EP0702736B1 - Waterless self-emulsifiable biodegradable chemical softening composition useful in fibrous cellulosic materials - Google Patents

Waterless self-emulsifiable biodegradable chemical softening composition useful in fibrous cellulosic materials Download PDF

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Publication number
EP0702736B1
EP0702736B1 EP94920030A EP94920030A EP0702736B1 EP 0702736 B1 EP0702736 B1 EP 0702736B1 EP 94920030 A EP94920030 A EP 94920030A EP 94920030 A EP94920030 A EP 94920030A EP 0702736 B1 EP0702736 B1 EP 0702736B1
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European Patent Office
Prior art keywords
ester
quaternary ammonium
compound
functional quaternary
diester
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EP94920030A
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German (de)
English (en)
French (fr)
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EP0702736A1 (en
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Robert Gene Laughlin
Dean Van Phan
Paul Dennis Trokhan
Toan Trinh
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Procter and Gamble Co
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Procter and Gamble Co
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    • 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
    • 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
    • D21H17/03—Non-macromolecular organic compounds
    • D21H17/05—Non-macromolecular organic compounds containing elements other than carbon and hydrogen only
    • D21H17/14—Carboxylic acids; Derivatives thereof
    • 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

Definitions

  • This invention relates to a method of producing a substantially waterless self-emulsifiable biodegradable chemical softener composition. More particularly, it relates to a method of producing a substantially waterless self-emulsifiable biodegradable 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).
  • Chemical debonding agents have been disclosed in various references such as US-A-3,554,862, issued to Hervey et al. on January 12, 1971. These materials include mono-long chain 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.
  • a polyhydroxy compound and a quaternary ammonium compound are mixed at elevated temperature to form a fluidised melt.
  • the fluidised melt is diluted with hot liquid carrier (e.g. water at 66°C) to form an aqueous solution.
  • 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 biodegradable. Applicants have discovered that biodegradable mono- and di-ester variations of these quaternary ammonium salts also function effectively as chemical debonding agents and enhance the softness 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 biodegradable chemical softening composition useful for treating fibrous cellulose materials.
  • the waterless self-emulsifiable biodegradable chemical softening composition comprises a mixture of :
  • 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 about 5 % by weight.
  • These compounds can be considered to be mono or diester variations of the well-known dialkyldimethylammonium salts such as diester ditallow dimethyl ammonium chloride, diester distearyl dimethyl ammonium chloride, monoester ditallow dimethyl ammonium chloride, diester di(hydrogenated)tallow dimethyl ammonium methylsulfate, diester di(hydrogenated)tallow dimethyl ammonium chloride, monoester di(hydrogenated)tallow dimethyl ammonium chloride, and mixtures thereof, with the diester variations of di(non hydrogenated)tallow dimethyl ammonium chloride, Di(Touch Hydrogenated)Tallow DiMethyl Ammonium Chloride (DEDTHTDMAC) and Di(Hydrogenated)Tallow DiMethyl Ammonium Chloride (DEDHTDMAC), and mixtures thereof being preferred.
  • the saturation level of the ditallow can be tailored from non hydrogenated (soft) to touch, partially or completely hydrogen
  • ester moiety(ies) lends biodegradability to these compounds.
  • ester-functional quaternary ammonium compounds used herein biodegrade more rapidly than do conventional dialkyl dimethyl ammonium chemical softeners.
  • polyhydroxy compounds useful in the present invention include glycerol polyglycerols having a weight average molecular weight 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.
  • viscous fluid refers to a fluid having a viscosity greater than or equal to about 10,000 mPa (10,000 centipoise) at 20°C.
  • homogenous mixture refers to compositions wherein the ester-functional 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.
  • ester-functional quaternary ammonium compound refers to quats that contain one or more ester groups.
  • 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 ester-functional 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.
  • other cellulose fibrous pulps such as cotton liners, bagasse, rayon, etc.
  • 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.
  • the present invention contains as an essential component a mixture of an ester-functional quaternary ammonium compound and a polyhydroxy compound.
  • the ratio of the ester-functional quaternary ammonium compound to the polyhydroxy compound ranges from about 1 : 0.1 to about 0.1 : 1; preferably, the weight ratio of the ester-functional quaternary ammonium compound to the polyhydroxy compound is about 1 : 0.3 to about 0.3 : 1; more preferably, the weight ratio of the ester-functional quaternary ammonium compound to the polyhydroxy compound is about 1 : 0.7 to about 0.7 : 1 , although this ratio will vary depending upon the molecular weight of the particular polyhydroxy compound and/or ester-functional quaternary ammonium compound used.
