WO2000022233A1 - Procede relatif a la fabrication de papier de soie doux - Google Patents

Procede relatif a la fabrication de papier de soie doux Download PDF

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Publication number
WO2000022233A1
WO2000022233A1 PCT/US1999/023592 US9923592W WO0022233A1 WO 2000022233 A1 WO2000022233 A1 WO 2000022233A1 US 9923592 W US9923592 W US 9923592W WO 0022233 A1 WO0022233 A1 WO 0022233A1
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WO
WIPO (PCT)
Prior art keywords
alkyl
softening
group
composition
slurry
Prior art date
Application number
PCT/US1999/023592
Other languages
English (en)
Inventor
David Dale Mckay
John Ernest Rice
Kenneth Douglas Vinson
James Robert Mcfarland
Amy Jo Karl
Errol Hoffman Wahl
Gayle Marie Frankenbach
Original Assignee
The Procter & Gamble Company
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by The Procter & Gamble Company filed Critical The Procter & Gamble Company
Priority to AU64240/99A priority Critical patent/AU753313B2/en
Priority to CA002346658A priority patent/CA2346658C/fr
Priority to EP99951897A priority patent/EP1131486B1/fr
Priority to AT99951897T priority patent/ATE245724T1/de
Priority to BR9914577-4A priority patent/BR9914577A/pt
Priority to JP2000576116A priority patent/JP2002527641A/ja
Priority to DE69909821T priority patent/DE69909821T2/de
Publication of WO2000022233A1 publication Critical patent/WO2000022233A1/fr

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D17/00—Detergent materials or soaps characterised by their shape or physical properties
    • C11D17/04—Detergent materials or soaps characterised by their shape or physical properties combined with or containing other objects
    • C11D17/041—Compositions releasably affixed on a substrate or incorporated into a dispensing means
    • C11D17/046—Insoluble free body dispenser
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/38—Cationic compounds
    • C11D1/40—Monoamines or polyamines; Salts thereof
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/38—Cationic compounds
    • C11D1/52—Carboxylic amides, alkylolamides or imides or their condensation products with alkylene oxides
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/38—Cationic compounds
    • C11D1/62—Quaternary ammonium compounds
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/38—Cationic compounds
    • C11D1/645—Mixtures of compounds all of which are cationic
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/66—Non-ionic compounds
    • C11D1/72—Ethers of polyoxyalkylene glycols
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/66—Non-ionic compounds
    • C11D1/75—Amino oxides
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/66—Non-ionic compounds
    • C11D1/835—Mixtures of non-ionic with cationic compounds
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D17/00—Detergent materials or soaps characterised by their shape or physical properties
    • C11D17/04—Detergent materials or soaps characterised by their shape or physical properties combined with or containing other objects
    • C11D17/049—Cleaning or scouring pads; Wipes
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/02—Inorganic compounds ; Elemental compounds
    • C11D3/04—Water-soluble compounds
    • C11D3/046—Salts
    • 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
    • D21H17/71—Mixtures of material ; Pulp or paper comprising several different materials not incorporated by special processes
    • 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
    • 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
    • D21H23/04—Addition to the pulp; After-treatment of added substances in the pulp
    • 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
    • D21H27/00—Special paper not otherwise provided for, e.g. made by multi-step processes
    • D21H27/30—Multi-ply
    • D21H27/38—Multi-ply at least one of the sheets having a fibrous composition differing from that of other sheets
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/38—Cationic compounds
    • C11D1/52—Carboxylic amides, alkylolamides or imides or their condensation products with alkylene oxides
    • C11D1/525—Carboxylic amides (R1-CO-NR2R3), where R1, R2 or R3 contain two or more hydroxy groups per alkyl group, e.g. R3 being a reducing sugar rest
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H17/00—Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
    • D21H17/03—Non-macromolecular organic compounds
    • D21H17/05—Non-macromolecular organic compounds containing elements other than carbon and hydrogen only
    • D21H17/06—Alcohols; Phenols; Ethers; Aldehydes; Ketones; Acetals; Ketals
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H17/00—Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
    • D21H17/03—Non-macromolecular organic compounds
    • D21H17/05—Non-macromolecular organic compounds containing elements other than carbon and hydrogen only
    • D21H17/07—Nitrogen-containing compounds
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H17/00—Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
    • D21H17/63—Inorganic compounds
    • D21H17/66—Salts, e.g. alums

