WO1994029520A1 - Composition d'adoucissant chimique autoemulsifiant sans eau pour produits cellulosiques fibreux - Google Patents

Composition d'adoucissant chimique autoemulsifiant sans eau pour produits cellulosiques fibreux Download PDF

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Publication number
WO1994029520A1
WO1994029520A1 PCT/US1994/005777 US9405777W WO9429520A1 WO 1994029520 A1 WO1994029520 A1 WO 1994029520A1 US 9405777 W US9405777 W US 9405777W WO 9429520 A1 WO9429520 A1 WO 9429520A1
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WIPO (PCT)
Prior art keywords
quaternary ammonium
chemical softening
compound
mixture
softening composition
Prior art date
Application number
PCT/US1994/005777
Other languages
English (en)
Inventor
Robert Gene Laughlin
Dean Van Phan
Paul Dennis Trokhan
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 KR1019950705460A priority Critical patent/KR100336444B1/ko
Priority to AU69559/94A priority patent/AU694433B2/en
Priority to BR9406738A priority patent/BR9406738A/pt
Priority to DE69423352T priority patent/DE69423352T2/de
Priority to NZ267305A priority patent/NZ267305A/en
Priority to EP94918091A priority patent/EP0701640B1/fr
Publication of WO1994029520A1 publication Critical patent/WO1994029520A1/fr
Priority to NO954868A priority patent/NO954868L/no
Priority to FI955789A priority patent/FI955789A/fi
Priority to HK98114419A priority patent/HK1013134A1/xx

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Classifications

    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H17/00—Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
    • D21H17/03—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
    • D21H17/03—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
    • 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
    • D21H21/24—Surfactants

