit granular form is preferred.
  • the starch is preferably sufficiently cooked to induce swelling of the granules.
  • the starch granules are swollen, as by cooking, to a point just prior to dispersion of the starch granule.
  • Such highly swollen starch granules shall be referred to as being "fully cooked.”
  • the conditions for dispersion in general can vary depending upon the size of the starch granules, the degree of crystallinity of the granules, and the amount of amylose present.
  • Fully cooked amioca starch for example, can be prepared by heating an aqueous slurry of about 4% consistency of starch granules at about 190°F (about 88°C) for between about 30 and about 40 minutes.
  • modified starch materials which may be used include modified cationic starches such as those modified to have nitrogen containing groups such as amino groups and methylol groups attached to nitrogen, available from National Starch and Chemical Company, (Bridgewater, New Jersey).
  • modified starch materials have heretofore been used primarily as a pulp furnish additive to increase wet and/or dry strength. However, when applied in accordance with this invention by application to an overdried tissue paper web they may have reduced effect on wet strength relative to wet-end addition of the same modified starch materials. Considering that such modified starch materials are more expensive than unmodified starches, the latter have generally been preferred.
  • These wet and dry strength resins may be added to the pulp furnish in addition to being added by the process described in this invention. It is to be understood that the addition of chemical compounds such as the wet strength and temporary wet strength resins discussed above to the pulp furnish is optional and is not necessary for the practice of the present development.
  • the strength additive is preferably applied to the heated transfer roll in an aqueous solution.
  • Methods of application include, the same previously described with reference to application of other chemical additives preferably by spraying; and, less preferably, by printing.
  • the strength additive may be applied to the tissue paper web alone, simultaneously with, prior to, or subsequent to the addition of softener, absorbency, and/or aesthetic additives.
  • At least an effective amount of a strength additive, preferably starch, to provide lint control and concomitant strength increase upon drying relative to a non-binder treated but otherwise identical sheet is preferably applied to the sheet.
  • a strength additive is retained in the dried sheet, calculated on a dry fiber weight basis; and, more preferably, between about 0.1% and about 1.0% of a strength additive material, preferably starch-based, is retained.
  • the chemical softener additives are selected from the group consisting of lubricants, plasticizers, cationic debonders, noncationic debonders and mixtures thereof.
  • Debonders which are preferred for use in the present invention are noncationic; and, more preferably, are nonionic surfactants.
  • cationic surfactants may be used.
  • Noncationic surfactants include anionic, nonionic, amphoteric, and zwitterionic surfactants.
  • the surfactant is substantially nonmigratory in situ after the tissue paper has been manufactured in order to substantially obviate post-manufacturing changes in the tissue paper's properties which might otherwise result from the inclusion of surfactant.
  • surfactants having melt temperatures greater than the temperatures commonly encountered during storage, shipping, merchandising, and use of tissue paper product embodiments of the invention: for example, melt temperatures of about 50°C or higher.
  • the surfactant is preferably water-soluble when applied to the wet web.
  • the level of noncationic surfactant applied to tissue paper webs to provide the aforementioned softness/tensile benefit ranges from the minimum effective level needed for imparting such benefit, on a constant tensile basis for the end product, to about 2%: preferably between about 0.01% and about 2% noncationic surfactant is retained by the web; more preferably, between about 0.05% and about 1.0%; and, most preferably, between about 0.05% and about 0.3%.
  • the surfactants preferably have alkyl chains with eight or more carbon atoms.
  • Exemplary anionic surfactants are linear alkyl sulfonates, and alkylbenzene sulfonates.
  • nonionic surfactants are alkylglycosides including alkylglycoside esters such as CrodestaTM SL-40 which is available from Croda, Inc. (New York, NY); alkylglycoside ethers as described in U.S. -A-4,011,389, issued to W. K. Langdon, et al. on March 8, 1977; alkylpolyethoxylated esters such as PegosperseTM 200 ML available from Glyco Chemicals, Inc.