Definitions

  • This invention relates, in general, to softening cellulosic structures with cationic bond inhibiting compounds; and more specifically, to a composition having rheological properties which facilitate its use for enhancing the softness thereof. Most particularly, the invention relates to softening tissue paper webs and methods of producing such softened webs.
  • Sanitary paper tissue products are widely used. Such items are commercially offered in formats tailored for a variety of uses such as facial tissues, toilet tissues and absorbent towels.
  • Softness is a complex tactile impression evoked by a product when it is stroked against the skin.
  • Objectionable discharges of urine, menses, and fecal matter from the perineal area or otorhinolaryngogical mucus discharges do not always occur at a time convenient for one to perform a thorough cleansing, as with soap and copious amounts of water for example.
  • a thorough cleansing a wide variety of tissue and toweling products are offered to aid in the task of removing from the skin and retaining such discharges for disposal in a sanitary fashion.
  • the use of these products does not approach the level of cleanliness that can be achieved by the more thorough cleansing methods, and producers of tissue and toweling products are constantly striving to make their products compete more favorably with thorough cleansing methods.
  • Patent 4,874,465 issued October 17, 1989, and Hermans, et. al. in U. S. Statutory Invention Registration HI 672, published on August 5, 1997, all of which disclose methods for selecting or upgrading fiber sources to tissue and toweling of superior properties.
  • Applicable art is further illustrated by Carstens in U.S. Patent 4,300,981, issued November 17, 1981, which discusses how fibers can be incorporated to be compliant to paper structures so that they have maximum softness potential. While such techniques as illustrated by these prior art examples are recognized broadly, they can only offer some limited potential to make tissues truly effective comfortable cleaning implements. Another area which has received a considerable amount of attention is the addition of chemical softening agents (also referred to herein as "chemical softeners”) to tissue and toweling products.
  • chemical softening agents also referred to herein as "chemical softeners”
  • the term "chemical softening agent” refers to any chemical ingredient which improves the tactile sensation perceived by the consumer who holds a particular paper product and rubs it across the skin. Although somewhat desirable for towel products, softness is a particularly important property for facial and toilet tissues. Such tactilely perceivable softness can be characterized by, but is not limited to, friction, flexibility, and smoothness, as well as subjective descriptors, such as a feeling like lubricious, velvet, silk or flannel. Suitable materials include those which impart a lubricious feel to tissue.
  • basic waxes such as paraffin and beeswax and oils such as mineral oil and silicone oil as well as petrolatum and more complex lubricants and emollients such as quaternary ammonium compounds with long alkyl chains, functional silicones, fatty acids-, fatty alcohols and fatty esters.
  • the field of work in the prior art pertaining to chemical softeners has taken two paths.
  • the first path is characterized by the addition of softeners to the tissue paper web during its formation either by adding an attractive ingredient to the vats of pulp which will ultimately be formed into a tissue paper web, to the pulp slurry as it approaches a paper making machine, or to the wet web as it resides on a Fourdrinier cloth or dryer cloth on a paper making machine.
  • the second path is categorized by the addition of chemical softeners to tissue paper web after the web is dried. Applicable processes can be incorporated into the paper making operation as, for example, by spraying onto the dry web before it is wound into a roll of paper.
  • Exemplary art related to the former path categorized by adding chemical softeners to the tissue paper prior to its assembly into a web includes U S. Patent 5,264,082, issued to Phan and Trokhan on November 23, 1993 and in US Patent 5,543067, issued to Phan on August 6, 1996, the disclosure of each being incorporated herein by reference.
  • Such methods have found broad use in the industry.
  • prior art compositions are either solids or viscous liquids at room temperature.
  • such prior art chemical softening composition must be heated before dilution to a use concentration for addition to the papermaking furnish. Such heating adds complexity to the papermaking process and poses an additional capital requirement for the necessary equipment
  • the '626 Patent discloses a method for prepa ⁇ ng soft tissue paper by applying a polysiloxane to a dry web.
  • '545 Patent discloses a similar method utilizing a heated transfer surface.
  • the '345 Patent discloses methods of application including roll coating and extrusion for applying particular compositions to the surface of a dry tissue web.
  • the Vinson, et al. application discloses compositions that are particularly suitable for surface application onto a tissue web.
  • the present invention desc ⁇ bes softening compositions that, when added to the wet end of a wet laid process for producing cellulosic structures, reduce the fiber to fiber bonding thereof, providing a structure with improved softness while providing acceptable strength and absorbency.
  • the softening composition compnses. an effective amount of a softening active ingredient, a vehicle in which the softening active ingredient is dispersed; an electrolyte dissolved in the vehicle, the electrolyte causing the viscosity of the composition to be less than the viscosity of a dispersion of the softening composition m the vehicle alone, and a bilayer disrupter to further reduce the viscosity of the softening composition
  • cellulosic structure as used herein is defined as a wet laid fab ⁇ c, web, or sheet compnsed of fibers containing cellulose. In its broadest sense, such structures possess a basis weight ranging from 10 g/m 2 to about 1 kg/m 2 and possess densities ranging from about 0.1 g/cc to as high as about 1 g/cc.
  • the cellulosic structures of the present invention preferably de ⁇ ve at least a portion of their strength from the natural fiber to fiber bonds which form when a web of short cellulosic fibers is drained and d ⁇ ed from a aqueous slurry. Consequently, so called wet laid papermaking is the most common process employing the present invention.
  • the softening compositions of the present invention have desirable low viscosity at room temperature allowing dilution as a part of the papermaking process without the complexity and added cost of a heating step.
  • the term "vehicle” as used herein means 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 vehicle may also serve as a earner that contains a chemical additive or aids in the delivery of a chemical papermaking additive. All references are meant to be interchangeable and not limiting.
  • the dispersion is the fluid containing the chemical papermaking additive.
  • dispensersion as used herein includes true solutions, suspensions, and emulsions. For purposes for this invention, all terms are interchangeable and not limiting.
  • the amount of the softening composition added to the cellulosic structure is preferably, between about 0.05% and about 10% based on the total weight of the softening composition compared to the total weight of the resulting cellulosic structure.
  • the cellulosic structure is preferably a tissue paper, most preferably a tissue paper having a basis weight of from about 10 to about 100 g/m 2 and a fiber density of less than about 0.6 g/cc.
  • Figure 1 is a schematic representation illustrating a creped papermaking process of the present invention for producing a strong, soft tissue paper comprising papermaking fibers using the softening composition of the present invention.
  • Figure 2 is a schematic representation illustrating the steps for preparing the aqueous papermaking furnish for a creped papermaking process, according to one embodiment of the present invention.
  • the present invention provides a composition useful for softening cellulosic structures. Preferably, it is added to the wet end of a process for making the cellulosic structure. Most preferably, the cellulosic structure is a tissue paper. The resulting tissue paper comprising the composition of the present invention has enhanced tactilely perceivable softness.
  • the softening composition, a method for producing the combination, and a method of adding it to wet end of a paper-making process are described.
  • the composition of the present invention is a dispersion of a softening active ingredient in a vehicle.
  • the composition also comprises a bilayer disrupter which allows the composition to have both a particularly high level of ingredients effective in softening tissue paper webs and, at the same time, a low viscosity at room temperature.
  • Such compositions are particularly desirable for addition to the wet end of a papermaking process so as to provide paper made using such a process with desirable softness.
  • Such compositions are especially desirable for use in processes used in the production of tissue paper products used for personal cleaning.
  • 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 about 10 g/m 2 and about 100 g/m 2 , and density of about 0.60 g/cc or less.
  • the basis weight will be between about 10 g/m 2 and about 80 g/m 2 , and the density will be about 0.30 g/cc or less. Most preferably, the density will be between about 0.04 g/cc and about 0.20 g/cc.
  • Conventionally pressed tissue paper and methods for making such paper are known in the art. Such paper is typically made by depositing a papermaking furnish on a foraminous forming wire. This forming wire is often referred to in the art as a Fourdrinier wire. Once the furnish is deposited on the forming wire, it is referred to as a web. Overall, water is removed from the web by vacuum, mechanical pressing and thermal means. The web is dewatered by pressing the web and by drying at elevated temperature.
  • 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.
  • 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 compression forces while the fibers are moist and are then d ⁇ ed while m a compressed state. The resulting structure is strong and generally of singular density, but very low m bulk, absorbency and in softness.
  • Pattern densified tissue paper is characte ⁇ zed 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 characte ⁇ zed 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 3,301,746, issued to Sanford and Sisson on January 31, 1967, U.S. Patent 3,974,025, issued to Ayers on August 10, 1976, and U.S. Patents 4,191,609 and 4,637,859, issued to Trokhan on March 4, 1980 and on January 20, 1987 respectively; the disclosure of each of which is incorporated herein by reference.
  • 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 as it is transferred from the forming wire to a structure comprising such supports for further drying.
  • the web is pressed against the array of supports, thereby resulting in densified zones m 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 du ⁇ ng 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 pred ⁇ ed, 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 dewate ⁇ ng, optional predrymg and formation of the densified zones may be integrated or partially integrated to reduce the total number of processing steps performed.
  • the web is d ⁇ ed to completion, preferably still avoiding mechanical pressing.
  • the tissue paper surface comp ⁇ ses densified knuckles, the knuckles preferably having a relative density of at least 125% of the density of the high-bulk field.
  • the structure comp ⁇ sing an array of supports is preferably an impnnttng earner fab ⁇ c 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.
  • Impnnting earner fabncs are disclosed in U.S Patent 3,301,746, issued to Sanford and Sisson on January 31, 1967, U.S. Patent 3,821,068, issued to Salvucci, Jr. et al. on May 21, 1974, U.S. Patent 3,974,025, issued to Ayers on August 10, 1976, U.S. Patent 3,573,164, issued to F ⁇ edberg, et al. on March 30, 1971, U.S. Patent 3,473,576, issued to Amneus on October 21, 1969, U.S. Patent 4,239,065, issued to Trokhan on December 16, 1980, and U.S. Patent 4,528,239, issued to Trokhan on July 9, 1985, the disclosure of each of which is incorporated herein by reference.
  • the furnish is first formed into a wet web on a foraminous forming earner, such as a Fourdnmer wire.
  • the web is dewatered and transferred to an impnnting fabnc
  • the furnish may alternately be initially deposited on a foraminous supporting earner which also operates as an impnnting fabnc.