Definitions

  • This invention relates to a substantially waterless self-emulsifiable chemical softener composition. More particularly, it relates to substantially waterless self-emulsifiable chemical softener compositions useful for treating fibrous cellulose materials, such as tissue paper webs.
  • the treated tissue webs can be used to make soft, absorbent paper products such as toweling, napkin, facial tissue, and toilet tissue products.
  • Paper webs or sheets sometimes called tissue or paper tissue webs or sheets, find extensive use in modern society. Such items as paper towels, napkins, facial and toilet tissues are staple items of commerce. It has long been recognized that three important physical attributes of these products are their softness; their absorbency, particularly their absorbency for aqueous systems; and their strength, particularly their strength when wet. Research and development efforts have been directed to the improvement of each of these attributes without seriously affecting the others as well as to the improvement of two or three attributes simultaneously.
  • Softness is the tactile sensation perceived by the consumer as he/she holds a particular product, rubs it across his/her skin, or crumples it within his/her hand. This tactile sensation is provided by a combination of several physical properties.
  • One of the most important physical properties related to softness is generally considered by those skilled in the art to be the stiffness of the paper web from which the product is made. Stiffness, in turn, is usually considered to be directly dependent on the dry tensile strength of the web and the stiffness of the fibers which make up the web.
  • Strength is the ability of the product, and its constituent webs, to maintain physical integrity and to resist tearing, bursting, and shredding under use conditions, particularly when wet.
  • Absorbency is the measure of the ability of a product, and its constituent webs, to absorb quantities of liquid, particularly aqueous solutions or dispersions. Overall absorbency as perceived by the consumer is generally considered to be a combination of the total quantity of liquid a given mass of tissue paper will absorb at saturation as well as the rate at which the mass absorbs the liquid.
  • wet strength resins to enhance the strength of a paper web is widely known.
  • Westfelt described a number of such materials and discussed their chemistry in Cellulose Chemistry and Technology, Volume 13, at pages 813-825 (1979).
  • Freimark et al. go on to teach the use of wet strength resins in conjunction with the use of debonding agents to off ⁇ set the undesirable effects of the debonding agents. These debonding agents do reduce both dry tensile strength and wet tensile strength.
  • Chemical debonding agents have been disclosed in various references such as U.S. Pat. No. 3,554,862, issued to Hervey et al. on January 12, 1971 . These materials include quaternary ammonium salts such as cocotrimethylammonium chloride, oleyltrimethylammonium chloride, di(hydrogenated)tallow dimethyl ammonium chloride and stearyltrimethyl ammonium chloride.
  • Armak Company of Chicago, Illinois, in their bulletin 76-17 (1977) disclose the use of dimethyl di(hydrogenated)tallow ammonium chloride in combination with fatty acid esters of polyoxyethylene glycols to impart both softness and absorbency to tissue paper webs.
  • quaternary ammonium compounds such as the well known dialkyl dimethyl ammonium salts (e.g. ditallow dimethyl ammonium chloride, ditallow dimethyl ammonium methyl sulfate, di(hydrogenated)tallow dimethyl ammonium chloride etc ). are effective chemical debonding agents. Unfortunately, these quaternary ammonium compounds are not hydrophilic. Applicants have discovered that the chemical softening compositions of the present invention enhance both softness and absorbency rate of fibrous cellulose materials.
  • dialkyl dimethyl ammonium salts e.g. ditallow dimethyl ammonium chloride, ditallow dimethyl ammonium methyl sulfate, di(hydrogenated)tallow dimethyl ammonium chloride etc .
  • the present invention also provides environmental safety advantages because of the elimination of the organic solvents, especially volatile organic solvents typically used in the preparation of concentrated softening compositions.
  • the present invention provides a substantially waterless self- emulsifiable chemical softening composition useful for treating fibrous cellulose materials.
  • the waterless self-emulsifiable chemical softening composition comprises a mixture of :
  • each R2 substituent is a C1 - C6 alkyl or hydroxyalkyl group, or mixture thereof; each Ri substituent is a C14 - C22 hydrocarbyl group, or mixture thereof; and X" is a suitable anion; and
  • a polyhydroxy compound selected from the group consisting of glycerol, polyglycerols having a weight average molecular weight of from about 150 to about 800 and polyoxyethylene glycols and polyoxypropylene glycols having a weight average molecular weight from about 200 to 4000;
  • the chemical softening composition of the present invention is a stable, homogenous, solid or viscous fluid at a temperature greater than or about 20°C .
  • the fluid may have either a liquid or a liquid crystal phase structure.
  • the moisture content of the substantially self-emulsifiable chemical softening composition is less than about 20 % by weight, preferably the moisture content of the chemical softening composition is less than about 10 % by weight and more preferably the moisture content of the chemical softening composition is less than 5 % by weight.
  • quaternary ammonium compounds suitable for use in the present invention include the well-known dialkyldimethylammonium salts such as DiTallow DiMethyl Ammonium Chloride (DTDMAC), DiTallow DiMethyl Ammonium Methyl Sulfate (DTDMAMS), Di(Hydrogenated)Tallow DiMethyl Ammonium Methyl Sulfate (DHTDMAMS), Di(Hydrogenated)Tallow DiMethyl Ammonium Chloride (DHTDMAC).
  • DTDMAC DiTallow DiMethyl Ammonium Chloride
  • DTDMAMS DiTallow DiMethyl Ammonium Methyl Sulfate
  • DHTDMAMS Di(Hydrogenated)Tallow DiMethyl Ammonium Methyl Sulfate
  • DHTDMAC Di(Hydrogenated)Tallow DiMethyl Ammonium Chloride
  • polyhydroxy compounds useful in the present invention include glycerol, polyglycerols having a weight average molecular weight of from about 150 to about 800 and polyoxyethylene glycols having a weight average molecular weight of from about 200 to about 4000, with polyoxyethylene glycols having a weight average molecular weight of from about 200 to about 600 being preferred.
  • the process for making the tissue webs of the present invention comprises the steps of formation of a papermaking furnish from the aforementioned components, deposition of the papermaking furnish onto a foraminous surface such as a Fourdrinier wire, and removal of the water from the deposited furnish.
  • Figure 1 are the phase diagrams of DiOctadecyl DiMethyl Ammonium Methyl Sulfate (DODMAMS) and of DHTDMAMS.
  • Figure 2 is a phase diagram of the DODMAMS / PEG-400 system.
  • Figure 3 is a cryo-transmission photo-micrograph taken at X 63,000 of the 2% dispersion formed by diluting a solid premix of a 1 : 1 by weight ratio of a DHTDMAMS and PEG-400 system.
  • Figure 4 is a cryo-transmission photo-micrograph taken at X 63,000 of the 2% dispersion formed by diluting a liquid premix of a 1 : 1 by weight ratio of a DHTDMAMS and PEG-400 system.
  • Figure 5 is a cryo-transmission photo-micrograph taken at X 63,000 of the 2% dispersion formed by diluting a liquid premix of a 1 : 1 by weight ratio of a DHTDMAC and a mixture of glycerol and PEG-400 system.
  • viscous fluid refers to a fluid having a viscosity greater than or equal to 10,000 centipoise at 20°C.
  • homogenous mixture refers to compositions wherein the quaternary ammonium and polyhydroxy compounds are dissolved or dispersed in each other.
  • self-emulsifiable refers to compositions that will form a uniform colloidal dispersion with a minimum of shear, heat, dispersing aids, etc. ... when added to a liquid carrier such as water.
  • tissue paper web, paper web, web, paper sheet and paper product all refer to sheets of paper made by a process comprising the steps of forming an aqueous papermaking furnish, depositing this furnish on a foraminous surface, such as a Fourdrinier wire, and removing the water from the furnish as by gravity or vacuum-assisted drainage, with or without pressing, and by evaporation.
  • an "aqueous papermaking furnish” is an aqueous slurry of papermaking fibers and the chemicals described hereinafter.
  • the first step in the process of this invention is the forming of an aqueous papermaking furnish.
  • the furnish comprises papermaking fibers (hereinafter sometimes referred to as wood pulp), and a mixture of at least one quaternary ammonium compound and at least one polyhydroxy compound, all of which will be hereinafter described.
  • wood pulp in all its varieties will normally comprise the papermaking fibers used in this invention.
  • wood pulps useful herein include chemical pulps such as Kraft, sulfite and sulfate pulps as well as mechanical pulps including for example, ground wood, thermomechanical pulps and chemically modified thermomechanical pulp (CTMP).
  • CMP chemically modified thermomechanical pulp
  • Pulps derived from both deciduous and coniferous trees can be used.
  • fibers derived from recycled paper which may contain any or all of the above categories as well as other non-fibrous materials such as fillers and adhesives used to facilitate the original papermaking.
  • the papermaking fibers used in this invention comprise Kraft pulp derived from northern softwoods. Waterless Self-emulsifiable Chemical Softener Compositions
  • the present invention contains as an essential component a mixture of a quaternary ammonium compound and a polyhydroxy compound.