  • the chemical softening composition contains as an essential component a ester-functional quaternary ammonium compound having the formula : wherein each R 2 substituent is a C - C alkyl or hydroxyalkyl group, benzyl group or mixtures thereof; each R 1 substituent is a C - C hydrocarbyl group, or substituted hydrocarbyl group or mixtures thereof; each R 3 substituent is a C - C hydrocarbyl group, or substituted hydrocarbyl or mixtures thereof; Y is - O - C(O) - or - C(O) - O - or - NH - C(O) or - C(O) - NH - or mixtures thereof; n is 1 to 4 and X - is a suitable anion, for example, chloride, bromide, methylsulfate, ethyl sulfate, nitrate and the like.
  • 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. Typically, half of the fatty acids present in tallow are unsaturated, primarily in the form of oleic acid. Synthetic as well as natural "tallows" fall within the scope of the present invention. It is also known that depending upon the product characteristic requirements, the saturation level of the ditallow can be tailored from non hydrogenated (soft) to touch, partially or completely hydrogenated (hard). All of above-described levels of saturations are expressly meant to be included within the scope of the present invention.
  • substituents R 1 , R 2 and R 3 may optionally be substituted with various groups such as alkoxyl, hydroxyl, or can be branched, but such materials are not preferred herein.
  • each R 1 is C - C alkyl and / or alkenyl, most preferably each R 1 is straight-chain C - C alkyl and / or alkenyl.
  • each R 2 is methyl or hydroxyethyl.
  • R 3 is C -C alkyl and / or alkenyl, most preferably R 3 is straight chain C - C alkyl and / or alkenyl, and X - is chloride or methyl sulfate.
  • ester-functional quaternary ammonium compounds can optionally contain up to about 10% of the mono(long chain alkyl) derivatives, e.g., (R 2 ) 2 -N + - ((CH 2 ) 2 OH) ((CH 2 ) 2 OC(O)R 3) X - as minor ingredients.
  • These minor ingredients can act as emulsifiers and are useful in the present invention.
  • ester-functional quaternary ammonium compound can also be used, and are meant to fall within the scope of the present invention. These compounds have the formula:
  • each R 2 is a C - C alkyl or hydroxyalkyl group
  • R 3 is C -C 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 R 3 is C -C alkyl and / or alkenyl, most preferably each R 3 is straight-chain C - C alkyl and / or alkenyl, and R 2 is a methyl.
  • 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 from about 150 to about 800 (e.g., about 2 to about 10 glycerol units) 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 a 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 about 1000, more preferably from about 200 to about about 200 to about 1000, more preferably from about 200 to about 600 are useful in the present invention.
  • the weight ratio of glycerol to polyoxyethylene glycol ranges from about 10 : 1 to about 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 biodegradable chemical softening composition described above i.e. mixture of a ester-functional 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 ester-functional 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 ester-functional quaternary ammonium compound to the hot polyhydroxy compound to form a homogenous fluid.
  • the weight ratio of the ester-functional quaternary ammonium compound to the polyhydroxy compound ranges from about 1 : 0.1 to about 0.1 : 1; preferably, the weight ratio of the ester-functional quaternary ammonium compound to the compound is about 1 : 0.3 to about 0.3 : 1; more preferably, the weight ratio of the ester-functional quaternary ammonium compound to the compound is about 1 : 0.7 to about 0.7 : 1, although this ratio will vary depending upon the molecular weight of the particular compound and/or ester-functional 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 about 5 % by weight.
  • the chemical softening composition is a stable, homogenous, solid or viscous fluid at a temperature at least about 20°C.
  • the substantially waterless self-emulsifiable biodegradable 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 biodegradable 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 ester-functional quaternary ammonium compound / polyhydroxy compound mixture, which is then added to the papermaking furnish.
  • a liquid carrier i.e., water
  • the homogenous mixture of ester-functional quaternary ammonium and 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 ester-functional 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 pH of the liquid carrier preferably ranges from about 2 to about 6.
  • the temperature of the liquid carrier preferably ranges from about 20°C to about 60°C at the time of make-up.
  • the ester-functional 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 about 10 micrometers, most preferably from about 0.1 to about 1.0 micrometer. 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 ester-functional quaternary ammonium compound and added to the paper by the above described process.
  • at least about 20% of the polyhydroxy compound and the ester-functional quaternary ammonium compound added to the fibrous cellulose are retained; preferably, the retention level of ester-functional 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.
  • DEDTHTDMAC DiEster Di(Touch Hardened)Tallow DiMethyl Ammonium Chloride
  • ester-functional quaternary ammonium compound promotes the adsorption of the polyhydroxy compound onto paper.