  • the wet web is dewatered and, preferably, thermally predned to a selected fiber consistency of between about 40% and about 80%.
  • Dewate ⁇ ng is preferably performed with suction boxes or other vacuum devices, with blow-through dryers, or combinations thereof.
  • the knuckle imp ⁇ nt of the impnnting fab ⁇ c is impressed in the web as discussed above, p ⁇ or to drying the web to completion.
  • One method for accomplishing this is through application of mechanical pressure This can be done, for example, by pressing a nip roll which supports the impnnting fabnc 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 impnnting fab ⁇ c pnor 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 dunng initial dewate ⁇ ng, m a separate, subsequent process stage, or a combination thereof.
  • uncompacted, non pattern-densified tissue paper structures are prepared by depositing a papermaking furnish on a foraminous forming wire such as a Fourdnmer 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 dewate ⁇ ng 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.
  • the softening composition of the present invention can also be useful for softening uncreped tissue paper.
  • Uncreped tissue paper a term as used herein, refers to tissue paper which is non-compressively dried, most preferably by through air drying. Resultant through air dried webs are pattern densified such that zones of relatively high density are dispersed within a high bulk field, including pattern densified tissue wherein zones of relatively high density are continuous and the high bulk field is discrete.
  • an embryonic web is transferred from the foraminous forming carrier upon which it is laid, to a slower moving, high fiber support transfer fabric carrier. The web is then transferred to a drying fabric upon which it is dried to a final dryness.
  • Papermaking Fibers 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.
  • One exemplary polyethylene fiber which may be utilized is Pulpex®, available from Hercules, Inc. (Wilmington, DE).
  • 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 are preferred since they impart a supenor tactile sense of softness to tissue sheets made therefrom.
  • Pulps denved from both deciduous trees hereinafter, also referred to as "hardwood”
  • coniferous trees hereinafter, also referred to as "softwood”
  • fibers denved from recycled paper which may contain any or all of the above categories as well as other non-fibrous matenals such as fillers and adhesives used to facilitate the original papermaking.
  • Particularly preferred cellulosic pulps include long fibers such as Northern softwood Kraft
  • NNK short fibers, such as Eucalyptus
  • secondary fibers such as pre and post consumer white ledger, coated book stock, and office waste.
  • Such fibers may be used m any desired combination, with or without laye ⁇ ng.
  • the softening composition of the present invention compnses a dispersion of a softening active ingredient in a vehicle.
  • a furnish used to produce tissue paper or other cellulosic structures as descnbed herein such compositions are effective in softening the structures.
  • the softening composition of the present invention has properties (e.g., ingredients, rheology, pH, etc.) permitting easy application thereof on a commercial scale. It is well known to those skilled in the art that quaternary ammonium compounds which compnse the preferred active ingredient of the softening composition of the present invention are not usually readily dispersible m water.
  • the preferred quaternary compounds are solids at room temperature and when added to water are difficult to disperse into a uniform dispersion even with the application of mechanical action. It is also well known that the desired form for softening composition is a cold-water dispersible liquid. Previous attempts to solve this conflict have not been entirely satisfactory.
  • One method has been to use highly active organic solvents capable of solubi zing the quaternary ammonium compound liquid at room temperature and making it dispersible in water.
  • a low molecular weight alcohol such as isopropanol can be used.
  • VOC process safety and environmental burden
  • Solvents which are less active can be employed, but much larger quantities are required with resulting negative cost and environmental consequences as well.
  • Quaternary ammonium compounds can also be made more fluid and more dispersible by increasing their hydrophihcity by, for example, ethoxylatmg the alkyl chains thereof. This method decreases the effectiveness of the quaternary ammonium compound as a softening ingredient and involves additional processing cost as well.
  • composition of the present invention is a highly concentrated form of a preferred softening active ingredient, a quaternary ammonium compound, that is still readily water dispersible.
  • a preferred softening active ingredient a quaternary ammonium compound
  • the following discusses each of the components of the softening composition of the present invention, the properties of the composition, methods of producing the composition, and methods of applying the composition.
  • each R ] is a C j -Cg alkyl group, hydroxyalkyl group, hydrocarbyl or substituted hydrocarbyl group, alkoxylated group, benzyl group, or mixtures thereof; each R2 is a C14-C22 alkyl group, hydroxyalkyl group, hydrocarbyl or substituted hydrocarbyl group, alkoxylated group, benzyl group, or mixtures thereof; and
  • X is any softener-compatible anion are suitable for use in the present invention.
  • each R ⁇ is methyl and X" is chlo ⁇ de or methyl sulfate.
  • each R2 is Ci g-Ci g linear or branched alkyl or alkenyl, most preferably each R2 is straight-chain Ci g alkyl or alkenyl.
  • the R2 substituent can be denved from vegetable oil sources. Several types of the vegetable oils (e.g., olive, canola, safflower, sunflower, etc.) can used as sources of fatty acids to synthesize the quaternary ammonium compound. Branched chain actives (e.g.
  • Suitable branched chain fatty acids that can serve as a starting point for such quaternary ammonium compounds include: 2-n-heptylundecano ⁇ c acid, 2-n-butyloctano ⁇ c acid, 5,7,9-tnmethylnonano ⁇ c acid, 3,5,7,9-tetramethylnonano ⁇ c, alpha-heptyldecanoic acid, and isostea ⁇ c acid, with isosteanc acid being particularly preferred.
  • Such structures include the well-known dialkyldimethylamrnonium salts (e.g. ditallowdimethylammonium chlonde, ditallowdimethylammomum methyl sulfate, d ⁇ (hydrogenated tallow)d ⁇ methyl ammonium chlonde, etc.), m which R ⁇ are methyl groups, R2 are tallow groups of varying levels of saturation, and X" is chlonde or methyl sulfate.
  • dialkyldimethylamrnonium salts e.g. ditallowdimethylammonium chlonde, ditallowdimethylammomum methyl sulfate, d ⁇ (hydrogenated tallow)d ⁇ methyl ammonium chlonde, etc.
  • m which R ⁇ are methyl groups
  • R2 are tallow groups of varying levels of saturation
  • X" is chlonde or methyl sulfate.
  • tallow is a naturally occurnng matenal having a vanable composition.
  • Table 6.13 m the above-identified reference edited by Swem indicates that, typically, 78% or more of the fatty acids of tallow contain 16 or 18 carbon atoms. Typically, half of the fatty acids present in tallow are unsaturated, p ⁇ manly in the form of oleic acid. Synthetic as well as natural "tallows" fall within the scope of the present invention.
  • the saturation level of the ditallow can be tailored from non hydrogenated (soft) to touch hydrogenated (partially hydrogenated) or completely hydrogenated (hard). All of above-descnbed saturation levels of are expressly meant to be included within the scope of the present invention.
  • Particularly preferred vanants of these softening active ingredients are what are considered to be mono or diester vanations of these quaternary ammonium compounds having the formula:
  • Y is -0-(0)C-, or -C(0)-0-, or -NH-C(O)-, or -C(0)-NH-; m is 1 to 3;
  • X is any softener-compatible anion
  • each R substituent is preferably a C ⁇ - C3, alkyl group, with methyl being most preferred.
  • each R3 is C13 -C17 alkyl and/or alkenyl, more preferably R3 is straight chain C15 - Ci 7 alkyl and/or alkenyl, C15-C17 alkyl, most preferably each R3 is straight-chain C17 alkyl
  • the R3 substituent can be denved from vegetable oil sources.
  • ⁇ vegetable oils e.g., olive, canola, safflower, sunflower, etc
  • olive oils, canola oils, high oleic safflower, and/or high erucic rapeseed oils are used to synthesize the quaternary ammonium compound.
  • X can be any softener-compatible amon, for example, acetate, chlonde, bromide, methylsulfate, formate, sulfate, nitrate and the like can also be used m the present invention.
  • X" is chlonde or methyl sulfate.
  • diester dialkyl dimethyl ammonium salts such as diester ditallow dimethyl ammonium chlonde, monoester ditallow dimethyl ammonium chlonde, diester ditallow dimethyl ammonium methyl sulfate, diester d ⁇ (hydrogenated)tallow dimethyl ammonium methyl sulfate, diester d ⁇ (hydrogenated)tallow di
  • Diester ditallow dimethyl ammonium chlonde and diester d ⁇ (hydrogenated)tallow dimethyl ammonium chlonde are particularly preferred.
  • the diester ditallow dimethyl ammonium chlonde and diester d ⁇ (hydrogenated)tallow dimethyl ammonium chlonde is available commercially from Witco Chemical Company Inc. of Dublin, OH under the tradename ADOGEN SDMC.
  • ADOGEN SDMC As mentioned above, typically, half of the fatty acids present in tallow are unsaturated, p ⁇ ma ⁇ ly in the form of oleic acid. Synthetic as well as natural "tallows" fall within the scope of the present invention.
  • the degree of saturation for such tallows can be tailored from non hydrogenated (soft), to partially hydrogenated (touch), or completely hydrogenated (hard) All of above- desc ⁇ bed saturation levels of are expressly meant to be included within the scope of the present invention. At least a minimal level of hydrogenation is preferred in order to remove, in particular, the multiply unsaturated species (e.g. linolenic derivatives) which are known to be more susceptible to oxidation with resulting rancidity.
  • the multiply unsaturated species e.g. linolenic derivatives
  • substituents Ri , R2 and R3 may optionally be substituted with various groups such as alkoxyl, hydroxyl, or can be branched.
  • each R ⁇ is methyl or hydroxyethyl.
  • each R2 is C12 - Ci g alkyl and/or alkenyl, most preferably each R2 is straight-chain Ci g - Ci alkyl and/or alkenyl, most preferably each R2 is straight-chain Ci g alkyl or alkenyl.
  • R3 is C13 - C17 alkyl and/or alkenyl, most preferably R3 is straight chain C15 - C17 alkyl and/or alkenyl.
  • X" is chloride or methyl sulfate.
  • the ester-functional quaternary ammonium compounds can optionally contain up to about 10% of the mono(long chain alkyl) derivatives, e.g.:
  • each R1 is a C1 - Cgalkyl or hydroxyalkyl group
  • R3 is C1 1 -C21 hydrocarbyl group
  • n is 2 to 4
  • X" is a suitable anion, such as an halide (e.g., chloride or bromide) or methyl sulfate.
  • each R3 is C13-C17 alkyl and/or alkenyl, most preferably each R3 is straight-chain C15 - Ci 7 alkyl and/or alkenyl, and R ⁇ is a methyl.
  • ester moiety(ies) of the aforementioned quaternary compounds provides a measure of biodegradability to such compounds.
  • ester-functional quaternary ammonium compounds used herein biodegrade more rapidly than do conventional dialkyl dimethyl ammonium chemical softeners.
  • plasticizer refers to an ingredient capable of reducing the melting point and viscosity at a given temperature of a quaternary ammonium ingredient.
  • the plasticizer can be added during the quaternizing step in the manufacture of the quaternary ammonium ingredient or it can be added subsequent to the quaternization but prior to the application as a softening active ingredient.
  • the plasticizer is characterized by being substantially inert during the chemical synthesis of the quaternary ammonium compound where it can act as a viscosity reducer to aid in the synthesis.
  • Preferred plasticizers are non-volatile polyhydroxy compounds.
  • Preferred polyhydroxy compounds include glycerol and polyethylene glycols having a molecular weight of from about 200 to about 2000, with polyethylene glycol having a molecular weight of from about 200 to about 600 being particularly preferred.
  • plasticizers When such plasticizers are added during manufacture of the quaternary ammonium ingredient, they comprise between about 5% and about 75% percent of the product of such manufacture. Particularly preferred mixtures comprise between about 15% and about 50% plasticizer.
  • Vehicle As used herein a "vehicle” is used to dilute the active ingredients of the compositions described herein forming the dispersion of the present invention.
  • a vehicle may dissolve such components (true solution or micellar solution) or such components may be distributed throughout the vehicle (dispersion, emulsion, or sponge phase).