  • the ratio of the quaternary ammonium compound to the polyhydroxy compound ranges from about 1 : 0.1 to 0.1 : 1 ; preferably, the weight ratio of the quaternary ammonium compound to the polyhydroxy compound is about 1 : 0.3 to 0.3 : 1 ; more preferably, the weight ratio of the quaternary ammonium compound to the polyhydroxy compound is about 1 : 0.7 to 0.7 : 1 , although this ratio will vary depending upon the molecular weight of the particular polyhydroxy compound and/or quaternary ammonium compound used.
  • the substantially waterless self-emulsifiable chemical softening composition contains as an essential component a quaternary ammonium compound having the formula :
  • each Ri is C14-C22 hydrocarbon group, preferably tallow
  • R2 is a C1 - C6 alkyl or hydroxyalkyl group, preferably C1 -C3 alkyl
  • X " is a suitable anion, such as an halide (e.g. chloride or bromide) or methyl sulfate.
  • tallow is a naturally occurring material having a variable composition. Table 6.13 in the above-identified reference edited by Swern indicates that typically 78% or more of the fatty acids of tallow contain 16 or 18 carbon atoms.
  • each Ri is C16-C18 alkyl, most preferably each Ri is straight-chain C18 alkyl.
  • each R2 is methyl and X" is chloride or methyl sulfate.
  • quaternary ammonium compounds suitable for use in the present invention include the well-known dialkyldimethylammonium salts such as ditallow dimethyl ammonium chloride, ditallow dimethylammonium methyl sulfate, di(hydrogenated)tallow dimethyl ammonium chloride; with di(hydrogenated)tallow dimethyl ammonium methyl sulfate being preferred.
  • This particular material is available commercially from Sherex Chemical Company Inc. of Dublin, Ohio under the tradename "Varisoft ® 137".
  • the chemical softening composition contains as an essential component a polyhydroxy compound.
  • polyhydroxy compounds useful in the present invention include glycerol, polyglycerols having a weight average molecular weight of from about 150 to about 800 and polyoxyethylene glycols and polyoxypropylene glycols having a weight average molecular weight of from about 200 to about 4000, preferably from about 200 to about 1000, most preferably from about 200 to about 600.
  • Polyoxyethylene glycols having an weight average molecular weight of from about 200 to about 600 are especially preferred.
  • Mixtures of the above-described polyhydroxy compounds may also be used.
  • mixtures of glycerol and polyoxyethylene glycols having a weight average molecular weight from about 200 to 1000, more preferably from about 200 to 600 are useful in the present invention.
  • the weight ratio of glycerol to polyoxyethylene glycol ranges from about 10 : 1 to 1 : 10.
  • a particularly preferred polyhydroxy compound is polyoxyethylene glycol having an weight average molecular weight of about 400. This material is available commercially from the Union Carbide Company of Danbury, Connecticut under the tradename "PEG- 400".
  • the waterless self-emulsifiable chemical softening composition described above i.e. mixture of a quaternary ammonium compounds and a polyhydroxy compound are preferably diluted to a desired concentration to form a dispersion of the quat and polyhydroxy compounds before being added to the aqueous slurry of papermaking fibers, or furnish, in the wet end of the papermaking machine at some suitable point ahead of the Fourdrinier wire or sheet forming stage.
  • applications of the above described chemical softening composition subsequent to formation of a wet tissue web and prior to drying of the web to completion will also provide significant softness, absorbency, and wet strength benefits and are expressly included within the scope of the present invention.
  • the chemical softening composition is more effective when the quaternary ammonium compound and the polyhydroxy compound are first pre-mixed together before being added to the papermaking furnish.
  • a preferred method consists of first heating the polyhydroxy compound to a temperature of about 66°C (150°F), and then adding the quaternary ammonium compound to the hot polyhydroxy compound to form a homogenous fluid.
  • the weight ratio of the quaternary ammonium compound to the polyhydroxy compound ranges from about 1 : 0.1 to 0.1 : 1 ; preferably, the weight ratio of the quaternary ammonium compound to the compound is about 1 : 0.3 to 0.3 : 1 ; more preferably, the weight ratio of the quaternary ammonium compound to the compound is about 1 : 0.7 to 0.7 : 1 , although this ratio will vary depending upon the molecular weight of the particular compound and/or quaternary ammonium compound used.
  • the moisture content of the chemical softening composition is less than about 20 % by weight, preferably the moisture content of the chemical softening composition is less than about 10 % by weight and more preferably the moisture content of the chemical softening composition is less than 5 % by weight.
  • the chemical softening composition is a stable, homogenous, solid or viscous fluid at a temperature greater than or about 20°C .
  • the substantially waterless self-emulsifiable chemical softener composition can be pre-mixed at the chemical supplier (e.g. Sherex company of Dublin, Ohio).
  • the chemical supplier e.g. Sherex company of Dublin, Ohio.
  • Providing chemical softening compositions containing these softener compounds in substantially waterless forms results in cost saving on shipping the product (less weight), cost savings on packaging material and cost savings on machinery for processing the chemical softening compositions (less equipment needed to make-up the aqueous dispersion).
  • the present invention also provides environmental safety advantages because of the elimination of the organic solvents, especially volatile organic solvents.
  • the ultimate users of the chemical softening composition simply dilute the mixture with a liquid carrier (i.e., water) to form an aqueous dispersion of the quaternary ammonium compound / polyhydroxy compound mixture, which is then added to the papermaking furnish.
  • a liquid carrier i.e., water
  • the homogenous mixture of the quaternary ammonium compound and the polyhydroxy compound can exist either in a solid state or in a fluid state before being dispersed in the aqueous media.
  • the mixture of the quaternary ammonium compound and polyhydroxy compound is diluted with a liquid carrier such as water to a concentration of from about 0.01 % to about 25% by weight of the softening composition before being added to the papermaking furnish.
  • the temperature of the liquid carrier preferably ranges from about 20°C to about 80°C.
  • the quaternary ammonium compound and the polyhydroxy compound are present as particles dispersed in the liquid carrier.
  • the average particle size preferably ranges from about 0.01 to 10 microns, most preferably from about 0.1 to about 1 .0 micron. As shown in Figures 3 - 5, the dispersed particles are in the form of either closed vesicles or open particles.
  • the adsorption of the polyhydroxy compound onto paper is significantly enhanced when it is premixed with the quaternary ammonium compound and added to the paper by the above described process.
  • at least 20% of the polyhydroxy compound and the quaternary ammonium compound added to the fibrous cellulose are retained; preferably, the retention level of quaternary ammonium compound and the polyhydroxy compound is from about 50% to about 90% of the added levels.
  • adsorption occurs at a concentration and within a time frame that are practical for use during paper making.
  • DHTDMAMS Di(Hydrogenated)Tailow DiMethyl Ammonium Methyl Sulfate
  • polyoxyethylene glycol 400 were studied.
  • DODMAMS may exist in any of four phase states ( Figure 1 ): two polymorphic crystals (X ⁇ and X ⁇ ), a lamellar (Lam) liquid crystal, or a liquid phase.
  • the XP crystal exists from below room temperature to 47 °C. At this temperature it is transformed into the polymorphic X ⁇ crystal, which at 72°C is transformed into the Lam liquid crystal phase. This phase, in turn, is transformed into an isotropic liquid at 150°C.
  • DHTDMAMS is expected to resemble DODMAMS in its physical behavior, except that the temperatures of the phase transitions will be lowered and broadened.
  • the transition from the x ⁇ to the X ⁇ crystal occurs at 27°C in DHTDMAMS instead of 47°C as in DODMAMS.
  • calorimetric data indicate that several crystal 0 Lam phase transitions occur in DHTDMAMS rather than one as in DODMAMS. The onset temperature of the highest of these transitions is 56°C, in good agreement with the X-ray data.
  • DODMAC DiOctadecyl DiMethyl Ammonium Chloride
  • a 1 : 1 weight ratio mixture of these two materials is studied, and a plausible model for the phase behavior of this system is suggested in Figure 2.
  • DODMAMS and PEG are shown to be immiscible at high temperatures, where they coexist as two liquid phases. As mixtures of the two liquids within this region are cooled, a Lam phase separates from the mixture. This study therefore shows that these two materials, while immiscible at high temperatures do become miscible at lower temperatures within the Lam liquid crystal phase. At still lower temperatures crystal phases are expected to separate from the Lam phase, and the compounds are again immiscible.
  • Dispersions of either of these materials may be prepared by diluting a premix, that is held at a temperature at which the polyhydroxy compound and the quaternary ammonium salt are miscible, with water. It does not matter greatly whether they are miscible as a liquid crystalline phase (as in the case of DHTDMAMS), or as a liquid phase (as in the case of DHTDMAC). Neither DHTDMAMS nor DHTDMAC are soluble in water, so that dilution of either dry phase with water will precipitate the quaternary ammonium compound as small particles. Both quaternary ammonium compounds will precipitate at elevated temperatures as a liquid-crystal phase in dilute aqueous solutions, regardless of whether the dry solution was liquid or liquid crystalline. The polyhydroxy compound is soluble with water in all proportions, so is not precipitated.