  • DEDTHTDMAC DiEster Di(Touch Hardened)Tallow DiMethyl Ammonium Chloride
  • a 1 : 1 weight ratio mixture of DEDTHTDMAC and glycerol appears (from direct observation and X-ray data) to be a liquid phase. While glycerol is capable of forming liquid crystal phases in combination with other surfactants, it appears not to do so in this system at this composition.
  • Dispersions of either of these materials may be prepared by diluting a mixture, that is held at a temperature at which the polyhydroxy compound and the ester-functional quaternary ammonium salt are miscible, with water.
  • a mixture that is held at a temperature at which the polyhydroxy compound and the ester-functional quaternary ammonium salt are miscible, with water.
  • Neither DEDTHTDMAC nor DEDHTDMAC are soluble in water, so the dilution of either dry phase with water will precipitate the ester-functional quaternary ammonium compound as small particles.
  • the polyhydroxy compound is soluble with water in all proportions, so it is not precipitated.
  • the liquid crystal phase in the diluted mixtures exists as vesicles which, for the most part, are closed and spherical.
  • the formation of such dispersion likely results from the large osmotic pressure gradients that momentarily exist during the process.
  • the origin of these pressure gradients is the spatial gradients in the composition (and thermodynamic activity) of water that are created. Since the liquid phase of DEDTHTDMAC / glycerol mixtures may exist over a wide range of temperature, one may also produce dispersions over a wide range of temperatures.
  • Cryoelectron microscopy demonstrates that the particles present 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 ester-functional quaternary ammonium ion to the paper, strongly promotes the adsorption of the polyhydroxy compound onto paper, and produces the desired modification of softness and retention of wettability.
  • the partial crystallization of the material within the colloidal particles may occur.
  • the attainment of the equilibrium state will require a long time (perhaps months), so that a disordered particle whose membranes are either a liquid crystal or a disordered crystal phase is interacting with the paper.
  • the chemical softening compositions described herein are used before the equilibrium state has been attained.
  • the vesicles containing quats and polyhydroxy compounds break apart upon drying of the fibrous cellulosic material.
  • the majority of the PEG component may penetrate into the interior of the cellulose fibers where it enhances the fiber flexibility.
  • 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 interaction, the cationic portion of the quats component stays on the surface of the cellulose fiber, where it enhances the surface feel and softness of the paper product.
  • a preferred 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 then removing 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 US-A-3,994,771, Morgan, Jr. et al. issued November 30, 1976.
  • 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 2 and about 65 g/m 2 , and density of about 0.60 g/cc or less.
  • basis weight will be below about 35 g/m 2 or less; and density will be about 0.30 g/cc or less.
  • density will be between 0.04 g/cc and about 0.20 g/cc.
  • Such paper is typically made by depositing papermaking furnish on a foraminous forming wire.
  • This forming wire is often referred to in the art as a Fourdrinier wire.
  • the web is dewatered by transfering 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 US-A-3,301,746, issued to Sanford and Sisson on January 31, 1967, US-A-3,974,025, issued to Peter G. Ayers on August 10, 1976, and US-A-4,191,609, issued to Paul D. Trokhan on March 4, 1980, and US-A-4,637,859, issued to Paul D. Trokhan on January 20, 1987.
  • pattern densified webs are preferably prepared by depositing a papermaking furnish on a foraminous forming wire such as a Fourdrinier wire to form a wet web and then juxtaposing the web against an array of supports.
  • the web is pressed against the array of supports, thereby resulting in densified zones in the web at the locations geographically corresponding to the points of contact between the array of supports and the wet web.
  • the remainder of the web not compressed during this operation is referred to as the high bulk field.
  • This high bulk field can be further dedensified by application of fluid pressure, such as with a vacuum type device or a blow-through dryer.
  • 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 US-A-3,301,746, Sanford and Sisson, issued January 31, 1967, US-A-3,821,068, Salvucci, Jr.
  • 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 US-A-3,812,000 issued to Joseph L. Salvucci, Jr. and Peter N. Yiannos on May 21, 1974 and US-A-4,208,459, issued to Henry E. Becker, Albert L. McConnell, and Richard Schutte on June 17, 1980,
  • 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.
  • Compacted non-pattern-densified tissue structures are commonly known in the art as conventional tissue structures.
  • compacted, non-pattern-densified tissue paper structures are prepared by depositing a papermaking furnish on a foraminous wire such as a Fourdrinier wire to form a wet web, draining the web and removing additional water with the aid of a uniform mechanical compaction (pressing) until the web has a consistency of 25-50%, transferring the web to a thermal dryer such as a Yankee and creping the web. Overall, water is removed from the web by vacuum, mechanical pressing and thermal means.