  • the vehicle of a suspension or emulsion is typically the continuous phase thereof. That is, other components of the dispersion or emulsion are dispersed on a molecular level or as discrete particles or molecular aggregates throughout the vehicle.
  • one purpose that the vehicle serves is to dilute the concentration of softening active ingredients so that such ingredients may be efficiently and economically applied. Such diluted compositions are more readily diluted to a use concentration without the need for complex processing equipment. Vehicles and softening compositions comprising such vehicles have also been discovered that are particularly useful for facilitating the incorporation of softening active ingredients into webs of tissue on a commercial scale.
  • Suitable softening ingredients can be dissolved in a vehicle forming a solution therein, materials that are useful as solvents for suitable softening active ingredients are not commercially desirable for safety and environmental reasons. Therefore, to be suitable for use in the vehicle for purposes of the present invention, a material should be compatible with the softening active ingredients described herein and with the tissue substrate with which the softening compositions of the present invention will be used. Further a suitable material should not contain any ingredients that create safety issues (either in the tissue manufacturing process or to users of tissue products using the softening compositions described herein) and not create an unacceptable risk to the environment. Suitable materials for the vehicle of the present invention include hydroxyl functional liquids most preferably water. Electrolyte
  • water is a particularly preferred material for use in the vehicle of the present invention
  • water alone is not preferred as a vehicle.
  • the dispersion has an unacceptably high viscosity. While not being bound by theory, it is believed that combining water and the softening active ingredients of the present invention to form such dispersions creates a liquid crystalline phase having a high viscosity. Compositions having such a high viscosity are difficult to dilute for use in a process for producing tissue webs softening the web.
  • the electrolyte can create an osmotic pressure difference across vesicle walls which would tend to draw interior water through the vesicle wall reducing the size of the vesicles and providing more "free" water, again resulting in a decrease in viscosity.
  • Any electrolyte meeting the general criteria described above for materials suitable for use in the vehicle of the present invention and which is effective in reducing the viscosity of a dispersion of a softening active ingredient in water is suitable for use in the vehicle of the present invention.
  • any of the known water-soluble electrolytes meeting the above criteria can be included in the vehicle of the softening composition of the present invention.
  • the electrolyte can be used in amounts up to about 25% by weight of the softening composition, but preferably no more than about 15 % by weight of the softening composition.
  • the level of electrolyte is between about 0.1% and about 10% by weight of the softening composition based on the anhydrous weight of the electrolyte.
  • the electrolyte is used at a level of between about 0.3% and about 1.0% by weight of the softening composition.
  • the minimum amount of the electrolyte will be that amount sufficient to provide the desired viscosity.
  • the dispersions typically display a non-Newtonian rheology, and are shear thinning with a desired viscosity generally ranging from about 10 centipoise (cp) up to about 1000 cp, preferably in the range between about 10 and about 200 cp, as measured at 25° C and at a shear rate of 100 sec"* using the method described in the TEST METHODS section below.
  • Suitable electrolytes include the halide, nitrate, nitrite, and sulfate salts of alkali or alkaline earth metals, as well as the corresponding ammonium salts.
  • electrolytes include the alkali and alkaline earth salts of simple organic acids such as sodium formate and sodium acetate, as well as the corresponding ammonium salts.
  • Preferred electrolytes include the chloride salts of sodium, calcium, and magnesium.
  • Calcium chloride is a particularly preferred electrolyte for the softening composition of the present invention. While not being bound by theory, it is believed that the divalent nature of the calcium ion makes it particularly effective in reducing the viscosity of the vesicular dispersions of the softening active ingredient. If desired, compatible blends of the various electrolytes are also suitable.
  • a bilayer disrupter is an essential component of the invention. While, as has been shown above, the vehicle, particularly the electrolyte component dissolved therein, performs an essential function in preparing the cellulosic structures of the present invention, it is desirable also to maximize the concentration of softening active ingredient while maintaining an acceptable viscosity. As noted above, addition of electrolyte allows an increase in the concentration of softening active ingredient in the softening composition without unduly increasing viscosity. However, if too much electrolyte is used, phase separation can occur. It has been found that adding a bilayer disrupter to the softening composition allows more softening active ingredient to be incorporated therein while maintaining viscosity at an acceptable level.
  • bilayer disrupter is an organic material that, when mixed with a dispersion of a softening active ingredient in a vehicle, is compatible with at least one of the vehicle or the softening active ingredient and causes a reduction of the viscosity of the dispersion.
  • bilayer disrupters function by penetrating the palliside layer of the liquid crystalline structure of the dispersion of the softening active ingredient in the vehicle and disrupting the order of the liquid crystalline structure. Such disruption is believed to reduce the interfacial tension at the hydrophobic-water interface, thus promoting flexibility with a resulting reduction in viscosity.
  • the term "pallisade layer” it is meant describe the area between hydrophilic groups and the first few carbon atoms in the hydrophobic layer (M.J Rosen, Surfactants and interfacial phenomena, Second Edition, pages 125 and 126).
  • materials suitable for use as a bilayer disrupter should be compatible with other components of the softening composition.
  • a suitable material should not react with other components of the softening composition so as to cause the softening composition to lose softening capability.
  • Bilayer disrupters useful in the compositions of the present invention are preferably surface active materials. Such materials comprise both hydrophobic and hydrophilic moieties.
  • a preferred hydrophilic moiety is a polyalkoxylated group, preferably a polyethoxylated group.
  • Such preferred materials are used at a level of between about 1% and about 15% of the level of the softening active ingredient.
  • the bilayer disrupter is present at a level of between about 2% and about 10% of the level of the softening active ingredient.
  • bilayer disrupters are nonionic surfactants derived from saturated and/or unsaturated primary and/or secondary, amine, amide, amine-oxide fatty alcohol, fatty acid, alkyl phenol, and or alkyl aryl carboxylic acid compounds, each preferably having from about 6 to about 22, more preferably from about 8 to about 18, carbon atoms in a hydrophobic chain, more preferably an alkyl or alkylene chain, wherein at least one active hydrogen of said compounds is ethoxylated with ⁇ 50, preferably ⁇ 30, more preferably from about 3 to about 15, and even more preferably from about 5 to about 12, ethylene oxide moieties to provide an HLB of from about 6 to about 20, preferably from about 8 to about 18, and more preferably from about 10 to about 15.
  • Suitable bilayer disrupters also include nonionic surfactants with bulky head groups selected from: a. surfactants having the formula
  • R is selected from the group consisting of saturated or unsaturated, pnmary, secondary or branched chain alkyl or alkyl-aryl hydrocarbons; said hydrocarbon chain having a length of from about 6 to about 22
  • Y' is selected from the following groups: -0-; -N(A)-; and mixtures thereof
  • A is selected from the following groups: H; R 1 ; -(R 2 -0) z -H; -(CH 2 ) CH 3 ; phenyl, or substituted aryl, wherein 0 ⁇ x ⁇ about 3 and z is from about 5 to about 30;
  • each R 2 is selected from the following groups or combinations of the following groups: -(CH 2 ) n - and/or - [CH(CH 3 )CH : ]-; and each R 5 is selected from the following
  • each R 5 is selected independently from the following:
  • one R 5 is -H
  • two R 5 are -0-(R 2 0)z-H
  • at least one R 5 is the following structure -CH(CH 2 -(OR 2 ) z -H)- CH 2 -(OR 2 ) z -C(0) R 1 with 8 ⁇ z + z' + z" ⁇ 20 and R
  • each R is H, C1-C4 hydrocarbyl, C1-C4 alkoxyalkyl, or hydroxyalkyl; and R 2 is a C5- C31 hydrocarbyl moiety; and each Z is a polyhydroxyhydrocarbyl moiety having a linear hydrocarbyl chain with at least 3 hydroxyls directly connected to the chain, or an ethoxylated derivative thereof; and each R' is H or a cyclic mono- or poly- saccharide, or alkoxylated derivative thereof; and
  • Suitable phase stabilizers also include surfactant complexes formed by one surfactant ion being neutralized with surfactant ion of opposite charge or an electrolyte ion that is suitable for reducing dilution viscosity.
  • bilayer disrupters examples include:
  • Suitable alkyl alkoxylated nonionic surfactants are generally derived from saturated or unsaturated primary, and secondary fatty alcohols, fatty acids, alkyl phenols, or alkyl aryl (e.g., benzoic) carboxylic acid, where the active hydrogen(s) is alkoxylated with ⁇ about 30 alkylene, preferably ethylene, oxide moieties (e.g. ethylene oxide and or propylene oxide).
  • nonionic surfactants for use herein preferably have from about 6 to about 22 carbon atoms on the alkyl or alkenyl chain, and are in a straight chain configuration, preferably straight chain configurations having from about 8 to about 18 carbon atoms, with the alkylene oxide being present, preferably at the primary position, in average amounts of ⁇ about 30 moles of alkylene oxide per alkyl chain, more preferably from about 3 to about 15 moles of alkylene oxide, and most preferably from about 6 to about 12 moles of alkylene oxide.
  • Preferred materials of this class also have pour points of less than about 70°F (21°C) and/or do not solidify in these softening compositions.
  • alkyl alkoxylated surfactants with straight chains include Neodol ® 91-8, 23-5, 25-9, 1-9, 25-12, 1-9, and 45-13 from Shell, Plurafac ® B-26 and C-17 from BASF, and Brij ® 76 and 35 from ICI Surfactants.
  • alkyl-aryl alkoxylated surfactants include: Surfonic N-120 from Huntsman, Igepal ® CO-620 and CO-710, from Rhone Poulenc, Triton ® N-l l l and N-150 from Union Carbide, Dowfax ® 9N5 from Dow and Lutensol ® AP9 and API 4, from BASF.
  • Suitable alkyl alkoxylated nonionic surfactants with amine functionality are generally derived from saturated or unsaturated, primary, and secondary fatty alcohols, fatty acids, fatty methyl esters, alkyl phenol, alkyl benzoates, and alkyl benzoic acids that are converted to amines, amine-oxides, and optionally substituted with a second alkyl or alkyl-aryl hydrocarbon with one or two alkylene oxide chains attached at the amine functionality each having ⁇ about 50 moles alkylene oxide moieties (e.g. ethylene oxide and/or propylene oxide) per mole of amine.
  • alkylene oxide moieties e.g. ethylene oxide and/or propylene oxide
  • the amine, amide or amine-oxide surfactants for use herein have from about 6 to about 22 carbon atoms, and are in either straight chain or branched chain configuration, preferably there is one hydrocarbon in a straight chain configuration having about 8 to about 18 carbon atoms with one or two alkylene oxide chains attached to the amine moiety, in average amounts of ⁇ 50 about moles of alkylene oxide per amine moiety, more preferably from about 3 to about 15 moles of alkylene oxide, and most preferably a single alkylene oxide chain on the amine moiety containing from about 6 to about 12 moles of alkylene oxide per amine moiety.
  • Preferred materials of this class also have pour points less than about 70°F (21°C)and/or do not solidify in these softening compositions.
  • ethoxylated amine surfactants include Berol ® 397 and 303 from Rhone Poulenc and Ethomeens ® C/20, C25, T/25, S/20, S/25 and Ethodumeens ® T/20 and T25 from Akzo.
  • the compounds of the alkyl or alkyl-aryl alkoxylated surfactants and alkyl or alkyl-aryl amine, amide, and amine-oxide alkoxylated have the following general formula: i _ _ 2