  • alkylglycoside esters such as CrodestaTM SL-40 which is available from Croda, Inc. (New York, NY)
  • alkylglycoside ethers as described in U.S. -A-4,011,389, issued to W. K. Langdon, et al. on March 8, 1977
  • alkylpolyethoxylated esters such as PegosperseTM 200 ML available from Glyco Chemicals, Inc.
  • alkylpolyethoxylated ethers and esters such as Neodol® 25-12 available from Shell Chemical Co
  • sorbitan esters such as Span 60 from ICI America, Inc, ethoxylated sorbitan esters, propoxylated sorbitan esters, mixed ethoxylated/propoxylated sorbitan esters, and polyethoxylated sorbitan alcohols such as Tween 60 also from ICI America, Inc.
  • Alkylpolyglycosides are particularly preferred for use in the present invention.
  • the surfactant may be applied to the hot transfer surface by spraying, gravure printing, or flexographic printing. Any surfactant other than the chemical papermaking additive emulsifying surfactant material, is hereinafter referred to as "surfactant,” and any surfactant present as the emulsifying component of emulsified chemical papermaking additives is hereinafter referred to as "emulsifying agent".
  • surfactant Any surfactant other than the chemical papermaking additive emulsifying surfactant material, is hereinafter referred to as "surfactant,” and any surfactant present as the emulsifying component of emulsified chemical papermaking additives is hereinafter referred to as "emulsifying agent".
  • the surfactant may be applied to the tissue paper alone or simultaneously with, after, or before other chemical papermaking additives. In a typical process, if another additive is present, the surfactant is applied to an overdried web simultaneously with the other additive(s).
  • binder refers to the various wet and dry strength additives known in the art.
  • the binder may be applied to the tissue paper simultaneously with, after or before the debonder and an absorbency aid, if used.
  • binders are added to the overdried tissue webs simultaneously with the debonder (i.e., the binder is included in the dilute debonder solution applied to the heated transfer surface).
  • a chemical softener that functions primarily by imparting a lubricous feel
  • it can be chosen from the following group of chemicals.
  • Organic materials such as mineral oil or waxes such as parafin or carnuba, or lanolin
  • polysiloxanes such as the compounds described in U.S.-A-5,059,282 issued to Ampulski. It has been found, surprisingly, that low levels of polysiloxane applied to hot, overdried tissue paper webs can provide a softened, silky, flannel-like, nongreasy tactile sense of feel to the tissue paper without the aid of additional materials such as oils or lotions.
  • tissue paper treated with polysiloxane in accordance with the present invention comprises about 0.75% or less polysiloxane. It is an unexpected benefit of this invention that tissue paper treated with about 0.75% or less polysiloxane can have imparted thereto substantial softness and silkiness benefits by such a low level of polysiloxane.
  • tissue paper having less than about 0.75% polysiloxane, preferably less than about 0.5% can provide substantial increases in softness and silkiness and flannel-like quality yet remain sufficiently wettable for use as toilet paper without requiring the addition of surfactant to offset any negative impact on wettability which results from the polysiloxane.
  • the minimum level of polysiloxane to be retained by the tissue paper is at least an effective level for imparting a tactile difference in softness or silkiness or flannel-like quality to the paper.
  • the minimum effective level may vary depending upon the particular type of sheet, the method of application, the particular type of polysiloxane, and whether the polysiloxane is supplemented by starch, surfactant, or other additives or treatments.
  • the range of applicable polysiloxane retention by the tissue paper preferably at least about 0.004%, more preferably at least about 0.01%, and most preferably at least about 0.05% polysiloxane is retained by the tissue paper.
  • a sufficient amount of polysiloxane to impart a tactile sense of softness is disposed uniformly on both surfaces of the tissue paper: i.e., disposed on the outwardly facing surfaces of the surface-level fibers.