  • the resulting structure is strong and generally of singular density, but very low in bulk, absorbency and in softness.
  • tissue paper web of this invention can be used in any application where soft, absorbent tissue paper webs are required. Particularly advantageous uses of the tissue paper web of this invention are in paper towel, toilet tissue and facial tissue products.
  • tissue paper webs of this invention can be embossed and adhesively secured together in face to face relation as taught by US-A-3,414,459, which issued to Wells on December 3, 1968 to form 2-ply paper towels.
  • polymeric materials The essential distinguishing characteristic of polymeric materials is their molecular size.
  • the level of the ester-functional quaternary ammonium compound, such as DiEster Di(Hydrogenated)Tallow DiMethyl Ammonium Chloride (DEDHTDMAC) (i.e., ADOGEN DDMC®), retained by the tissue paper can be determined by solvent extraction of the DEDHTDMAC 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.
  • 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.
  • 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 11 .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.”
  • Suitable substantially waterless self-emulsifiable biodegradable chemical softening composition for use in the present invention are biodegradable.
  • biodegradability refers to the complete breakdown of a substance by microorganisms to carbon dioxide, water, biomass, and inorganic materials.
  • the biodegradation potential can be estimated by measuring carbon dioxide evolution and dissolved organic carbon removal from a medium containing the substance being tested as the sole carbon and energy source and a dilute bacterial inoculum obtained from the supernatant of homogenized activated sludge.
  • 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 US-A-4.011,389, issued to W.
  • 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 711 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 US-A-3,855,158 issued to Petrovich on December 17, 1974; US-A-3,899,388 issued to Petrovich on August 12, 1975; US-A-4,129,528 issued to Petrovich on December 12, 1978; US-A-4,147,586 issued to Petrovich on April 3, 1979; and US-A-4,222,921 issued to Van Eenam on September 16, 1980.
  • water-soluble cationic resins useful herein are the polyacrylamide resins such as those sold under the Parez trademark, such as Parez 631NC, by American Cyanamid Company of Stanford, Connecticut. These materials are generally described in US-A-3,556,932 issued to Coscia et al . on January 19, 1971; and US-A-3,556,933 issued to Williams et al . on January 19, 1971,
  • 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 US-A-3,844,880, Meisel, Jr. et al ., issued October 29, 1974.
  • 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.
  • polyethylenimine type resins find utility in the present invention.
  • water-soluble resins include their manufacture, and their manufacture.
  • the term "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 US-A-4,675,394, Solarek, et al ., issued June 23, 1987. Preferred temporary wet strength resins include those described in US-A-4,981,557, Bjorkquist, issued January 1, 1991.
  • the purpose of this example is to illustrate a method that can be used to make-up a substantially waterless self-emulsifiable biodegradable chemical softener composition
  • a substantially waterless self-emulsifiable biodegradable chemical softener composition comprising a mixture of DiEster Di(Touch Hardened)Tallow DiMethyl Ammonium Chloride (DEDTHTDMAC) and Polyoxyethylene Glycol 400 (PEG-400).
  • DEDTHTDMAC DiEster Di(Touch Hardened)Tallow DiMethyl Ammonium Chloride
  • PEG-400 Polyoxyethylene Glycol 400
  • a waterless self-emulsifiable biodegradable chemical softener composition is prepared according to the following procedure : 1. An equivalent weight of DEDTHTDMAC and PEG-400 is weighed separately; 2. PEG is heated up to about 66°C (150°F); 3. DEDTHTDMAC is dissolved in the PEG to form a melted solution at about 66°C (150°F); 4. Adequate mixing is provided to form a homogenous mixture of DEDTHTDMAC in PEG; 5. The homogenous mixture of (4) is cooled down to a solid form at room temperature.
  • the substantially waterless self-emulsifiable biodegradable 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 biodegradable chemical softener composition which comprises a mixture of DiEster Di(Touch Hardened)Tallow DiMethyl Ammonium Chloride (DEDTHTDMAC) and a mixture of Glycerol and PEG-400.
  • DEDTHTDMAC DiEster Di(Touch Hardened)Tallow DiMethyl Ammonium Chloride
  • a substantially waterless self-emulsifiable biodegradable chemical softener composition is prepared according to the following procedure : 1. A mixture of Glycerol and PEG-400 is blended at about 75 : 25 by weight ratio; 2. Equivalent weights of DEDTHTDMAC and the mixture of (1) are weighted separately; 3. Mixture of (1) is heated up to about 66°C (150°F); 4. DEDTHTDMAC 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 DEDTHTDMAC in (3); 6. The homogenous mixture of (5) is cooled down to a solid form at room temperature.