  • each R is selected from the group consisting of saturated or unsaturated, primary, secondary or branched chain alkyl or alkyl-aryl hydrocarbons; said hydrocarbon chain preferably having a length of from about 6 to about 22, more preferably from about 8 to about 18 carbon atoms, and even more preferably from about 8 to about 15 carbon atoms, preferably, linear and with no aryl moiety; wherein each R 2 is selected from the following groups or combinations of the following groups: -(CH 2 ) n - and/or -[CH(CH 3 )CH 2 ]-; wherein about 1 ⁇ n ⁇ about 3; Y is selected from the following groups: -0-; -N(A) q -; -C(0)0-; - (0 ⁇ -)N(A) q -; -B-R 3 -0-; -B-R 3 - N(A) q
  • each alkoxy chain can be replaced by a short chain C ⁇ _ 4 alkyl or acyl group to "cap" the alkoxy chain, z is from about 5 to about 30.
  • p is the number of ethoxylate chains, typically one or two, preferably one and m is the number of hydrophobic chains, typically one or two, preferably one and q is a number that completes the structure, usually one.
  • Suitable alkoxylated and non-alkoxylated bilayer disrupters with bulky head groups are generally denved from saturated or unsaturated, pnmary and secondary fatty alcohols, fatty acids, alkyl phenol, and alkyl benzoic acids that are de ⁇ vatized with a carbohydrate group or heterocyclic head group.
  • This structure can then be optionally substituted with more alkyl or alkyl-aryl alkoxylated or non-alkoxylated hydrocarbons.
  • the heterocyclic or carbohydrate is alkoxylated with one or more alkylene oxide chains (e.g. ethylene oxide and/or propylene oxide) each having ⁇ about 50, preferably ⁇ about 30, moles per mole of heterocyclic or carbohydrate.
  • the hydrocarbon groups on the carbohydrate or heterocyclic surfactant for use herein have from about 6 to about 22 carbon atoms, and are in a straight chain configuration, preferably there is one hydrocarbon having from about 8 to about 18 carbon atoms with one or two alkylene oxide chains carbohydrate or heterocyclic moiety with each alkylene oxide chain present in average amounts of ⁇ about 50, preferably ⁇ about 30, moles of carbohydrate or heterocyclic moiety, more preferably from about 3 to about 15 moles of alkylene oxide per alkylene oxide chain, and most preferably between about 6 and about 12 moles of alkylene oxide total per surfactant molecule including alkylene oxide on both the hydrocarbon chain and on the heterocyclic or carbohydrate moiety.
  • Examples of bilayer disrupters in this class are Tween ® 40, 60, and 80 available from ICI Surfactants.
  • the compounds of the alkoxylated and non-alkoxylated nonionic surfactants with bulky head groups have the following general formulas:
  • R is selected from the group consisting of saturated or unsaturated, pnmary, secondary or branched chain alkyl or alkyl-aryl hydrocarbons; said hydrocarbon chain having a length of from about 6 to about 22
  • Y' is selected from the following groups: -0-; -N(A)-; and mixtures thereof
  • A is selected from the following groups: H; R 1 ; -(R 2 -0) z -H; -(CH 2 ) X CH 3 ; phenyl, or substituted aryl, wherein 0 ⁇ x ⁇ about 3 and z is from about 5 to about 30;
  • each R 2 is selected from the following groups or combinations of the following groups: -(CH 2 ) deliberately- and/or - [CH(CH 3 )CH 2 ]-; and each R 5 is selected from the following groups
  • each R 5 is selected independently from the following: -H, -OH, -(CH 2 )xCH 3 , -(OR 2 ) z -H, -OR 1 , - OC(0)R', and -CH 2 (CH 2 -(OR 2 )_-H)-CH 2 -(OR 2 ) z -C(0) R 1 , with x R , and R 2 as defined above in section D above and z, z', and z" are all from about 5 ⁇ to ⁇ about 20, more preferably the total number of z + z' + z" is from about 5 ⁇ to ⁇ about 20.
  • Another group of surfactants that can be used are polyhydroxy fatty acid amide surfactants of the formula:
  • each R 7 is H, C1 -C4 hydrocarbyl, C1 -C4 alkoxyalkyl, or hydroxyalkyl, e.g., 2- hydroxyethyl, 2-hydroxypropyl, etc., preferably C1 -C4 alkyl, more preferably C ] or C2 alkyl, most preferably C ⁇ alkyl (i.e., methyl) or methoxyalkyl; and R 6 is a C5-C31 hydrocarbyl moiety, preferably straight chain C7-C19 alkyl or alkenyl, more preferably straight chain C9-C17 alkyl or alkenyl, most preferably straight chain C j j-Cj alkyl or alkenyl, or mixture thereof; and W is a polyhydroxyhydrocarbyl moiety having a linear hydrocarbyl chain with at least 3 hydroxyls directly connected to the chain, or an alkoxy
  • W preferably will be selected from the group consisting of -CH 2 -(CHOH) n -CH 2 OH, -CH(CH 2 OH)-(CHOH) n -CH 2 OH, -CH 2 - (CHOH)2(CHOR')(CHOH)-CH OH, where n is an integer from 3 to 5, inclusive, and R' is H or a cyclic mono- or poly- sacchande, and alkoxylated denvatives thereof. Most preferred are glycityls wherein n is 4, particularly -CH2-(CHOH)4-CH2 ⁇ . Mixtures of the above W moieties are desirable.
  • R6 can be, for example, N-methyl, N-ethyl, N-propyl, N-isopropyl, N-butyl, N-isobutyl, N- 2-hydroxyethyl, N-1-methoxypropyl, or N-2-hydroxypropyl.
  • R6-CO-N ⁇ can be, for example, cocamide, stearamide, oleamide, lauramide, my ⁇ stamide, capncamide, palmitamide, tallowamide, etc.
  • W can be 1-deoxygluc ⁇ tyl, 2-deoxyfruct ⁇ tyl, 1 -deoxymaltityl, 1-deoxylact ⁇ tyl, 1- deoxygalactityl, 1-deoxymann ⁇ tyl, 1-deoxymaltotnot ⁇ tyl, etc.
  • Alkoxylated cationic quaternary ammonium surfactants suitable for this invention are generally denved from fatty alcohols, fatty acids, fatty methyl esters, alkyl substituted phenols, alkyl substituted benzoic acids, and/or alkyl substituted benzoate esters, and/or fatty acids that are converted to amines which can optionally be further reacted with another long chain alkyl or alkyl-aryl group; this amine compound is then alkoxylated with one or two alkylene oxide chains each having ⁇ about 50 moles alkylene oxide moieties (e.g. ethylene oxide and/or propylene oxide) per mole of amine.
  • alkylene oxide moieties e.g. ethylene oxide and/or propylene oxide
  • Typical of this class are products obtained from the quatermzation of aliphatic saturated or unsaturated, primary, secondary, or branched amines having one or two hydrocarbon chains from about 6 to about 22 carbon atoms alkoxylated with one or two alkylene oxide chains on the amine atom each having less than ⁇ about 50 alkylene oxide moieties.
  • the amine hydrocarbons for use herein have from about 6 to about 22 carbon atoms, and are in either straight chain or branched chain configuration, preferably there is one alkyl hydrocarbon group in a straight chain configuration having about 8 to about 18 carbon atoms.
  • Suitable quaternary ammonium surfactants are made with one or two alkylene oxide chains attached to the amine moiety, in average amounts of ⁇ about 50 moles of alkylene oxide per alkyl chain, more preferably from about 3 to about 20 moles of alkylene oxide, and most preferably from about 5 to about 12 moles of alkylene oxide per hydrophobic, e.g., alkyl group.
  • Preferred matenals of this class also have a pour points below about 70°F (21°C)and/or do not solidify m these softening compositions.
  • bilayer disrupters of this type include Ethoquad ® 18/25, C/25, and 0/25 from Akzo and Va ⁇ quat ® -66 (soft tallow alkyl b ⁇ s(polyoxyethyl) ammonium ethyl sulfate with a total of about 16 ethoxy units) from Witco.
  • the compounds of the ammonium alkoxylated cationic surfactants have the following general formula:
  • X is an anion which is compatible with the softening active ingredient and other components of the softening composition.
  • Suitable surfactants have the formula:
  • R is C 7 . 21 linear alkyl, C7. 21 branched alkyl, C 7 . 1 linear alkenyl, C7. 21 branched alkenyl, and mixtures thereof.
  • R is C 8 . ⁇ s linear alkyl or alkenyl.
  • R 1 is -CH 2 -CH2-
  • R 2 is C3-C4 linear alkyl, C 3 -C 4 branched alkyl, and mixtures thereof; preferably R 2 is -CH(CH 3 )-CH -.
  • Surfactants which comp ⁇ se a mixture of R 1 and R 2 units preferably comp ⁇ se from about 4 to about 12 -CH 2 -CH 2 - units in combination with from about 1 to about 4 -CH(CH 3 )-CH 2 - units.
  • the units may be alternating or grouped together m any combination suitable to the formulator.
  • the ratio of R 1 units to R 2 units is from about 4: 1 to about 8: 1.
  • an R 2 unit i.e. -C(CH 3 )H-CH 2 -
  • R 3 is hydrogen, C C 4 linear alkyl, C 3 -C 4 branched alkyl, and mixtures thereof; preferably hydrogen or methyl, more preferably hydrogen.
  • R 4 is hydrogen, C C 4 linear alkyl, C 3 -C 4 branched alkyl, and mixtures thereof; preferably hydrogen.
  • the index m is 1 or 2, the index n is 0 or 1, provided that m + n equals 2; preferably m is equal to 1 and n is equal to 1, resulting in one - [(R 1 0) x (R 2 0) y R 3 ] unit and R4 being present on the nitrogen.
  • the index x is from 0 to about 50, preferably from about 3 to about 25, more preferably from about 3 to about 10.
  • the index y is from 0 to about 10, preferably 0, however when the index y is not equal to 0, y is from 1 to about 4.
  • Preferably all the alkyleneoxy units are ethyleneoxy units.
  • ethoxylated alkyl amide surfactants examples include Rewopal ® C 6 from Witco, Amidox ® C5 from Stepan, and Ethomid ® O / 17 and Ethomid ® HT / 60 from Akzo.
  • the vehicle can also compnse minor ingredients as may be known to the art.
  • minor ingredients include- mineral acids or buffer systems for pH adjustment (may be required to maintain hydrolytic stability for certain softening active ingredients) and antifoam ingredients (e. g., a silicone emulsion as is available from Dow Coming, Corp. of Midland, MI as Dow Coming 2310) as a processing aid to reduce foaming when the softening composition of the present invention is used.
  • Stabilizers may also be used to improve the uniformity and shelf life of the dispersion.
  • an ethoxylated polyester, HOE S 4060, available from Cla ⁇ ant Corporation of Charlotte, NC may be included for this purpose.
  • the softening composition of the present invention is a dispersion of a softening active ingredient in a vehicle.
  • the level of softening active ingredient may vary between about 10% of the composition and about 50% of the composition.
  • the softening active ingredient comp ⁇ ses between about 25% and about 45% of the composition. More preferably, the softening active ingredient comp ⁇ ses between about 30% and about 40% of the composition.
  • the nonionic surfactant is present at a level between about 1% and about 15% of the level of the softening active ingredient, preferably between about 2% and about 10%.
  • the softening composition may also comp ⁇ se between about 2% and about 30%, preferably between about 5% and about 25% of a plasticizer.
  • the preferred primary component of the vehicle is water.
  • the vehicle preferably comprises an alkali or alkaline earth halide electrolyte and may comprise minor ingredients to adjust pH, to control foam, or to aid in stability of the dispersion. The following describes preparation of a particularly preferred softening composition of the present invention.
  • composition 1 A particularly preferred softening composition of the present invention (Composition 1) is prepared as follows. The materials are more specifically defined in the table detailing Composition 1 which follows this description. Amounts used in each step are sufficient to result in the finished composition detailed in that table. The appropriate quantity of water is heated (extra added to compensate for evaporation loss) to about 165°F (75°C). The hydrochloric acid (25%o solution) and antifoam ingredient are added. Concurrently, the blend of softening active ingredient, plasticizer, and nonionic surfactant is melted by heating it to a temperature of about 150°F (65°C).
  • the melted mixture of softening active ingredient, plasticizer, and nonionic surfactant is then slowly added to the heated acidic aqueous phase with mixing to evenly distribute the disperse phase throughout the vehicle.
  • the water solubility of the polyethylene glycol probably carries it into the continuous phase, but this is not essential to the invention and plasticizers which are more hydrophobic and thus remain associated with the alkyl chains of the quaternary ammonium compound are also allowed within the scope of the present invention.
  • part of the calcium chloride is added (as a 2.5% solution) intermittently with mixing to provide an initial viscosity reduction.
  • the stabilizer is then slowly added to the mixture with continued agitation.
  • the remainder of the calcium chloride(as a 25% solution) is added with continued mixing.
  • Silicone Emulsion (10% active) Dow Coming 2310 ® , marketed by Dow Coming Corp., Midland, MI
  • Suitable nonionic surfactants are available from Shell Chemical of Houston, TX under the trade name NEODOL 91-8.
  • Bilayer disrupter, plasticizer, and softening active ingredient obtained pre- blended from Witco Chemical Company of Dublin OH (about 2 parts Neodol 91-8, about 29 parts polyethylene glycol 400, and about 69 parts tallow diester quaternary)
  • Stabilizer is HOE S 4060, from Clariant Corp., Charlotte, NC