  • polysiloxane When polysiloxane is applied to one surface of the tissue paper, some of it will, generally, at least partially penetrate to the tissue paper interior. However, preferably, the polysiloxane is applied to both sides of the tissue paper to ensure that both surfaces have imparted thereto the benefits of the polysiloxane.
  • tissue paper having in excess of about 0.3% polysiloxane is preferably treated with surfactant when contemplated for uses wherein high wettability is desired.
  • a noncationic surfactant is applied to the hot, overdried tissue paper web, in order to obtain an additional softness benefit, on a constant tensile basis, as previously discussed.
  • the amount of surfactant required to increase hydrophilicity to a desired level will depend upon the type and level of polysiloxane and the type of surfactant. However, as a general guideline, between about 0.01% and about 2% surfactant retained by the tissue paper, preferably between about 0.05% and about 1.0%, is believed to be sufficient to provide sufficiently high wettability for most applications, including toilet paper, for polysiloxane levels of about 0.75% or less.
  • a chemical softener that functions primarily by plasticizing the structure
  • it can be chosen from the following group of chemicals: polyethylene glycol (such as PEG 400); dimethylamine; and/or glycerine.
  • a cationic chemical softener that functions primarily by debonding
  • it can be chosen from the following group of chemicals.
  • Cationic quaternary compounds such as dihydrogenated tallow dimethyl ammonium methyl sulfate (DTDMAMS) or dihydrogenated tallow dimethyl ammonium chloride (DTDMAC) both produced by Sherex Corporation of Dudlin, OH; Berocel 579 (produced by Eka Nobel of Stennungsund, Sweden); materials described in U.S.-A-4,351,699 and US-A-4,447,294 issued to Osborn; and/or diester derivitives of DTDMAMS or DTDMAC.)
  • DTDMAMS dihydrogenated tallow dimethyl ammonium methyl sulfate
  • DTDMAC dihydrogenated tallow dimethyl ammonium chloride
  • an absorbency aid that enhances the rate of absorbency it can be chosen from the following group of chemicals: polyethoxylates (such as PEG 400); alkyl ethoxylated esters (such as Pegosperse 200ML from Lonza Inc.); alkyl ethoxylated alcohols (such as Neodol®); alkyl polyethoxylated nonylphenols (such as Igepal CO produced by Rhone-Poulenc/GAF) and/or materials described in U.S.-A-4,959,125 and US-A-4,940,513 issued to Spendel.
  • polyethoxylates such as PEG 400
  • alkyl ethoxylated esters such as Pegosperse 200ML from Lonza Inc.
  • alkyl ethoxylated alcohols such as Neodol®
  • alkyl polyethoxylated nonylphenols such as Igepal CO produced by Rhone-Poulenc/GAF
  • a wetting agent e.g., a second surfactant
  • a sorbitan stearate ester can be mixed with an alkyl polyethoxylated alcohol to produce a soft wettable paper.
  • an absorbency aid that decreases the rate of absorbency it can be chosen from the following group of chemicals.
  • Alkylketenedimers such as Aquapel® 360XC Emulsion manufactured by Hercules Inc., Wilmington, DE.
  • fluorocarbons such as Scotch Guard by 3M of Minneapolis, MN.
  • the absorbency additive can be used alone or in combination with a strength additive.
  • Starch based strength additives have been found to be the preferred binder for use in the present invention.
  • the tissue paper is treated with an aqueous solution of starch, and, as mentioned above, the sheet is overdried at the time of application.
  • low levels of starch also imparts a modest improvement in the tensile strength of tissue paper without imparting boardiness (i.e., stiffness) which would result from additions of high levels of starch.
  • tissue paper having improved strength/softness relationship compared to tissue paper which has been strengthened by traditional methods of increasing tensile strength: for example, sheets having increased tensile strength due to increased refining of the pulp; or through the addition of other dry strength additives.