  • Cryoelectron microscopy demonstrates that the particles present in the dispersion are about 0.1 to 1.0 micrometers in size, and highly varied in structure. Some are sheets (curved or flat), while others are closed vesicles. The membranes of all these particles are bilayers of molecular dimensions in which the head groups are exposed to water, the tails are together. The PEG is presumed to be associated with these particles.
  • the application of dispersions prepared in this manner to paper results in attachment of the quaternary ammonium ion to the paper, strongly promotes the adsorption of the polyhydroxy compound onto paper, and produces the desired enhancement of softness with retention of wettability. State of the dispersions.
  • the vesicles containing DHTDMAMS and PEG break apart upon drying of the fibrous cellulosic material. Once the vesicle is broken, the majority of the PEG component may penetrate into the interior of the cellulose fibers where it enhances the fiber flexibility. Importantly, some of the PEG is retained on the surface of the fiber where it acts to enhance the absorbency rate of the cellulose fibers. Due to ionic interactions, the majority of the DHTDMAMS component stays on the surface of the cellulose fiber, where it enhances the surface feel and softness of the paper product.
  • the second step in the process of this invention is the depositing of the papermaking furnish using the above described chemical softener composition as an additive on a foraminous surface and the third step is the removing of the water from the furnish so deposited.
  • Techniques and equipment which can be used to accomplish these two processing steps will be readily apparent to those skilled in the papermaking art.
  • Preferred tissue paper embodiments of the present invention contain from about 0.005% to about 5.0%, more preferably from about 0.03% to 0.5% by weight, on a dry fiber basis of the chemical softening composition described herein.
  • the present invention is applicable to tissue paper in general, including but not limited to conventionally felt-pressed tissue paper; high bulk pattern densified tissue paper; and high bulk, uncompacted tissue paper.
  • 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.
  • Tissue structures formed from layered paper webs are described in U.S. Patent 3,994,771 , Morgan, Jr. et al. issued November 30, 1976, and incorporated herein by reference.
  • a wet-laid composite, soft, bulky and absorbent paper structure is prepared from two or more layers of furnish which are preferably comprised of different fiber types.
  • the layers are preferably formed from the deposition of separate streams of dilute fiber slurries, the fibers typically being relatively long softwood and relatively short hardwood fibers as used in tissue papermaking, upon one or more endless foraminous screens.
  • the layers are subsequently combined to form a layered composite web.
  • the layered web is subsequently caused to conform to the surface of an open mesh drying/imprinting fabric by the application of a fluid force to the web and thereafter thermally predried on said fabric as part of a low density papermaking process.
  • the layered web may be stratified with respect to fiber type or the fiber content of the respective layers may be essentially the same.
  • the tissue paper preferably has a basis weight of between 10 g/m ⁇ and about 65 g/m 2 , and density of about 0.60 g/cm 3 or less.
  • basis weight will be below about 35 g/m 2 or less; and density will be about 0.30 g/cm ⁇ or less.
  • density will be between 0.04 g/c ⁇ .3 and about 0.20 g/cm 3 .
  • Such paper is typically made by depositing papermaking furnish on a foraminous forming wire.
  • This forming wire is often referred to in the art as a Fourdrinier wire.
  • the furnish is deposited on the forming wire, it is referred to as a web.
  • the web is dewatered by transferring to a dewatering felt, pressing the web and drying at elevated temperature.
  • the particular techniques and typical equipment for making webs according to the process just described are well known to those skilled in the art.
  • a , low consistency pulp furnish is provided in a pressurized headbox.
  • the headbox has an opening for delivering a thin deposit of pulp furnish onto the Fourdrinier wire to form a wet web.
  • the web is then typically dewatered to a fiber consistency of between about 7% and about 25% (total web weight basis) by vacuum dewatering and further dewatered 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 during transfer and being dried by a stream drum apparatus known in the art as a Yankee dryer.
  • Pressure can be developed at the Yankee dryer by mechanical means such as an opposing cylindrical drum pressing against the web. Vacuum may also be applied to the web as it is pressed against the Yankee surface. Multiple Yankee dryer drums may be employed, whereby additional pressing is optionally incurred between the drums.
  • the tissue paper structures which are formed are referred to hereinafter as conventional, pressed, tissue paper structures. Such sheets are considered to be compacted since the web is subjected to substantial mechanical compression forces while the fibers are moist and are then dried while in a compressed state.
  • Pattern densified tissue paper is characterized by having a relatively high bulk field of relatively low fiber density and an array of densified zones of relatively high fiber density.
  • the high bulk field is alternatively characterized as a field of pillow regions.
  • the densified zones are alternatively referred to as knuckle regions.
  • the densified zones may be discretely spaced within the high bulk field or may be interconnected, either fully or partially, within the high bulk field.
  • Preferred processes for making pattern densified tissue webs are disclosed in U.S. Patent No. 3,301 ,746, issued to Sanford and Sisson on January 31 , 1967, U.S. Patent No. 3,974,025, issued to Peter G. Ayers on August 10, 1976, and U.S. Patent No.
  • pattern densified webs are preferably prepared by depositing a papermaking furnish on a foraminous forming wire such as a Fourdrinier wire to form a wet web and then juxtaposing the web against an array of supports.
  • the web is pressed against the array of supports, thereby resulting in densified zones in the web at the locations geographically corresponding to the points of contact between the array of supports and the wet web.
  • the remainder of the web not compressed during this operation is referred to as the high bulk field.
  • This high bulk field can be further dedensified by application of fluid pressure, such as with a vacuum type device or a blow-through dryer.
  • the web is dewatered, and optionally predried, in such a manner so as to substantially avoid compression of the high bulk field.
  • the web is dried to completion, preferably still avoiding mechanical pressing.
  • the tissue paper surface comprises densified knuckles having a relative density of at least 125% of the density of the high bulk field.
  • the array of supports is preferably an imprinting carrier fabric having a patterned displacement of knuckles which operate as the array of supports which facilitate the formation of the densified zones upon application of pressure.
  • the pattern of knuckles constitutes the array of supports previously referred to.
  • Imprinting carrier fabrics are disclosed in U.S. Patent No. 3,301 ,746, Sanford and Sisson, issued January 31 , 1967, U.S. Patent No. 3,821 ,068, Salvucci, Jr. et al ., issued May 21 , 1974, U.S. Patent No. 3,974,025, Ayers, issued August 10, 1976, U.S. Patent No. 3,573,164, Friedberg et al ., issued March 30, 1971 , U.S. Patent No.
  • the furnish is first formed into a wet web on a foraminous forming carrier, such as a Fourdrinier wire.
  • the web is dewatered and transferred to an imprinting fabric.
  • the furnish may alternately be initially deposited on a foraminous supporting carrier which also operates as an imprinting fabric.
  • the wet web is dewatered and, preferably, thermally predried to a selected fiber consistency of between about 40% and about 80%.
  • Dewatering can be performed with suction boxes or other vacuum devices or with blow- through dryers.
  • the knuckle imprint of the imprinting fabric is impressed in the web as discussed above, prior to drying the web to completion.
  • One method for accomplishing this is through application of mechanical pressure.
  • nip roll which supports the imprinting fabric against the face of a drying drum, such as a Yankee dryer, wherein the web is disposed between the nip roll and drying drum.
  • the web is molded against the imprinting fabric prior to completion of drying by application of fluid pressure with a vacuum device such as a suction box, or with a blow-through dryer. Fluid pressure may be applied to induce impression of densified zones during initial dewatering, in a separate, subsequent process stage, or a combination thereof.
  • uncompacted, nonpattern-densified tissue paper structures are described in U.S. Patent No. 3,812,000 issued to Joseph L. Salvucci, Jr. and Peter N. Yiannos on May 21 , 1974 and U.S. Patent No. 4,208,459, issued to Henry E. Becker, Albert L. McConnell, and Richard Schutte on June 17, 1980, both of which are incorporated herein by reference.
  • uncompacted, non pattern densified tissue paper structures are prepared by depositing a papermaking furnish on a foraminous forming wire such as a Fourdrinier wire to form a wet web, draining the web and removing additional water without mechanical compression until the web has a fiber consistency of at least 80%, and creping the web. Water is removed from the web by vacuum dewatering and thermal drying. The resulting structure is a soft but weak high bulk sheet of relatively uncompacted fibers. Bonding material is preferably applied to portions of the web prior to creping.