  • the resulting chemical softening composition is a milky, low viscosity dispersion suitable for application to cellulosic structures as described below for providing desirable tactile softness to such structures. It displays a shear-thinning non-Newtonian viscosity.
  • the composition has a viscosity less than about 1000 centipoise (cp), as measured at 25° C and at a shear rate of 100 sec"l using the method described in the TEST METHODS section below.
  • the composition has a viscosity less than about 500 cp. More preferably, the viscosity is less than about 300 cp.
  • the chemical composition is easily handled as a liquid and is easily shipped from the point of manufacture to point of use since it has a relatively high concentration of active ingredient. At point the of use, it is convenient to dilute the concentrate to a use concentration. This dilution step is necessary in order to allow proper metenng of the softening active ingredient into the papermaking process. That is, in a commercial papermaking process, a fairly large quantity of a dispersion having a low concentration of the softener active ingredient is metered into an approp ⁇ ate process stream.
  • the use concentration depends on several factors including: process capability for the metenng step, the desired add-on of the softening active ingredient, the flow rates of the vanous process steams, and other factors as will be recognized by those having skill in the art
  • a suitable range of use concentrations has been found to be between about 0.5% and about 10% where the concentration is expressed as weight percent softening active ingredient.
  • the use concentration is between about 0.5% and about 5%, more preferably between about 0.5% and about 2%
  • a particularly preferred use concentration is about 1%.
  • aqueous papermaking furnish or the embryonic web can be added to the aqueous papermaking furnish or the embryonic web to impart other desirable characteristics to the product or improve the papermaking process so long as they are compatible with the chemistry of the softening composition and do not significantly and adversely affect the softness or strength character of the present invention.
  • the following materials are expressly included, but their inclusion is not offered to be all-inclusive.
  • Other materials can be included as well so long as they do not interfere or counteract the advantages of the present invention.
  • a cationic charge biasing species it is common to add a cationic charge biasing species to the papermaking process to control the zeta potential of the aqueous papermaking furnish as it is delivered to the papermaking process. These materials are used because most of the solids in nature have negative surface charges, including the surfaces of cellulosic fibers and fines and most inorganic fillers.
  • One traditionally used cationic charge biasing species is alum. More recently in the art, charge biasing is done by use of relatively low molecular weight cationic synthetic polymers preferably having a molecular weight of no more than about 500,000 and more preferably no more than about
  • the charge densities of such low molecular weight cationic synthetic polymers are relatively high. These charge densities range from about 4 to about 8 equivalents of cationic nitrogen per kilogram of polymer.
  • An exemplary material is Cypro 514®, a product of Cytec, Inc. of Stamford, CT. The use of such materials is expressly allowed within the practice of the present invention.
  • Common materials for this purpose are silica colloid, or bentonite clay. The incorporation of such materials is expressly included within the scope of the present invention.
  • the group of chemicals including polyamide- epichlorohydrin, polyacrylamides, styrene-butadiene lattices; insolubilized polyvinyl alcohol; urea-formaldehyde; polyethyleneimine; chitosan polymers and mixtures thereof can be added to the papermaking furnish or to the embryonic web.
  • Preferred resins are cationic wet strength resins, such as polyamide-epichlorohydrin resins. Suitable types of such resins are described in U.S. Patents 3,700,623, issued on October 24, 1972, and 3,772,076, issued on November 13, 1973, both to Keim, the disclosure of both being hereby incorporated by reference.
  • One commercial source of useful polyamide-epichlorohydrin resins is Hercules, Inc. of Wilmington, Delaware, which markets such resin under the mark Kymene 557H®.
  • the binder materials can be chosen from the group consisting of dialdehyde starch or other resins with aldehyde functionality such as Co-Bond 1000® offered by National Starch and Chemical Company of Scarborough, ME; Parez 750® offered by Cytec of Stamford, CT; and the resin described in U.S. Patent 4,981,557, issued on January 1, 1991, to Bjorkquist, the disclosure of which is incorporated herein by reference, and other such resins having the decay properties described above as may be known to the art.
  • surfactants may be used to treat the tissue paper webs of the present invention.
  • the level of surfactant, if used, is preferably from about 0.01% to about 2.0% by weight, based on the dry fiber weight of the tissue web.
  • the surfactants preferably have alkyl chains with eight or more carbon atoms.
  • Exemplary anionic surfactants include linear alkyl sulfonates and alkylbenzene sulfonates.
  • Exemplary nonionic surfactants include alkylglycosides including alkylglycoside esters such as Crodesta SL-40® which is available from Croda, Inc. (New York, NY); alkylglycoside ethers as described in U.S.
  • Patent 4,011,389 issued to Langdon, et al. on March 8, 1977; and alkylpolyethoxylated esters such as Pegosperse 200 ML available from Glyco Chemicals, Inc. (Greenwich, CT) and IGEPAL RC-520® available from Rhone Poulenc Corporation (Cranbury, NJ).
  • alkylpolyethoxylated esters such as Pegosperse 200 ML available from Glyco Chemicals, Inc. (Greenwich, CT) and IGEPAL RC-520® available from Rhone Poulenc Corporation (Cranbury, NJ).
  • cationic softener active ingredients with a high degree of unsaturated (mono and/or poly) and/or branched chain alkyl groups can greatly enhance absorbency.
  • the cellulosic structures of the present invention can contain other types of chemical softeners as well.
  • another class of papermaking-added chemical softening agents comprise the well-known organo-reactive polydimethyl siloxane
  • Filler materials may also be incorporated into the tissue papers of the present invention.
  • U.S. Patent 5,611,890, issued to Vinson et al. on March 18, 1997, and, incorporated herein by reference discloses filled tissue paper products that are acceptable as substrates for the present invention.
  • the above listings of optional chemical additives is intended to be merely exemplary in nature, and are not meant to limit the scope of the invention.
  • Figure 2 is a schematic representation illustrating a preparation of the aqueous papermaking furnish for the creped papermaking operation yielding a product according to the present invention The following discussion refers to Figure 2:
  • a storage vessel 8 is a repository for the low viscosity chemical softening composition of the present invention.
  • Pipe 9 provides dilution water for reducing the concentration of the softening active ingredient to a suitable use concentration.
  • Pump 10 acts to convey the diluted vesicular dispersion of the softening active ingredient.
  • the dispersion is optionally conditioned m a mixer 12 to aid in formation of the vesicles.
  • Resultant dispersion 13 is conveyed to a point where it is mixed with an aqueous dispersion of refined relatively long fiber papermaking fibers.
  • a storage vessel 1 is provided for staging an aqueous slurry of relatively long papermaking fibers.
  • the slurry is conveyed by means of a pump 2 and optionally through a refiner 3 to fully develop the strength potential of the long papermaking fibers.
  • Pipe 27 positioned between pump 2 and refiner 3 may be used to add a cationic debonder, if desired, to compensate for charged fines so as to minimize usage of other matenals added at later stages in the process.
  • additive pipe 4 conveys a resm to provide for wet or dry strength, m the finished product.
  • the slurry is then further conditioned in mixer 5 to aid m absorption of the resin. After mixing with the vesicular dispersion of softening active ingredient 13, it becomes the relatively long fiber based aqueous papermaking slurry 17.
  • the slurry may be conditioned in mixer 25 to aid m absorption of the softening active ingredient.
  • the suitably conditioned slurry is then diluted with white water 7 in a fan pump 6 forming a dilute long papermaking fiber slurry 29.
  • Pipe 20 adds a cationic flocculant to the slurry 29, producing a flocculated relatively long fibered slurry 22.
  • a relatively short papermaking fiber slurry originates from a repository 1 1, from which it is conveyed through pipe 49 by pump 14 through a refiner 15 where it becomes a refined slurry of relatively short papermaking fibers 16.
  • White water 7 is mixed with slurry 16 in a fan pump 18 at which point the slurry becomes a dilute aqueous papermaking slurry 19.
  • Pipe 21 directs a cationic flocculant into slurry 19, after which the slurry becomes a flocculated aqueous relatively short fiber based papermaking slurry 23.
  • the flocculated relatively short-fiber based aqueous papermaking slurry 23 is directed to the creped papermaking process illustrated in Figure 1 and is divided into two approximately equal streams which are then directed into headbox chambers 82 and 83 ultimately evolving into off- Yankee-side-layer 75 and Yankee-side- layer 71 , respectively of the strong, soft creped tissue paper.
  • the aqueous flocculated relatively long papermaking fiber slurry 22, referring to Figure 2 is preferably directed into headbox chamber 82b ultimately evolving into center layer 73 of the strong, soft creped tissue paper.
  • FIG 1 is a schematic representation illustrating a creped papermaking process for producing a strong, soft creped tissue paper. These preferred embodiments are described in the following discussion, wherein reference is made to Figure 1.
  • Figure 1 is a side elevational view of a preferred papermaking machine 80 for manufacturing paper according to the present invention.
  • papermaking machine 80 comprises a layered headbox 81 having a top chamber 82 a center chamber 82b, and a bottom chamber 83, a slice roof 84, and a Fourdrinier wire 85 which is looped over and about breast roll 86, deflector 90, vacuum suction boxes 91, couch roll 92, and a plurality of turning rolls 94.
  • one papermaking furnish is pumped through top chamber 82 a second papermaking furnish is pumped through center chamber 82b, while a third furnish is pumped through bottom chamber 83 and thence out of the slice roof 84 in over and under relation onto Fourdrinier wire 85 to form thereon an embryonic web 88 comprising layers 88a, and 88b, and 88c.
  • Dewatering occurs through the Fourdrinier wire 85 and is assisted by deflector 90 and vacuum boxes 91.
  • showers 95 clean it prior to its commencing another pass over breast roll 86.
  • the embryonic web 88 is transferred to a foraminous carrier fabric 96 by the action of vacuum transfer box 97.
  • Carrier fabric 96 carries the web from the transfer zone 93 past vacuum dewatering box 98, through blow-through predryers 100 and past two turning rolls 101 after which the web is transferred to a Yankee dryer 108 by the action of pressure roll 102.
  • the carrier fabric 96 is then cleaned and dewatered as it completes its loop by passing over and around additional turning rolls 101, showers 103, and vacuum dewatering box 105.
  • the predried paper web is adhesively secured to the cylindrical surface of Yankee dryer 108 aided by adhesive applied by spray applicator 109. Drying is completed on the steam heated Yankee dryer 108 and by hot air which is heated and circulated through drying hood 110 by means not shown.
  • the web is then dry creped from the Yankee dryer 108 by doctor blade 111 after which it is designated paper sheet 70 comprising a Yankee-side layer 71 a center layer 73, and an off- Yankee-side layer 75.
  • Paper sheet 70 then passes between calendar rolls 112 and 113, about a circumferential portion of reel 115, and thence is wound into a roll 116 on a core 117 disposed on shaft 118.
  • the genesis of Yankee-side layer 71 of paper sheet 70 is the furnish pumped through bottom chamber 83 of headbox 81, and which furnish is applied directly to the Fourdrinier wire 85 whereupon it becomes layer 88c of embryonic web 88.
  • the genesis of the center layer 73 of paper sheet 70 is the furnish delivered through chamber 82.5 of headbox 81, and which furnish forms layer 88b on top of layer 88c.
  • the genesis of the off-Yankee-side layer 75 of paper sheet 70 is the furnish delivered through top chamber 82 of headbox 81, and which furnish forms layer 88a on top of layer 88b of embryonic web 88.
  • Figure 1 shows papermachine 80 having headbox 81 adapted to make a three-layer web, headbox 81 may alternatively be adapted to make unlayered, two layer or other multi-layer webs.