  • This result is especially surprising since starch has traditionally been used to build strength at the expense of softness in applications wherein softness is not an important characteristic: for example, paperboard. Additionally, parenthetically, starch has been used as a filler for printing and writing paper to improve surface printability.
  • an aesthetic additive it can be chosen from the following group of chemicals: inks; dyes; perfumes; opacifiers (such as TiO2 or calcium carbonate), optical brighteners, and mixtures thereof.
  • the aesthetics of the paper can also be improved utilizing the process described in this invention.
  • Inks, dyes, and/or perfumes are preferably added to the application fluid which is subsequently applied to the hot transfer roll.
  • the aesthetics additive may be applied alone or in combination with the wetting, softening, and/or strength additives.
  • the level of polysiloxane retained by the tissue paper can be determined by solvent extraction of the polysiloxane with an organic solvent followed by atomic absorption spectroscopy to determine the level of silicon in the extract;
  • the level of nonionic surfactants, such as alkylglycosides can be determined by extraction in an organic solvent followed by gas chromatography to determine the level of surfactant in the extract;
  • the level of anionic surfactants, such as linear alkyl sulfonates can be determined by water extraction followed by colorimetry analysis of the extract;
  • the level of starch can be determined by amylase digestion of the starch to glucose followed by colorimetry analysis to determine glucose level.
  • Hydrophilicity of tissue paper refers, in general, to the propensity of the tissue paper to be wetted with water. Hydrophilicity of tissue paper may be somewhat quantified by determining the period of time required for dry tissue paper to become completely wetted with water. This period of time is referred to as "wetting time.”
  • wetting time the following procedure may be used for wetting time determinations: first, a conditioned sample unit sheet (the environmental conditions for testing of paper samples are 23 ⁇ 1°C and 50 ⁇ 2% RH as specified in TAPPI Method T 402), approximately 11.1 cm x 12 cm (about 4-3 ⁇ 8 inch x 4-3 ⁇ 4 inch x 12 cm) of tissue paper structure is provided; second, the sheet is folded into four (4) juxtaposed quarters, and then crumpled into a ball approximately 1.9 cm (about 0.75 inches) to about 2.5 cm (about 1 inch) in diameter; third, the balled sheet is placed on the surface of a body of distilled water at 23 ⁇ 1°C
  • tissue paper used in a variety of applications, e.g., toilet paper, to completely wet in a relatively short period of time to prevent clogging once the toilet is flushed.
  • wetting time is 2 minutes or less. More preferably, wetting time is 30 seconds or less. Most preferably, wetting time is 10 seconds or less.
  • Hydrophilicity characters of tissue paper embodiments of the present invention may, of course, be determined immediately after manufacture. However, substantial increases in hydrophobicity may occur during the first two weeks after the tissue paper is made: i.e., after the paper has aged two (2) weeks following its manufacture. Thus, the above stated wetting times are preferably measured at the end of such two week period. Accordingly, wetting times measured at the end of a two week aging period at room temperature are referred to as "two week wetting times.”
  • the density of tissue paper is the average density calculated as the basis weight of that paper divided by the caliper, with the appropriate unit conversions incorporated therein.
  • Caliper of the tissue paper is the thickness of the paper when subjected to a compressive load of 15.5 g/cm 2 (95 g/in 2 ).
  • the purpose of this example is to illustrate one method that can be used to make soft tissue paper sheets treated with a softening additive in accordance with the present invention.
  • a pilot scale Fourdrinier papermaking machine is used in the practice of the present invention.
  • the paper machine has a layered headbox having a top chamber, a center chamber, and a bottom chamber. Where applicable as indicated in the following examples, the procedure described below also applies to such later examples. Briefly, first a fibrous slurry comprised primarily of short papermaking fibers is pumped through the top and bottom headbox chambers and, simultaneously, a second fibrous slurry comprised primarily of long papermaking fibers is pumped through the center headbox chamber and delivered in superposed relation onto the Fourdrinier wire to form thereon a three-layer embryonic web.