  • tissue paper web of this invention can be used in any application where soft, absorbent tissue paper webs are required.
  • tissue paper web of this invention are in paper towel, toilet tissue and facial tissue products.
  • two tissue paper webs of this invention can be embossed and adhesively secured together in face to face relation as taught by U.S. Pat. No. 3,414,459, which issued to Wells on December 3, 1968 and which is incorporated herein by reference, to form 2-ply paper towels.
  • polymeric materials The essential distinguishing characteristic of polymeric materials is their molecular size.
  • ⁇ Wj ⁇ Nj Mj w is a more useful means for expressing polymer molecular weights than n since it reflects more accurately such properties as melt viscosity and mechanical properties of polymers and is therefor used in the present invention.
  • Analysis of the amount of treatment chemicals used herein or retained on tissue paper webs can be performed by any method accepted in the applicable art.
  • the level of the quaternary ammonium compound, such as Di(Hydrogenated)Tallow DiMethyl Ammonium Methyl Sulfate (DHTDMAMS) retained by the tissue paper can be determined by solvent extraction of the DHTDMAMS by an organic solvent followed by an anionic/cationic titration using Dimidium Bromide as indicator;
  • the level of the polyhydroxy compound, such as PEG-400 can be determined by extraction in an aqueous solvent such as water followed by gas chromatography or colorimetry techniques to determine the level of PEG-400 in the extract.
  • Hydrophilicity of tissue paper refers, in general, to the propensity of the tissue paper to be wetted with water. Hydrophilicity of tissue paper may be somewhat quantified by determining the period of time required for dry tissue paper to become completely wetted with water. This period of time is referred to as "wetting time". In order to provide a consistent and repeatable test for wetting time, the following procedure may be used for wetting time determinations: first, a conditioned sample unit sheet (the environmental conditions for testing of paper samples are 23 + 1 °C and 50 + 2% R.H.
  • tissue paper structure approximately 4-3/8 inch x 4-3/4 inch (about 1 1.1 cm x 12 cm) of tissue paper structure is provided;
  • the sheet is folded into four (4) juxtaposed quarters, and then crumpled into a ball approximately 0.75 inches (about 1.9 cm) to about 1 inch (about 2.5 cm) in diameter;
  • the balled sheet is placed on the surface of a body of distilled water at 23 - ⁇ - 1 °C and a timer is simultaneously started; fourth, the timer is stopped and read when wetting of the balled sheet is completed. Complete wetting is observed visually.
  • Hydrophilicity characters of tissue paper embodiments of the present invention may, of course, be determined immediately after manufacture. However, substantial increases in hydrophobicity may occur during the first two weeks after the tissue paper is made: i.e., after the paper has aged two (2) weeks following its manufacture. Thus, the wetting times are preferably measured at the end of such two week period. Accordingly, wetting times measured at the end of a two week aging period at room temperature are referred to as "two week wetting times.”
  • the density of tissue paper is the average density calculated as the basis weight of that paper divided by the caliper, with the appropriate unit conversions incorporated therein.
  • Caliper of the tissue paper is the thickness of the paper when subjected to a compressive load of 95 g/in 2 (15.5 g/cm 2 ).
  • 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 paper.
  • the surfactants preferably have alkyl chains with eight or more carbon atoms.
  • Exemplary anionic surfactants are linear alkyl sulfonates, and alkylbenzene sulfonates.
  • Exemplary nonionic surfactants are 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 4.01 1 ,389 issued to W. K. 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, N.J.).
  • alkylpolyethoxylated esters such as Pegosperse 200 ML available from Glyco Chemicals, Inc. (Greenwich, CT) and IGEPAL RC-520 available from Rhone Poulenc Corporation (Cranbury, N.J.).
  • dry strength additives to increase the tensile strength of the tissue webs.
  • dry strength additives include carboxymethyl cellulose, and cationic polymers from the Acco chemical family such as Acco 71 1 and Acco 514, with the Acco chemical family being preferred. These materials are available commercially from the American Cyanamid Company of Wayne, New Jersey.
  • the level of dry strength additive, if used, is preferably from about 0.01 % to about 1.0%, by weight, based on the dry fiber weight of the tissue paper.
  • the present invention may contain as an optional component from about 0.01 % to about 3.0%, more preferably from about 0.3% to about 1.5% by weight, on a dry fiber weight basis, of a water-soluble permanent wet strength resin.
  • Permanent wet strength resins useful herein can be of several types. Generally, those resins which have previously found and which will hereafter find utility in the papermaking art are useful herein. Numerous examples are shown in the aforementioned paper by Westfelt, incorporated herein by reference.
  • the wet strength resins are water-soluble, cationic materials. That is to say, the resins are water-soluble at the time they are added to the papermaking furnish. It is quite possible, and even to be expected, that subsequent events such as cross-linking will render the resins insoluble in water. Further, some resins are soluble only under specific conditions, such as over a limited pH range.
  • Wet strength resins are generally believed to undergo a cross- linking or other curing reactions after they have been deposited on, within, or among the papermaking fibers. Cross-linking or curing does not normally occur so long as substantial amounts of water are present.
  • Base-activated polyamide-epichlorohydrin resins useful in the present invention are sold under the Santo Res trademark, such as Santo Res 31, by Monsanto Company of St. Louis, Missouri. These types of materials are generally described in U.S. Pat. Nos. 3,855, 158 issued to Petrovich on December 17, 1974; 3,899,388 issued to Petrovich on August 12, 1975; 4, 129,528 issued to Petrovich on December 12, 1978; 4,147,586 issued to Petrovich on April 3, 1979; and 4,222,921 issued to Van Eenam on September 16, 1980, all incorporated herein by reference.
  • water-soluble cationic resins useful herein are the polyacrylamide resins such as those sold under the Parez trademark, such as Parez 631 NC, by American Cyanamid Company of Stanford, Connecticut. These materials are generally described in U.S. Pat. Nos.
  • water-soluble resins useful in the present invention include acrylic emulsions and anionic styrene-butadiene latexes. Numerous examples of these types of resins are provided in U.S. Patent 3,844,880, Meisel, Jr. et al ., issued October 29, 1974, incorporated herein by reference.
  • Still other water-soluble cationic resins finding utility in this invention are the urea formaldehyde and melamine formaldehyde resins. These polyfunctional, reactive polymers have molecular weights on the order of a few thousand. The more common functional groups include nitrogen containing groups such as amino groups and methylol groups attached to nitrogen. Although less preferred, polyethylenimine type resins find utility in the present invention.
  • water-soluble resins include their manufacture, and their manufacture.
  • permanent wet strength resin refers to a resin which allows the paper sheet, when placed in an aqueous medium, to keep a majority of its initial wet strength for a period of time greater than at least two minutes.
  • wet strength additives typically result in paper products with permanent wet strength, i.e., paper which when placed in an aqueous medium retains a substantial portion of its initial wet strength over time.
  • permanent wet strength in some types of paper products can be an unnecessary and undesirable property.
  • Paper products such as toilet tissues, etc., are generally disposed of after brief periods of use into septic systems and the like. Clogging of these systems can result if the paper product permanently retains its hydrolysis-resistant strength properties.
  • manufacturers have added temporary wet strength additives to paper products for which wet strength is sufficient for the intended use, but which then decays upon soaking in water. Decay of the wet strength facilitates flow of the paper product through septic systems.
  • suitable temporary wet strength resins include modified starch temporary wet strength agents, such as National Starch 78-0080, marketed by the National Starch and Chemical Corporation (New York, New York). This type of wet strength agent can be made by reacting dimethoxyethyl-N-methyl-chloroacetamide with cationic starch polymers. Modified starch temporary wet strength agents are also described in U.S. Pat. No. 4,675,394, Solarek, et al ., issued June 23, 1987, and incorporated herein by reference. Preferred temporary wet strength resins include those described in U.S. Pat. No. 4,981 ,557, Bjorkquist, issued January 1 , 1991 , and incorporated herein by reference.
  • the purpose of this example is to illustrate a method that can be used to make-up a substantially waterless self-emulsifiable chemical softener composition
  • a substantially waterless self-emulsifiable chemical softener composition comprising a mixture of Di(Hydrogenated)Tallow DiMethyl Ammonium Methyl Sulfate (DHTDMAMS) and Polyoxyethylene Glycol 400 (PEG-400).
  • DHTDMAMS Di(Hydrogenated)Tallow DiMethyl Ammonium Methyl Sulfate
  • PEG-400 Polyoxyethylene Glycol 400