  • the Fourdrinier wire 85 must be of a fine mesh having relatively small spans with respect to the average lengths of the fibers constituting the short fiber furnish so that good formation will occur; and the foraminous carrier fabric 96 should have a fine mesh having relatively small opening spans with respect to the average lengths of the fibers constituting the long fiber furnish to substantially obviate bulking the fabric side of the embryonic web into the interfilamentary spaces of the fabric 96.
  • the paper web is preferably dried to about 80% fiber consistency, and more preferably to about 95% fiber consistency prior to creping.
  • the present invention is applicable to creped tissue paper in general, including but not limited to conventionally felt-pressed creped tissue paper; high bulk pattern densified creped tissue paper; and high bulk, uncompacted creped tissue paper.
  • process steps described above are exemplary and that other processes are equally within the scope of the present invention.
  • a homogeneous furnish can be provided wherein the furnish can comprise any desired blend of long and short papermaking fibers that have been treated with a vesicular dispersion of a chemical softening active ingredient using process steps similar to those described above.
  • Processes providing tissue structures having two layers, such as that shown in Examples 3 and 4 are also within the scope of the present invention.
  • Example 1 This Example illustrates preparation of a preferred embodiment of the softening composition of the present invention.
  • Stabilizer HOE S 4060 from Clariant Corp., Charlotte, NC. These materials are prepared as follows to form the softening composition of the present invention.
  • the chemical softening composition is prepared by first heating the required quantity of water to about 75°C.
  • the hydrochloric acid and the polydimethylsiloxane are then added to the heated water.
  • the pH of the water premix is about 4.
  • the premix of quaternary compound, PEG 400, and nonionic surfactant is then heated to about 65°C and metered into the water premix with stirring until the mixture is fully homogeneous.
  • About half of the calcium chloride is added as a 2.5% solution in water with continued stirring.
  • the stabilizer is then added with continued mixing.
  • Final viscosity reduction is achieved by adding the remainder of the calcium chloride (as a 25% solution) with continued mixing.
  • the components are blended in a proportion sufficient to provide a composition having the following approximate concentrations of each of the ingredients:
  • the composition After cooling and addition of make-up water, the composition has a viscosity of about 300 centipoise as measured at 25° C and at a shear rate of 100 sec'l using the method descnbed in the TEST METHODS section.
  • Example 2
  • This example illustrates the effect of nonionic surfactant chemical composition on a key softening composition property — viscosity.
  • Chemical softening compositions are made up by first prepanng a master batch containing all of the ingredients of the softening composition except a bilayer disrupter. The formula for this composition is given in Table 1.
  • Test softening compositions are then prepared by blending potential bilayer disrupters with the master batch at levels of 1%, 2%, 3%, and 4%. Viscosity of each of the test softening compositions is measured according to the method descnbed m the TEST METHODS section below. The viscosity of the master batch is also measured Table 2 lists the test matenals, their HLB (a measure of emulsifying effectiveness), and the viscosity for each of the compositions made
  • Neodol 23-3 7.9 0 1.8xl0 7*
  • each of these matenals substantially reduces the viscosity of the dispersion to less than that of the dispersion without the matenal.
  • the purpose of this example is to illustrate a method using a conventional drying papermaking technique to make soft and absorbent tissue paper treated with a prior art chemical softener composition compnsmg a premix of D ⁇ (Hydrogenated)Tallow DiMethyl Ammonium
  • DHTDMAMS Methyl Sulfate
  • PEG-400 Polyoxyethylene Glycol 400
  • a pilot scale S-wrap twin-wire papermaking machine is used in the practice of the present invention
  • the substantially waterless self-emulsifiable chemical softener composition is prepared according to US Patent 5,474,689 wherein the homogenous premix of DHTDMAMS and PEG-400 in solid state is dispersed in a conditioned water tank (Temperature about 66°C.) to form a sub-micron vesicle dispersion.
  • a 3% by weight aqueous slurry of Deinked Market Pulp is made up in a conventional re-pulper.
  • the DMP slurry is refined gently and a 0.25% solution of the wet strength resin (i.e. Kymene 557H as is available from Hercules of Wilmington, DE) is added to the DMP stock pipe at a rate of 0.7 pounds resin/ ton (.04%) by weight of the dry fibers.
  • the adsorption of the wet strength resm onto DMP fibers is enhanced by an m-hne mixer.
  • DHTDMAMS in the form of a chemical softener mixture according to US Patent 5,474,689 is also added to the DMP stock pipe (at a concentration of 1% softening active ingredient) before the stock pump, but after the wet strength resm, at a rate of about 2.5 pounds/ton (0.125%) by weight of the dry fibers.
  • the adsorption of the chemical softener mixture to DMP fibers can be enhanced by an in-line mixer.
  • the DMP slurry is diluted to about 0.2% consistency at the fan pump.
  • a 3% by weight aqueous slurry of Eucalyptus fibers is made up m a conventional re- pulper.
  • the Eucalyptus slurry is diluted to about 0.2% consistency at the fan pump.
  • the slur ⁇ es of DMP and eucalyptus are directed into a multi-channeled headbox suitably equipped with layenng leaves to maintain the streams as separate layers until discharge onto a traveling S-wrap twin-wire.
  • a three-chambered headbox is used.
  • the eucalyptus slurry, containing sufficient solids flow to achieve 34% of the dry weight of the ultimate paper is directed to chambers leading to the forming wire , while the DMP slurry compnsmg sufficient solids flow to achieve 66% of the dry weight of the ultimate paper is directed to the remaining two chambers.
  • the DMP and eucalyptus slur ⁇ es are combined at the discharge of the headbox into a composite slurry.
  • the composite slurry is discharged onto the traveling S-wrap twin-wire former and is dewatered. Dewatenng is assisted by a deflector and vacuum boxes.
  • the embryonic wet web is transferred from the S-wrap twm-wire former, at a fiber consistency of about 15% at the point of transfer, to a drying fabnc.
  • a suitable drying fabnc is a needle punched batt with a tnlayer base fabnc as is available from Albany International of Albany, NY as TRIO VENT. Further dewatenng is accomplished by vacuum assisted drainage until the web has a fiber consistency of about 28%.
  • the semi-dry web is then adhered to the surface of a Yankee dryer with a sprayed creping adhesive compnsmg a mixture of polyv yl alcohol and a polyamide based resin.
  • the creping adhesive is delivered to the Yankee surface at a rate of 0.125% adhesive solids based on the dry weight of the web
  • the doctor blade has a bevel angle of about 20 degrees and is positioned with respect to the Yankee dryer to provide an impact angle of about 76 degrees.
  • the percent crepe is adjusted to about 21-25% by operating the Yankee dryer at a speed of about 1000 fpm (feet per mmute) (about 305 meters per minute), while the dry web is formed into roll at a speed of about 770 fpm (235 meters per minutes).
  • the tissue paper has a basis weight of about 10 pounds/3000 ft 2 (16 grams/m 2 ), contains about 0.1% of the substantially waterless self-emulsifiable chemical softener mixture and about 0.1% of the wet strength resin. Importantly, the resulting tissue paper is soft, absorbent and is suitable for use as a facial and/or toilet tissues.
  • the purpose of this example is to illustrate a method using a conventional drying papermaking technique to make soft and absorbent tissue paper treated with a low viscosity chemical softener composition prepared according to Example 1 of the present invention and a wet strength res .
  • the makeup of the furnish is substantially the same as that used in Example 1, the only exception being that a 2.5 % dispersion of the chemical softener mixture from Example 1 was used instead of the pnor art chemical softening composition.
  • the separate furnishes are delivered to a headbox, deposited on a twm-wire former and dned in substantially the same manner as desc ⁇ bed in Example 1 to form a dned tissue web.
  • the tissue paper has a basis weight of about 10 pounds/3000 ft 2 (16 grams/m 2 ), contains about 0.05% of the substantially waterless self-emulsifiable chemical softener mixture and about 0.1% of the wet strength resin. Importantly, the resulting tissue paper is soft, absorbent and is suitable for use as a facial and/or toilet tissues.
  • Example 5
  • tissue papers made m Examples 3 and 4 have substantially the same physical properties
  • Analysis of the amounts of softening active ingredients descnbed herein that are retained on cellulosic structures can be performed by any method accepted in the applicable art. These methods are exemplary, and are not meant to exclude other methods which may be useful for determining levels of particular components retained by the tissue paper.
  • the following method is approp ⁇ ate for determining the quantity of the preferred quaternary ammonium compounds (QAC) that may deposited by the method of the present invention.
  • a standard anionic surfactant sodium dodecylsulfate — NaDDS
  • Preparation of Standard Solutions The following methods are applicable for the preparation of the standard solutions used in this titration method
  • Method 1 On an analytical balance, weigh approximately 0 5 grams of a specimen of the cellulosic fiber structure. Record the sample weight to the nearest 0.1 mg
  • X is a blank correction obtained by titrating a specimen without the QAC of the present invention.
  • the density of a cellulosic structure is the average density calculated as the basis weight of that paper divided by the caliper, with the approp ⁇ ate unit conversions incorporated therein.
  • Caliper of the paper is the thickness of the paper when subjected to a compressive load of 95 g/m 2 (15.5 g/cm 2 ).
  • This method is intended for use on finished paper products, reel samples, and unconverted stocks.
  • the tensile strength of such products may be determined on one inch wide st ⁇ ps of sample using a Thwing-Albert Intelect II Standard Tensile Tester (Thwing-Albert Instrument Co of Philadelphia, PA).
  • the paper samples to be tested Prior to tensile testing, the paper samples to be tested should be conditioned for at least 15 minutes at a relative humidity of 48 to 52% and within a temperature range of 22 to 24 °C. Sample preparation and all aspects of the tensile testing should also take place within the confines of the constant temperature and humidity room.
  • Thwing-Albert Intelect II Standard Tensile Tester Thiwing-Albert Instrument Co. of Philadelphia, PA. Insert the flat face clamps into the unit and calibrate the tester according to the instructions given the operation manual of the Thwing-Albert Intelect II. Set the instrument crosshead speed to 4.00 in/mm and the 1st and 2nd gauge lengths to 2.00 inches. The break sensitivity should be set to 20.0 grams and the sample width should be set to 1.00" and the sample thickness at 0.025". A load cell is selected such that the predicted tensile result for the sample to be tested lies between 25% and 75% of the range in use.
  • a 5000 gram load cell may be used for samples with a predicted tensile range of 1250 grams (25% of 5000 grams) and 3750 grams (75% of 5000 grams).
  • the tensile tester can also be set up in the 10% range with the 5000 gram load cell such that samples with predicted tensiles of 125 grams to 375 grams could be tested. Take one of the tensile st ⁇ ps and place one end of it in one clamp of the tensile tester.
  • the tensile strength should be converted into a "specific total tensile strength" defined as the sum of the tensile strength measured in the machine and cross machine directions, divided by the basis weight, and corrected in units to a value in meters.
  • Viscosity is measured at a shear rate of 100 (s"l) using a rotational viscometer.
  • the samples are subjected to a linear stress sweep, which applies a range of stresses, each at a constant amplitude.
  • Method Place the sample on the sample plate with the gap open. Close the gap and operate the rheometer according to the manufacturer's instructions to measure viscosity as a function of shear stress between the initial shear stress and the final shear stress using the stress increment defined above.