  • the first slurry has a fiber consistency of about 0.11% and its fibrous content is Eucalyptus Hardwood Kraft.
  • the second slurry has a fiber consistency of about 0.15% and its fibrous content is Northern Softwood Kraft.
  • Dewatering occurs through the Fourdrinier wire and is assisted by a deflector and vacuum boxes.
  • the Fourdrinier wire is of a 5-shed, satin weave configuration having 87 machine-direction and 76 cross-machine-direction monofilaments per 2.54 cm (per inch), respectively.
  • the embryonic wet web is transferred from the Fourdrinier wire, at a fiber consistency of about 22% at the point of transfer, to a carrier fabric having a 5-shed satin weave, 35 machine-direction and 33 cross-machine-direction monofilaments per inch, respectively.
  • the web is carried on the carrier fabric past the vacuum dewatering box, through the blow-through predryers after which the web is transferred onto a Yankee dryer.
  • the fiber consistency is about 27% after the vacuum dewatering box and, by the action of the predryers, about 65% prior to transfer onto the Yankee dryer; creping adhesive comprising a 0.25% aqueous solution of polyvinyl alcohol is spray applied by applicators; the fiber consistency is increased to an estimated 99% before dry creping the web with a doctor blade.
  • the doctor blade has a bevel angle of about 24 degrees and is positioned with respect to the Yankee dryer to provide an impact angle of about 83 degrees; the Yankee dryer is operated at about 177°C (350°F); the Yankee dryer is operated at about 244 meters per minute (800 fpm - feet per minute).
  • the heated calender rolls are sprayed with a chemical softener emulsion, further described below, using a 2 mm spray nozzle.
  • the web is then passed between the two heated calender rolls.
  • the two calender rolls are biased together at roll weight and operated at surface speeds of about 201 meters per minute (660 fpm).
  • the spray solution is made by diluting Neodol® 25-12 Shell Chemical to 5% by weight with water.
  • the surfactant solution is then sprayed onto a heated steel calender roll.
  • the volumetric flow rate of the aqueous solution through the nozzle is about 25 liters/hr cross-direction meter (about 2 gal/hr - ft).
  • the dry web which has a moisture content of about 1%, contacts the hot calender rolls.
  • the chemical softener compound is transferred to the dry web by direct pressure transfer.
  • the transfer efficiency of the chemical softener applied to the web in general, is about 45%.
  • the resulting tissue paper has a basis weight of 30g/m 2 , a density of 0.10g/cc, and contains 0.17% by weight, of the alkylpolyethoxylated alcohol compound and has an unequilibrated initial moisture content of 1.2%. Importantly the resulting tissue paper has an improved tactile sense of softness relative to the untreated control.
  • the purpose of this example is to illustrate one method that can be used to make soft tissue paper sheets wherein the tissue paper is treated with a softening additive and starch.
  • a 3-layer paper sheet is produced in accordance with the hereinbefore described process of Example I.
  • the tissue web is treated with CrodestaTM SL-40 (an alkyl glycoside polyester nonionic surfactant marketed by Croda Inc.) and with a fully cooked amioca starch prepared as described in the specification.
  • the surfactant and starch are applied simultaneously on the heated transfer roll as part of the aqueous solution sprayed through the paper machine spray nozzle.
  • Concentration of the CrodestaTM SL-40 nonionic surfactant in the aqueous solution is adjusted so that the level of surfactant retained is about 0.15%, based upon the weight of the dry fibers.
  • concentration of the starch in the aqueous solution is adjusted so that the level of amioca starch retained is about 0.2%, based upon the weight of the dry fibers.
  • the treating mixture is sprayed onto an upper and a lower heated transfer roll.
  • the water is evaporated from the rolls and the active surfactant, and binder are transferred to both sides of the tissue web.