  • a waterless self-emulsifiable chemical softener composition is prepared according to the following procedure : 1. An equivalent weight of DHTDMAMS and PEG-400 is weighed separately; 2. PEG is heated up to about 66°C (150°F); 3. DHTDMAMS is dissolved in the PEG to form a melted solution at 66°C (150°F); 4. Adequate mixing is provided to form a homogenous mixture of DHTDMAMS in PEG; 5. The homogenous mixture of (4) is cooled down to a solid form at room temperature.
  • the substantially waterless self-emulsifiable chemical softener composition of (5) can be pre-mixed (steps 1-5 above) at the chemical supplier (e.g. Sherex company of Dublin, Ohio) and then economically shipped to the ultimate users of the chemical softening composition where it can then be diluted to the desired concentration.
  • the chemical supplier e.g. Sherex company of Dublin, Ohio
  • the purpose of this example is to illustrate a method that can be used to make-up a substantially waterless self-emulsifiable chemical softener composition which comprises a mixture of Di(Hydrogenated)Tallow DiMethyl Ammonium Methyl Sulfate (DHTDMAMS) and a mixture of Glycerol and PEG-400.
  • DHTDMAMS Di(Hydrogenated)Tallow DiMethyl Ammonium Methyl Sulfate
  • Glycerol and PEG-400 a mixture of Glycerol and PEG-400.
  • a substantially waterless self-emulsifiable chemical softener composition is prepared according to the following procedure : 1. A mixture of Glycerol and PEG-400 is blended at 75 : 25 by weight ratio; 2. Equivalent weights of DHTDMAMS and the mixture of (1 ) are weighted separately; 3. The mixture of (1 ) is heated up to about 66°C (150°F); 4. DHTDMAMS is dissolved in (3) to form a melted solution at 66°C (150°F); 5. Adequate mixing is provided to form a homogenous mixture of DHTDMAMS in (3); 6. The homogenous mixture of (5) is cooled down to a solid form at room temperature.
  • the substantially waterless self-emulsifiable chemical softener composition of (6) can be pre-mixed (steps 1 -6 above) at the chemical supplier (e.g. Sherex company of Dublin, Ohio) and then economically shipped to the ultimate users of the chemical softening composition where it can then be diluted to the desired concentration.
  • the chemical supplier e.g. Sherex company of Dublin, Ohio
  • the purpose of this example is to illustrate a method using a blow through drying papermaking technique to make soft and absorbent paper towel sheets treated with a substantially waterless self- emulsifiable chemical softener composition
  • a substantially waterless self- emulsifiable chemical softener composition comprising a premix of Di(Hydrogenated)Tallow DiMethyl Ammonium Methyl Sulfate (DHTDMAMS) and a Polyoxyethylene Glycol 400 (PEG-400) in solid state, and a permanent wet strength resin .
  • DHTDMAMS Di(Hydrogenated)Tallow DiMethyl Ammonium Methyl Sulfate
  • PEG-400 Polyoxyethylene Glycol 400
  • a pilot scale Fourdrinier papermaking machine is used in the practice of the present invention.
  • the substantially waterless self- emulsifiable chemical softener composition is prepared according to the procedure in Example 1 wherein the homogenous pre-mixed of DHTDMAMS and PEG-400 in solid state is dispersed in a conditioned water tank (Temperature " 66°C) to form a sub-micron vesicle dispersion.
  • the particle size of the vesicle dispersion is determined using an optical microscopic technique. The particle size range is from about 0.1 to 1.0 micron.
  • Figure 3 illustrates a cryo-transmission micro- photograph taken at X 63,000 of a vesicle dispersion of a 1 : 1 by weight ratio of a DHTDMAMS and PEG-400 system.
  • Figure 3 indicates that the particles have membranes one or two bilayers thick, whose geometry ranges from closed/open vesicles, to disc-like structures and sheets.
  • a 3% by weight aqueous slurry of NSK is made up in a conventional re-pulper.
  • the NSK slurry is refined gently and a 2% solution of a permanent wet strength resin (i.e. Kymene® 557H marketed by Hercules Incorporated of Wilmington, DE) is added to the NSK stock pipe at a rate of 1 % by weight of the dry fibers.
  • Kymene® 557H to NSK is enhanced by an in-line mixer.
  • a 1 % solution of Carboxy Methyl Cellulose (CMC) is added after the in ⁇ line mixer at a rate of 0.2% by weight of the dry fibers to enhance the dry strength of the fibrous substrate.
  • CMC Carboxy Methyl Cellulose
  • the adsorption of CMC to NSK can be enhanced by an in-line mixer. Then, a 1 % solution of the chemical softener mixture (DHTDMAMS/ PEG) is added to the NSK slurry at a rate of 0.1 % by weight of the dry fibers. The adsorption of the chemical softener mixture to NSK can also enhanced via an in-line mixer. The NSK slurry is diluted to 0.2% by the fan pump.
  • DHTDMAMS/ PEG chemical softener mixture
  • a 3% by weight aqueous slurry of CTMP is made up in a conventional re-pulper.
  • a non-ionic surfactant (Pegosperse) is added to the re-pulper at a rate of 0.2% by weight of dry fibers.
  • a 1 % solution of the chemical softener mixture is added to the CTMP stock pipe before the stock pump at a rate of 0.1 % by weight of the dry fibers.
  • the adsorption of the chemical softener mixture to CTMP can be enhanced by an in-line mixer.
  • the CTMP slurry is diluted to 0.2% by the fan pump.
  • the treated furnish mixture (NSK / CTMP) is blended in the head box and deposited onto a Fourdrinier wire to form an embryonic web.
  • the Fourdrinier wire is of a 5-shed, satin weave configuration having 84 machine-direction and 76 cross-machine-direction monofilaments per inch, respectively.
  • the embryonic wet web is transferred from the Fourdrinier wire, at a fiber consistency of about 22% at the point of transfer, to a photo-polymer fabric having 240 linear Idaho cells per square inch, 34 percent knuckle areas and 14 mils of photo-polymer depth.
  • the name "linear Idaho” is based on the fact that the cross-section of conduits from which this pattern was derived, originally resembled the shape of a potato.
  • the walls of the conduits on four sides are formed by generally straight lines, thus the pattern is referred to as being a "linear" Idaho rather than simply as an Idaho pattern.
  • Further de-watering is accomplished by vacuum assisted drainage until the web has a fiber consistency of about 28%.
  • the patterned web is pre-dried by air blow- through to a fiber consistency of about 65% by weight.
  • the web is then adhered to the surface of a Yankee dryer with a sprayed creping adhesive comprising 0.25% aqueous solution of Polyvinyl Alcohol (PVA).
  • PVA Polyvinyl Alcohol
  • the doctor blade has a bevel angle of about 25 degrees and is positioned with respect to the Yankee dryer to provide an impact angle of about 81 degrees; the Yankee dryer is operated at about 800 fpm (feet per minute) (about 244 meters per minute).
  • the dry web is formed into roll at a speed of 700 fpm ( 214 meters per minutes).
  • the paper towel has about 26 #/3M Sq Ft basis weight, contains about 0.2% of the substantially waterless self-emulsifiable chemical softener mixture and about 1.0% of the permanent wet strength resin.
  • the resulting paper towel is soft, absorbent, and very strong when wetted.
  • the purpose of this example is to illustrate a method using a blow through drying and layered papermaking techniques to make soft and absorbent toilet tissue paper treated with a substantially waterless self- emulsifiable chemical softener composition
  • a substantially waterless self- emulsifiable chemical softener composition comprising a premix of Di(Hydrogenated)Tallow DiMethyl Ammonium Methyl Sulfate (DHTDMAMS) and a Polyoxyethylene Glycol 400 (PEG-400) in liquid state and a temporary wet strength resin.
  • DHTDMAMS Di(Hydrogenated)Tallow DiMethyl Ammonium Methyl Sulfate
  • PEG-400 Polyoxyethylene Glycol 400
  • a pilot scale Fourdrinier papermaking machine is used in the practice of the present invention.
  • the substantially waterless self- emulsifiable chemical softener composition is prepared according to the procedure in Example 1 wherein the homogenous premix of DHTDMAMS and polyhydroxy compounds in solid state is re-melted at a temperature of about 66°C (150°F). The melted mixture is then dispersed in a conditioned water tank (Temperature " 66°C) to form a sub-micron vesicle dispersion.
  • the particle size of the vesicle dispersion is determined using an optical microscopic technique. The particle size range is from about 0.1 to 1.0 micron.
  • Figure 4 illustrates a cryo- transmission micro-photograph taken at X 63,000 of a vesicle dispersion of a 1 : 1 by weight ratio of a DHTDMAMS and polyhydroxy compounds system.
  • Figure 4 indicates that the particles have membranes one or two bilayers thick, whose geometry ranges from closed/open vesicles, to disc-like structures and sheets.
  • a 3% by weight aqueous slurry of NSK is made up in a conventional re-pulper.
  • the NSK slurry is refined gently and a 2% solution of the temporary wet strength resin (i.e. National starch 78- 0080 marketed by National Starch and Chemical corporation of New- York, NY) is added to the NSK stock pipe at a rate of 0.75% by weight of the dry fibers.
  • the adsorption of the temporary wet strength resin onto NSK fibers is enhanced by an in-line mixer.
  • the NSK slurry is diluted to about 0.2% consistency at the fan pump.
  • a 3% by weight aqueous slurry of Eucalyptus fibers is made up in a conventional re-pulper.
  • a 1 % solution of the chemical softener mixture is added to the Eucalyptus stock pipe before the stock pump at a rate of 0.2% by weight of the dry fibers.
  • the adsorption of the substantially waterless self-emulsifiable chemical softener mixture to Eucalyptus fibers can be enhanced by an in-line mixer.
  • the Eucalyptus slurry is diluted to about 0.2% consistency at the fan pump.
  • the treated furnish mixture (30% of NSK / 70% of Eucalyptus) is blended in the head box and deposited onto a Fourdrinier wire to form an embryonic web. Dewatering occurs through the Fourdrinier wire and is assisted by a deflector and vacuum boxes.