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Abstract

L'invention concerne une composition permettant d'adoucir une structure cellulosique voie humide (de préférence, papier de soie absorbant). L'invention concerne d'autres structures adoucies par le biais de cette composition, qui comprend une quantité efficace de principe actif adoucissant; un vecteur de dispersion de ce principe actif; un électrolyte dissous dans le vecteur; et un dislocateur de bicouche. L'électrolyte et le dislocateur de bicouche coopèrent pour réduire la viscosité de la composition par rapport celle d'une dispersion du même principe actif dans le vecteur seul. De préférence, le principe actif est un composé à base d'ammonium quaternaire représenté par la formule: (R1)4-m-N+-[(CH2)n-Y-R3]m X-; le vecteur est de l'eau, l'électrolyte est du chlorure de calcium, et le dislocateur de bicouche est un tensioactif non ionique. L'invention concerne également un procédé relatif à l'utilisation du composé, sous forme d'adjonction suivant une concentration d'utilisation à l'extrémité voie humide d'un processus de fabrication du papier.
PCT/US1999/023592 1998-10-15 1999-10-08 Procede relatif a la fabrication de papier de soie doux WO2000022233A1 (fr)

Priority Applications (7)

Application Number Priority Date Filing Date Title
AU64240/99A AU753313B2 (en) 1998-10-15 1999-10-08 Process for making soft tissue paper
CA002346658A CA2346658C (fr) 1998-10-15 1999-10-08 Procede relatif a la fabrication de papier de soie doux
EP99951897A EP1131486B1 (fr) 1998-10-15 1999-10-08 Procede relatif a la fabrication de papier de soie doux
AT99951897T ATE245724T1 (de) 1998-10-15 1999-10-08 Verfahren zur herstellung von weichem seidenpapier
BR9914577-4A BR9914577A (pt) 1998-10-15 1999-10-08 Processo para fabricar papel fino macio
JP2000576116A JP2002527641A (ja) 1998-10-15 1999-10-08 柔らかいティッシュ・ペーパーを製造する方法
DE69909821T DE69909821T2 (de) 1998-10-15 1999-10-08 Verfahren zur herstellung von weichem seidenpapier

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
US10437198P 1998-10-15 1998-10-15
US60/104,371 1998-10-15
US13733699P 1999-06-03 1999-06-03
US60/137,336 1999-06-03

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JP (1) JP2002527641A (fr)
KR (1) KR20010085925A (fr)
CN (1) CN1323368A (fr)
AR (1) AR016741A1 (fr)
AT (1) ATE245724T1 (fr)
AU (1) AU753313B2 (fr)
BR (1) BR9914577A (fr)
CA (1) CA2346658C (fr)
DE (1) DE69909821T2 (fr)
ES (1) ES2203192T3 (fr)
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Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2002048458A1 (fr) * 2000-12-15 2002-06-20 The Procter & Gamble Company Papier hygienique doux contenant une composition adoucissante sur laquelle est depose un modificateur de viscosite extensionel
WO2007063182A2 (fr) 2005-12-01 2007-06-07 Metso Paper, Inc. Procede pour la fabrication de papier
US7282116B2 (en) * 1998-10-15 2007-10-16 The Procter & Gamble Company Paper softening compositions containing bilayer disrupter
US7311853B2 (en) 2002-09-20 2007-12-25 The Procter & Gamble Company Paper softening compositions containing quaternary ammonium compound and high levels of free amine and soft tissue paper products comprising said compositions
US7432309B2 (en) 2002-10-17 2008-10-07 The Procter & Gamble Company Paper softening compositions containing low levels of high molecular weight polymers and soft tissue paper products comprising said compositions
WO2008135900A2 (fr) * 2007-05-03 2008-11-13 The Procter & Gamble Company Lingettes dont une surface est enduite d'un agent adoucissant
WO2008135901A2 (fr) * 2007-05-03 2008-11-13 The Procter & Gamble Company Lingette dont une surface est enduite d'un agent adoucissant chimique
US11286620B2 (en) 2019-01-11 2022-03-29 The Procter & Gamble Company Quaternary ammonium compound compositions and methods for making and using same

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Publication number Priority date Publication date Assignee Title
CN101831845B (zh) * 2010-06-08 2011-07-13 泉州华祥纸业有限公司 废纸脱墨浆生产薄页包装纸的制造方法
US8518214B2 (en) * 2011-07-18 2013-08-27 Nalco Company Debonder and softener compositions
JP6217002B2 (ja) * 2013-05-20 2017-10-25 デュプロ精工株式会社 抄紙装置、製紙機及び抄紙方法
TW201734278A (zh) * 2016-03-24 2017-10-01 金百利克拉克國際公司 包含軟化組成物之紙巾

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US5573637A (en) * 1994-12-19 1996-11-12 The Procter & Gamble Company Tissue paper product comprising a quaternary ammonium compound, a polysiloxane compound and binder materials
US5753079A (en) * 1995-04-27 1998-05-19 Witco Corporation Obtaining enhanced paper production using cationic compositions containing diol and/or diol alkoxylate
US5814188A (en) * 1996-12-31 1998-09-29 The Procter & Gamble Company Soft tissue paper having a surface deposited substantive softening agent

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NZ268169A (en) * 1993-06-03 1997-11-24 Procter & Gamble Waterless self-emulsifiable chemical softening composition comprising ester functional quaternary ammonium compound and at least one of glycerol, polyglycerols and polyoxyethylene (or propylene)
US5405501A (en) * 1993-06-30 1995-04-11 The Procter & Gamble Company Multi-layered tissue paper web comprising chemical softening compositions and binder materials and process for making the same
KR100333211B1 (ko) * 1993-06-30 2002-11-04 더 프록터 앤드 갬블 캄파니 생분해성화학연화제조성물및결합제를포함하는다층의티슈종이웹,및이를포함하는제품
JP3235928B2 (ja) * 1993-12-28 2001-12-04 花王株式会社 紙用柔軟剤
US5415737A (en) * 1994-09-20 1995-05-16 The Procter & Gamble Company Paper products containing a biodegradable vegetable oil based chemical softening composition
EP0896045A1 (fr) * 1997-08-06 1999-02-10 Akzo Nobel N.V. Une composition pour le traitement des matériaux cellulosiques

Patent Citations (3)

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Publication number Priority date Publication date Assignee Title
US5573637A (en) * 1994-12-19 1996-11-12 The Procter & Gamble Company Tissue paper product comprising a quaternary ammonium compound, a polysiloxane compound and binder materials
US5753079A (en) * 1995-04-27 1998-05-19 Witco Corporation Obtaining enhanced paper production using cationic compositions containing diol and/or diol alkoxylate
US5814188A (en) * 1996-12-31 1998-09-29 The Procter & Gamble Company Soft tissue paper having a surface deposited substantive softening agent

Cited By (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US7282116B2 (en) * 1998-10-15 2007-10-16 The Procter & Gamble Company Paper softening compositions containing bilayer disrupter
WO2002048458A1 (fr) * 2000-12-15 2002-06-20 The Procter & Gamble Company Papier hygienique doux contenant une composition adoucissante sur laquelle est depose un modificateur de viscosite extensionel
US7311853B2 (en) 2002-09-20 2007-12-25 The Procter & Gamble Company Paper softening compositions containing quaternary ammonium compound and high levels of free amine and soft tissue paper products comprising said compositions
US7432309B2 (en) 2002-10-17 2008-10-07 The Procter & Gamble Company Paper softening compositions containing low levels of high molecular weight polymers and soft tissue paper products comprising said compositions
WO2007063182A2 (fr) 2005-12-01 2007-06-07 Metso Paper, Inc. Procede pour la fabrication de papier
WO2007063182A3 (fr) * 2005-12-01 2007-08-02 Metso Paper Inc Procede pour la fabrication de papier
WO2008135900A2 (fr) * 2007-05-03 2008-11-13 The Procter & Gamble Company Lingettes dont une surface est enduite d'un agent adoucissant
WO2008135901A2 (fr) * 2007-05-03 2008-11-13 The Procter & Gamble Company Lingette dont une surface est enduite d'un agent adoucissant chimique
WO2008135900A3 (fr) * 2007-05-03 2009-04-09 Procter & Gamble Lingettes dont une surface est enduite d'un agent adoucissant
WO2008135901A3 (fr) * 2007-05-03 2009-04-09 Procter & Gamble Lingette dont une surface est enduite d'un agent adoucissant chimique
US11286620B2 (en) 2019-01-11 2022-03-29 The Procter & Gamble Company Quaternary ammonium compound compositions and methods for making and using same

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DE69909821T2 (de) 2004-05-27
ES2203192T3 (es) 2004-04-01
ATE245724T1 (de) 2003-08-15
KR20010085925A (ko) 2001-09-07
DE69909821D1 (de) 2003-08-28
PE20001215A1 (es) 2001-01-12
AU753313B2 (en) 2002-10-17
AR016741A1 (es) 2001-07-25
NO20011806L (no) 2001-06-15
TW505721B (en) 2002-10-11
MX254453B (en) 2008-02-11
CA2346658A1 (fr) 2000-04-20
CA2346658C (fr) 2005-12-06
BR9914577A (pt) 2001-07-03
EP1131486B1 (fr) 2003-07-23
MXPA01003751A (es) 2001-07-01
NO20011806D0 (no) 2001-04-09
AU6424099A (en) 2000-05-01
JP2002527641A (ja) 2002-08-27
EP1131486A1 (fr) 2001-09-12
CN1323368A (zh) 2001-11-21

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