  • the volumetric flow rate through the upper and lower spray nozzle onto the heated rolls is about 12 liters/hr cross-direction meter (1 gal/hr - ft).
  • the combined flow rate through both nozzles is 25 liters/hr cross-direction meter (2 gal/hr - ft).
  • the resulting tissue paper has a basis weight of 30g/m 2 , a density of 0.10g/cc, and contains 0.15% by weight of CrodestaTM SL-40 nonionic surfactant and 0.2% by weight of the cooked amioca starch. Importantly, the resulting tissue paper has enhanced tactile softness and has higher wettability and lower propensity for lint than untreated tissue paper.
  • the purpose of this example is to illustrate one method that can be used to make soft tissue paper sheets wherein the tissue paper is treated in accordance with the present invention and converted into a two ply product.
  • a 2-layer paper sheet is produced in accordance with the hereinbefore described process of Example I with the following exceptions.
  • the volumetric flow rate through the nozzle is approximately 13.3 liters/hr cross-direction meter (about 1.05 gal/hr - ft).
  • the film thickness after 95% of the water is evaporated is calculated to about 0.035 x 10 -6 meters (.035 microns).
  • the resulting single ply tissue paper has a basis weight of 16 g/m 2 .
  • the resulting two-ply tissue paper product has a basis weight of 32 g/m 2 , a density of 0.10 g/cc, and contains 0.17% by weight, of the alkylpolyethoxylated alcohol.
  • the resulting tissue paper has enhanced tactile softness.
  • the purpose of this example is to illustrate one method that can be used to make soft tissue paper sheets wherein the tissue paper is treated with a mixed surfactant system containing a softener additive and an absorbency enhancing agent.
  • a 3-layer paper sheet is produced in accordance with the hereinbefore described process of Example I.
  • An aqueous dispersion of softener is prepared from 11.9% GLYCOMUL-S CG (a mixed sorbitan stearate ester surfactant made by Lonza, Inc.), 3.2% Neodol® 23-6.5T (an ethoxylated C 12 -C 13 linear alcohol dispersing surfactant and wetting agent made by Shell Chemical Company), 0.8% DOW 65 Additive (a silicone polymer foam suppressant made by Dow Corning Corporation), and 84.1% distilled water.
  • GLYCOMUL-S CG a mixed sorbitan stearate ester surfactant made by Lonza, Inc.
  • Neodol® 23-6.5T an ethoxylated C 12 -C 13 linear alcohol dispersing surfactant and wetting agent made by Shell Chemical Company
  • DOW 65 Additive a silicone polymer foam suppressant made by Dow Corning Corporation
  • the treating mixture is sprayed onto a lower heated calender (transfer) roll.
  • the water is evaporated from the roll and the active softener and absorbency enhancing agent are transferred to one side of the tissue web.
  • the flow rate through the spray nozzles is adjusted such that about 0.6% softener (Glycomul-S CG) is retained by the sheet.
  • the resulting tissue paper has a basis weight of 30g/m 2 , a density of 0.10g/cc, and contains about 0.6% by weight of the Glycomul-S CG surfactant.
  • the resulting tissue paper has an enhanced tactile softness and has high wettability.
  • a 3-layer paper sheet is produced in accordance with the hereinbefore described process of Example I.
  • a IX aqueous dispersion of softener is prepared from a mixture of diester dihydrogenated tallow dimethyl ammonium chloride (DEDTDMAC) (i.e., ADOGEN DDMC from the Sherex Chemical Company) and a polyethylene glycol wetting agent (i.e., PEG-400 from the Union Carbide Company).
  • DEDTDMAC diester dihydrogenated tallow dimethyl ammonium chloride
  • PEG-400 polyethylene glycol wetting agent
  • PEG is heated up to about 82°C (180oF); 3. DEDTDMAC is dissolved into PEG to form a melted solution; 4. Shear stress is applied to form a homogeneous mixture of DEDTDMAC in PEG; 5. The pH of the dilution water is adjusted to about 3 by the addition of hydrochloric acid; 6. The dilution water is then heated up to about 82°C (180°F); 7. The melted mixture of DEDTDMAC/PEG400 is diluted to a 1% solution; 8. Shear stress is applied to form an aqueous solution containing a vesicle suspension of DEDTDMAC/PEG-400 mixture.