  • the Fourdrinier wire is of a 5-shed, satin weave configuration having 84 machine-direction and 76 cross-machine-direction monofilaments per inch, respectively.
  • the embryonic wet web is transferred from the photo-polymer wire, at a fiber consistency of about 15% at the point of transfer, to a photo- polymer fabric having 562 Linear Idaho cells per square inch, 40 percent knuckle area and 9 mils of photo-polymer depth.
  • the patterned web is pre-dried by air blow-through to a fiber consistency of about 65% by weight.
  • the web is then adhered to the surface of a Yankee dryer with a sprayed creping adhesive comprising 0.25% aqueous solution of Polyvinyl Alcohol (PVA).
  • PVA Polyvinyl Alcohol
  • the fiber consistency is increased to an estimated 96% before the dry creping the web with a doctor blade.
  • the doctor blade has a bevel angle of about 25 degrees and is positioned with respect to the Yankee dryer to provide an impact angle of about 81 degrees; the Yankee dryer is operated at about 800 fpm (feet per minute) (about 244 meters per minute).
  • the dry web is formed into roll at a speed of 700 fpm (214 meters per minutes).
  • the web is converted into a one ply tissue paper product.
  • the tissue paper has about 18 #/3M Sq Ft basis weight, contains about 0.1 % of the chemical softener mixture and about 0.2% of the temporary wet strength resin.
  • the resulting tissue paper is soft, absorbent and is suitable for use as facial and/or toilet tissues.
  • the purpose of this example is to illustrate a method using a blow through drying papermaking technique to make soft and absorbent toilet tissue paper treated with a substantially waterless self-emulsifiable chemical softener composition
  • a substantially waterless self-emulsifiable chemical softener composition comprising a premix of Di(Hydrogenated)Tallow DiMethyl Ammonium Chloride (DHTDMAC) and a mixture of polyhydroxy compound (Glycerol / PEG-400) in liquid state and a dry strength additive resin.
  • DHTDMAC Di(Hydrogenated)Tallow DiMethyl Ammonium Chloride
  • Glycerol / PEG-400 polyhydroxy compound
  • a pilot scale Fourdrinier papermaking machine is used in the practice of the present invention.
  • the substantially waterless self- emulsifiable chemical softener composition is prepared according to the procedure in Example 2 wherein the homogenous premix of DHTDMAC and polyhydroxy compounds in solid state is re-melted at a temperature of about 66°C (150°F). The melted mixture is then dispersed in a conditioned water tank (Temperature ⁇ 66 °C) to form a sub-micron vesicle dispersion.
  • the particle size of the vesicle dispersion is determined using an optical microscopic technique. The particle size range is from about 0.1 to 1.0 micron.
  • Figure 5 illustrates a cryo- transmission micro-photograph taken at X 63,000 of a vesicle dispersion of a 1 : 1 by weight ratio of a DHTDMAC and polyhydroxy compounds system.
  • Figure 5 indicates that the particles have membranes one or two bilayers thick, whose geometry ranges from closed/open vesicles, to disc-like structures and sheets.
  • a 3% by weight aqueous slurry of NSK is made up in a conventional re-pulper.
  • the NSK slurry is refined gently and a 2% solution of the dry strength resin (i.e. Acco 514, Acco 71 1 marketed by American Cyanamid company of Fairfield, OH) is added to the NSK stock pipe at a rate of 0.2% by weight of the dry fibers.
  • the adsorption of the dry strength resin onto NSK fibers is enhanced by an in-line mixer.
  • the NSK slurry is diluted to about 0.2% consistency at the fan pump.
  • a 3% by weight aqueous slurry of Eucalyptus fibers is made up in a conventional re-pulper.
  • a 1 % solution of the chemical softener mixture is added to the Eucalyptus stock pipe before the stock pump at a rate of 0.2% by weight of the dry fibers.
  • the adsorption of the substantially waterless self-emulsifiable chemical softener mixture to Eucalyptus fibers can be enhanced by an in-line mixer.
  • the Eucalyptus slurry is diluted to about 0.2% consistency at the fan pump.
  • the treated furnish mixture (30% of NSK / 70% of Eucalyptus) is blended in the head box and deposited onto a Fourdrinier wire to form an embryonic web. Dewatering occurs through the Fourdrinier wire and is assisted by a deflector and vacuum boxes.
  • the Fourdrinier wire is of a 5-shed, satin weave configuration having 84 machine-direction and 76 cross-machine-direction monofilaments per inch, respectively.
  • the embryonic wet web is transferred from the photo-polymer wire, at a fiber consistency of about 15% at the point of transfer, to a photo- polymer fabric having 562 Linear Idaho cells per square inch, 40 percent knuckle area and 9 mils of photo-polymer depth.
  • the patterned web is pre-dried by air blow-through to a fiber consistency of about 65% by weight.
  • the web is then adhered to the surface of a Yankee dryer with a sprayed creping adhesive comprising 0.25% aqueous solution of Polyvinyl Alcohol (PVA).
  • PVA Polyvinyl Alcohol
  • the fiber consistency is increased to an estimated 96% before the dry creping the web with a doctor blade.
  • the doctor blade has a bevel angle of about 25 degrees and is positioned with respect to the Yankee dryer to provide an impact angle of about 81 degrees; the Yankee dryer is operated at about 800 fpm (feet per minute) (about 244 meters per minute).
  • the dry web is formed into roll at a speed of 700 fpm ( 214 meters per minutes).
  • tissue paper Two plies of the web are formed into tissue paper products and laminating them together using ply bonded technique.
  • the tissue paper has about 23 #/3M Sq Ft basis weight, contains about 0.1 % of the substantially waterless self-emulsifiable chemical softener mixture and about 0.1 % of the dry strength resin.
  • the resulting tissue paper is soft, absorbent and is suitable for use as 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 toilet tissue paper treated with a substantially waterless self-emulsifiable chemical softener composition
  • a substantially waterless self-emulsifiable chemical softener composition comprising a premix of Di(Hydrogenated)Tallow DiMethyl Ammonium Methyl Sulfate (DHTDMAMS) and a Polyoxyethylene Glycol 400 (PEG-400) in solid state and a dry strength additive resin .
  • DHTDMAMS Di(Hydrogenated)Tallow DiMethyl Ammonium Methyl Sulfate
  • PEG-400 Polyoxyethylene Glycol 400
  • a pilot scale Fourdrinier papermaking machine is used in the practice of the present invention.
  • the substantially waterless self- emulsifiable chemical softener composition is prepared according to the procedure in Example 1 wherein the homogenous premix of DHTDMAMS and PEG-400 in solid state is dispersed in a conditioned water tank (Temperature " 66°C) to form a sub-micron vesicle dispersion.
  • the particle size of the vesicle dispersion is determined using an optical microscopic technique. The particle size range is from about 0.1 to 1.0 micron.
  • Figure 3 illustrates a cryo-transmission micro- photograph taken at X 63,000 of a vesicle dispersion of a 1 : 1 by weight ratio of a DHTDMAMS and PEG-400 system.
  • Figure 3 indicates that the particles have membranes one or two bilayers thick, whose geometry ranges from closed/open vesicles, to disc-like structures and sheets.
  • a 3% by weight aqueous slurry of NSK is made up in a conventional re-pulper.
  • the NSK slurry is refined gently and a 2% solution of the dry strength resin (i.e. Acco 514, Acco 71 1 marketed by American Cyanamid company of Wayne, New Jersey) is added to the NSK stock pipe at a rate of 0.2% by weight of the dry fibers.
  • the adsorption of the dry strength resin onto NSK fibers is enhanced by an in-line mixer.
  • the NSK slurry is diluted to about 0.2% consistency at the fan pump.
  • a 3% by weight aqueous slurry of Eucalyptus fibers is made up in a conventional re-pulper.
  • a 1 % solution of the chemical softener mixture is added to the Eucalyptus stock pipe before the stock pump at a rate of 0.2% by weight of the dry fibers.
  • the adsorption of the chemical softener mixture to Eucalyptus fibers can be enhanced by an in-line mixer.
  • the Eucalyptus slurry is diluted to about 0.2% consistency at the fan pump.
  • the treated furnish mixture (30% of NSK / 70% of Eucalyptus) is blended in the head box and deposited onto a Fourdrinier wire to form an embryonic web.
  • Dewatering occurs through the Fourdrinier wire and is assisted by a deflector and vacuum boxes.
  • the Fourdrinier wire is of a 5-shed, satin weave configuration having 84 machine-direction and 76 cross-machine-direction monofilaments per inch, respectively.
  • the embryonic wet web is transferred from the Fourdrinier wire, at a fiber consistency of about 15% at the point of transfer, to a conventional felt. Further de-watering is accomplished by vacuum assisted drainage until the web has a fiber consistency of about 35%.
  • the web is then adhered to the surface of a Yankee dryer.
  • the fiber consistency is increased to an estimated 96% before the dry creping the web with a doctor blade.
  • the doctor blade has a bevel angle of about 25 degrees and is positioned with respect to the Yankee dryer to provide an impact angle of about 81 degrees; the Yankee dryer is operated at about 800 fpm (feet per minute) (about 244 meters per minute).
  • the dry web is formed into roll at a speed of 700 fpm (214 meters per minutes).
  • tissue paper Two plies of the web are formed into tissue paper products and laminating them together using ply bonded technique.
  • the tissue paper has about 23 #/3M Sq. Ft. basis weight, contains about 0.1 % of the substantially waterless self-emulsifiable chemical softener mixture and about 0.1 % of the dry strength resin.
  • the resulting tissue paper is soft, absorbent and is suitable for use as a facial and/or toilet tissues.