  • the treating mixture is sprayed onto a lower heated calender (transfer) roll.
  • the water is evaporated from the roll and the active softening compound and absorbency agent are transferred to one side of the tissue web.
  • the flow rate through the spray nozzles is adjusted such that about 0.05% softener (DEDTDMAC) is retained by the sheet.
  • the resulting tissue paper has a basis weight of 30g/m 2 , a density of 0.10g/cc, and contains about 0.05% by weight of the DEDTDMAC softener.
  • the resulting tissue paper has an enhanced tactile softness and has high wettability.

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Biochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Paper (AREA)
EP93920248A 1992-08-27 1993-08-20 Process for applying chemical papermaking additives from a thin film to tissue paper Expired - Lifetime EP0656971B1 (en)

Applications Claiming Priority (5)

Application Number Priority Date Filing Date Title
US07/936,439 US5246546A (en) 1992-08-27 1992-08-27 Process for applying a thin film containing polysiloxane to tissue paper
US07/936,161 US5246545A (en) 1992-08-27 1992-08-27 Process for applying chemical papermaking additives from a thin film to tissue paper
US936161 1992-08-27
US936439 1992-08-27
PCT/US1993/007852 WO1994005857A1 (en) 1992-08-27 1993-08-20 Process for applying chemical papermaking additives from a thin film to tissue paper

Publications (2)

Publication Number Publication Date
EP0656971A1 EP0656971A1 (en) 1995-06-14
EP0656971B1 true EP0656971B1 (en) 1996-10-23

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EP93920248A Expired - Lifetime EP0656971B1 (en) 1992-08-27 1993-08-20 Process for applying chemical papermaking additives from a thin film to tissue paper

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EP (1) EP0656971B1 (ko)
JP (1) JP3188464B2 (ko)
KR (1) KR100284677B1 (ko)
AT (1) ATE144568T1 (ko)
AU (1) AU666409B2 (ko)
BR (1) BR9306992A (ko)
CA (1) CA2143340C (ko)
CZ (1) CZ284239B6 (ko)
DE (1) DE69305647T2 (ko)
DK (1) DK0656971T3 (ko)
ES (1) ES2093452T3 (ko)
FI (1) FI950863A (ko)
GR (1) GR3021441T3 (ko)
HU (1) HU214780B (ko)
NO (1) NO305565B1 (ko)
NZ (1) NZ255839A (ko)
WO (1) WO1994005857A1 (ko)

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Publication number Priority date Publication date Assignee Title
DE59506319D1 (de) * 1994-09-16 1999-08-05 Sca Hygiene Prod Gmbh Verfahren zur herstellung von tissuepapier unter verwendung eines behandlungsmittels
ZA965679B (en) * 1995-07-21 1997-01-24 Kimberly Clark Co Method for making soft tissue with improved bulk softness and surface softness
FI108063B (fi) * 1997-09-09 2001-11-15 Runtech Systems Oy Menetelmä ja laitteisto materiaalirainan käsittelemiseksi
DE19963834C2 (de) * 1999-12-30 2002-03-28 Sca Hygiene Prod Gmbh Verfahren zur Applikation von Behandlungschemikalien auf ein flächiges Erzeugnis auf Faserbasis und damit hergestellte Produkte
DE19963826A1 (de) * 1999-12-30 2001-07-19 Sca Hygiene Prod Gmbh Verfahren zur Applikation von Behandlungschemikalien auf flächige Erzeugnisse auf Faser-Basis und damit hergestellte Produkte
DE19963835C2 (de) * 1999-12-30 2002-03-28 Sca Hygiene Prod Gmbh Verfahren zur Applikation von Behandlungschemikalien auf flächige Erzeugnisse auf Faserbasis, insbesondere Tissue, und damit hergestellte Produkte
US6860967B2 (en) 2001-01-19 2005-03-01 Sca Hygiene Products Gmbh Tissue paper penetrated with softening lotion
US6905697B2 (en) 2001-01-19 2005-06-14 Sca Hygiene Products Gmbh Lotioned fibrous web having a short water absorption time
MXPA05004553A (es) * 2002-11-22 2005-07-26 Procter & Gamble Estructura fibrosa que comprende un sistema de agente flexibilizante de la fibra.