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Abstract

Composition d'adoucissant autoémulsifiant pratiquement exempt d'eau, comportant un mélange d'un composé d'ammonium quaternaire et d'un composé polyhydroxy. Les composés d'ammonium quaternaire préférés comprennent des sels de dialkyldiméthylammonium tels que le chlorure de disuif(hydrogéné) diméthylammonium ou le sulfate méthylique de disuif(hydrogéné) diméthylammonium. Les composés polyhydroxy préférés sont choisis dans un groupe constitué de glycérol, de polyglycérols d'un poids moléculaire moyen compris entre environ 150 et 800, et de polyoxyéthylène-glycols et de polyoxypropylène-glycols d'un poids moléculaire moyen compris entre environ 200 et 4000. Lesdits adoucissants s'obtiennent en mélangeant le composé d'ammonium quaternaire au composé polyhydroxy à dans une plage de températures spécifique où le second est miscible avec le premier. Il en résulte un mélange stable, solide ou sous forme de concentré liquide, facile à expédier au consommateur ou à l'utilisateur final, qui n'ont plus qu'à le diluer dans un excipient liquide (p. ex. de l'eau) pour former une dispersion aqueuse se prêtant au traitement des produits fibreux cellulosiques. Les adoucissants chimiques automémulsifiants pratiquement exempts d'eau présentés ici sont principalement destinés à l'adoucissement de produits en papier jetables tels que mouchoirs et serviettes.
PCT/US1994/005777 1993-06-03 1994-05-23 Composition d'adoucissant chimique autoemulsifiant sans eau pour produits cellulosiques fibreux WO1994029520A1 (fr)

Priority Applications (9)

Application Number Priority Date Filing Date Title
KR1019950705460A KR100336444B1 (ko) 1993-06-03 1994-05-23 섬유성셀룰로즈물질에유용한,무수성의자가-유화성화학유연제조성물
AU69559/94A AU694433B2 (en) 1993-06-03 1994-05-23 Waterless self-emulsifiable chemical softening composition useful in fibrous cellulosic materials
BR9406738A BR9406738A (pt) 1993-06-03 1994-05-23 Composição de amaciamento químico auto-emulsionável substancialmente sem água e dispersão aquosa
DE69423352T DE69423352T2 (de) 1993-06-03 1994-05-23 Wasserfrei selbstemulgierbare chemische weichmachende zusammensetzung anwendbar in faserigen materialien aus zellulose
NZ267305A NZ267305A (en) 1993-06-03 1994-05-23 Waterless self-emulsifiable softening composition comprising a quaternary ammonium compound having at least two c14-22 hydrocarbon substituents and at least one of glycerol, polyglycerol and polyoxyethylene (or propylene)
EP94918091A EP0701640B1 (fr) 1993-06-03 1994-05-23 Composition d'adoucissant chimique autoemulsifiant sans eau pour produits cellulosiques fibreux
NO954868A NO954868L (no) 1993-06-03 1995-11-30 Vannfri selv-emulgerbar kjemisk mykgjörende blanding nyttig i fibröse cellulosematerialer
FI955789A FI955789A (fi) 1993-06-03 1995-12-01 Vedetön itse-emulgoituva kemiallinen pehmennyskoostumus, joka on käyttökelpoinen kuitumaisissa selluloosamateriaaleissa
HK98114419A HK1013134A1 (en) 1993-06-03 1998-12-21 Waterless self-emulsifiable chemical softening composition useful in fibrous cellulosic materials

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US7229993A 1993-06-03 1993-06-03
US08/072,299 1993-06-03

Publications (1)

Publication Number Publication Date
WO1994029520A1 true WO1994029520A1 (fr) 1994-12-22

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PCT/US1994/005777 WO1994029520A1 (fr) 1993-06-03 1994-05-23 Composition d'adoucissant chimique autoemulsifiant sans eau pour produits cellulosiques fibreux

Country Status (19)

Country Link
EP (1) EP0701640B1 (fr)
JP (1) JP3194958B2 (fr)
KR (1) KR100336444B1 (fr)
CN (1) CN1052050C (fr)
AU (1) AU694433B2 (fr)
BR (1) BR9406738A (fr)
CA (1) CA2162848A1 (fr)
CZ (1) CZ321395A3 (fr)
DE (1) DE69423352T2 (fr)
FI (1) FI955789A (fr)
HK (1) HK1013134A1 (fr)
HU (1) HUT74116A (fr)
MY (1) MY111219A (fr)
NO (1) NO954868L (fr)
NZ (1) NZ267305A (fr)
PE (1) PE53894A1 (fr)
PH (1) PH31624A (fr)
SG (1) SG66237A1 (fr)
WO (1) WO1994029520A1 (fr)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6306408B1 (en) 1997-03-19 2001-10-23 Sca Hygiene Products Gmbh Composition containing humidity regulators, for tissue products
US11286620B2 (en) 2019-01-11 2022-03-29 The Procter & Gamble Company Quaternary ammonium compound compositions and methods for making and using same

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103233380B (zh) * 2013-05-07 2016-08-03 金红叶纸业集团有限公司 纸张的制备工艺
KR101800510B1 (ko) * 2015-10-28 2017-11-22 김철성 수납장
JP7359365B2 (ja) * 2019-03-29 2023-10-11 学校法人神奈川大学 柔軟剤及び繊維の洗浄方法

Citations (4)

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Publication number Priority date Publication date Assignee Title
WO1993009288A1 (fr) * 1991-11-01 1993-05-13 The Procter & Gamble Company Papier mousseline doux absorbant a resistance elevee temporaire a l'humidite
WO1993009287A1 (fr) * 1991-11-01 1993-05-13 The Procter & Gamble Company Papier mousseline absorbant doux a resistance elevee a l'etat humide permanente
US5240562A (en) * 1992-10-27 1993-08-31 Procter & Gamble Company Paper products containing a chemical softening composition
US5279767A (en) * 1992-10-27 1994-01-18 The Procter & Gamble Company Chemical softening composition useful in fibrous cellulosic materials

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1993009288A1 (fr) * 1991-11-01 1993-05-13 The Procter & Gamble Company Papier mousseline doux absorbant a resistance elevee temporaire a l'humidite
WO1993009287A1 (fr) * 1991-11-01 1993-05-13 The Procter & Gamble Company Papier mousseline absorbant doux a resistance elevee a l'etat humide permanente
US5240562A (en) * 1992-10-27 1993-08-31 Procter & Gamble Company Paper products containing a chemical softening composition
US5279767A (en) * 1992-10-27 1994-01-18 The Procter & Gamble Company Chemical softening composition useful in fibrous cellulosic materials

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6306408B1 (en) 1997-03-19 2001-10-23 Sca Hygiene Products Gmbh Composition containing humidity regulators, for tissue products
US6641822B2 (en) 1997-03-19 2003-11-04 Sca Hygiene Products Gmbh Composition containing humidity regulators for preparing tissue products
US11286620B2 (en) 2019-01-11 2022-03-29 The Procter & Gamble Company Quaternary ammonium compound compositions and methods for making and using same
US11732417B2 (en) 2019-01-11 2023-08-22 The Procter & Gamble Company Quaternary ammonium compound compositions and methods for making and using same

Also Published As

Publication number Publication date
JPH08511068A (ja) 1996-11-19
AU6955994A (en) 1995-01-03
DE69423352D1 (de) 2000-04-13
NZ267305A (en) 1997-11-24
BR9406738A (pt) 1996-03-12
FI955789A0 (fi) 1995-12-01
JP3194958B2 (ja) 2001-08-06
FI955789A (fi) 1996-01-18
AU694433B2 (en) 1998-07-23
CN1052050C (zh) 2000-05-03
CN1128550A (zh) 1996-08-07
CZ321395A3 (en) 1996-07-17
NO954868D0 (no) 1995-11-30
HK1013134A1 (en) 1999-08-13
KR100336444B1 (ko) 2002-11-20
KR960702877A (ko) 1996-05-23
DE69423352T2 (de) 2000-10-19
SG66237A1 (en) 1999-07-20
EP0701640A1 (fr) 1996-03-20
MY111219A (en) 1999-09-30
HU9503464D0 (en) 1996-01-29
NO954868L (no) 1996-02-02
PH31624A (en) 1999-01-12
HUT74116A (en) 1996-11-28
CA2162848A1 (fr) 1994-12-22
PE53894A1 (es) 1995-01-02
EP0701640B1 (fr) 2000-03-08

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