US20060130989A1 (en) * 2004-12-22 2006-06-22 Kimberly-Clark Worldwide, Inc. Tissue products treated with a polysiloxane containing softening composition that are wettable and have a lotiony-soft handfeel
EP2689067A4 (en) * 2011-03-25 2014-11-12 Nanopaper Llc VOLATILE DELETING AGENT FORMULATIONS FOR MANUFACTURING PAPER
JP2014084533A (ja) * 2012-10-19 2014-05-12 Nippon Paper Crecia Co Ltd 衛生用紙の製造方法
JP6393997B2 (ja) * 2014-02-07 2018-09-26 王子ホールディングス株式会社 衛生薄葉紙製品の製造方法
JP6575338B2 (ja) * 2015-12-08 2019-09-18 日油株式会社 衛生紙用柔軟剤
EP3231939A1 (de) 2016-04-11 2017-10-18 Fuhrmann, Uwe Mehrlagiges papiertaschentuch zur reduzierung der übertragung von krankheitserregern
JP6366675B2 (ja) * 2016-12-20 2018-08-01 日本製紙クレシア株式会社 衛生用紙の製造方法

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FR1320917A (fr) * 1962-01-16 1963-03-15 Mead Corp Procédé de production de papier couché très brillant à enduit minéral
US4849278A (en) * 1985-08-27 1989-07-18 Kimberly-Clark Corporation Flexible, durable, stretchable paper base web
ES2070174T3 (es) * 1988-06-14 1995-06-01 Procter & Gamble Procedimiento para preparar papel tisu suave tratado con polisiloxano.
EP0347177B1 (en) * 1988-06-14 1995-05-10 The Procter & Gamble Company Process for preparing soft tissue paper treated with nonionic surfactant
US5215626A (en) * 1991-07-19 1993-06-01 The Procter & Gamble Company Process for applying a polysiloxane to tissue paper

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CZ50795A3 (en) 1995-11-15
CA2143340C (en) 2000-10-17
DE69305647D1 (de) 1996-11-28
JPH08500860A (ja) 1996-01-30
HU9500581D0 (en) 1995-04-28
BR9306992A (pt) 1999-01-12
GR3021441T3 (en) 1997-01-31
AU5084193A (en) 1994-03-29
DE69305647T2 (de) 1997-03-06
NO305565B1 (no) 1999-06-21
EP0656971A1 (en) 1995-06-14
FI950863A (fi) 1995-04-19
KR100284677B1 (ko) 2001-03-15
WO1994005857A1 (en) 1994-03-17
ATE144568T1 (de) 1996-11-15
FI950863A0 (fi) 1995-02-24
NO950699D0 (no) 1995-02-24
KR950703102A (ko) 1995-08-23
NO950699L (no) 1995-04-26
CA2143340A1 (en) 1994-03-17
HUT72350A (en) 1996-04-29
JP3188464B2 (ja) 2001-07-16
DK0656971T3 (da) 1996-11-18
AU666409B2 (en) 1996-02-08
CZ284239B6 (cs) 1998-10-14
HU214780B (hu) 1998-05-28
ES2093452T3 (es) 1996-12-16
NZ255839A (en) 1997-02-24

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