  • the substantially waterless self-emulsifiable biodegradable 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 biodegradable chemical softener composition
  • a substantially waterless self-emulsifiable biodegradable chemical softener composition comprising a premix of DiEster Di(Touch Hardened)tallow DiMethyl Ammonium Chloride (DEDTHTDMAC) and a Polyoxyethylene Glycol 400 (PEG-400) in solid state, and a permanent wet strength resin .
  • DEDTHTDMAC DiEster Di(Touch Hardened)tallow DiMethyl Ammonium Chloride
  • 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 biodegradable chemical softener composition is prepared according to the procedure in Example 1 wherein the homogenous premixed of DEDTHTDMAC and PEG-400 in solid state is dispersed in a conditioned water tank (pH ⁇ 3; Temperature ⁇ 66°C) to form a sub-micrometer 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 about 1.0 micrometer.
  • Figure 3 illustrates a cryo-transmission photo-micrograph taken at X 63,000 of a 2% concentration of the vesicle dispersion of a 1 : 1 by weight ratio of a DEDTHTDMAC and PEG-400 system in the solid state.
  • 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 nominal 3% by weight aqueous slurry of NSK is made up in a conventional re-pulper.
  • the NSK slurry is refined gently and a nominal 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 about 1% by weight of the dry fibers.
  • Kymene® 557H to NSK is enhanced by an in-line mixer.
  • a nominal 1% solution of Carboxy Methyl Cellulose (CMC) is added after the in-line mixer at a rate of about 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 (DEDTHTDMAC/ 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 about 0.2% by the fan pump.
  • 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 about 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 about 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 about 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 3.31 machine direction and 2.99 cross-machine direction monofilaments per mm (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 0.37 cells per mm 2 (240 Linear Idaho cells per square inch), 34 percent knuckle areas and 0.36 mm (14 mils) of photo-polymer depth.
  • 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, however, 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 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) 244 meters per minute.
  • the dry web is formed into roll at a speed of about (700 fpm) 214 meters per minutes.
  • the paper towel has about 42 g/m 2 (26 #/3M Sq Ft) basis weight, contains about 0.2% of the substantially waterless self-emulsifiable biodegradable 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 biodegradable chemical softener composition
  • a substantially waterless self-emulsifiable biodegradable chemical softener composition comprising a premix of DiEster Di(Touch Hardened)tallow DiMethyl Ammonium Methyl Chloride (DEDTHTDMAC) and a Polyoxyethylene Glycol 400 (PEG-400) in liquid state and a temporary wet strength resin.
  • DEDTHTDMAC DiEster Di(Touch Hardened)tallow DiMethyl Ammonium Methyl Chloride
  • 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 biodegradable chemical softener composition is prepared according to the procedure in Example 1 wherein the homogenous premix of DEDTHTDMAC 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 (pH ⁇ 3; Temperature ⁇ 66°C) to form a sub-micrometer 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 micrometer.
  • Figure 4 illustrates a cryo-transmission photo-micrograph taken at X 63,000 of a 2% concentration of the vesicle dispersion of a 1 : 1 by weight ratio of a DEDTHTDMAC and polyhydroxy compounds system in the liquid state.
  • 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 about 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 about 0.2% by weight of the dry fibers.
  • the adsorption of the substantially waterless self-emulsifiable biodegradable 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 3.31 machine direction and 2.99 cross-machine direction monofilaments per mm (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 photopolymer fabric having 0.87 cells per mm (562 Linear Idaho cells per square inch), 40 percent knuckle area and 0.23 mm (9 mils) of photo-polymer depth. 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 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) 244 meters per minute.
  • the dry web is formed into roll at a speed of about (700 fpm) 214 meters per minutes.
  • the web is convened into a one ply tissue paper product.
  • the tissue paper has about 29 g/m 2 (18 #/3M Sq Ft) basis weight, contains about 0.1% of the biodegradable 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 biodegradable chemical softener composition
  • a substantially waterless self-emulsifiable biodegradable chemical softener composition comprising a premix of DiEster Di(Touch Hardened)Tallow DiMethyl Ammonium Chloride (DEDTHTDMAC) and a mixture of polyhydroxy compound (Glycerol / PEG-400) in liquid state and a dry strength additive resin.
  • DEDTHTDMAC DiEster Di(Touch Hardened)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 biodegradable chemical softener composition is prepared according to the procedure in Example 2 wherein the homogenous premix of DEDTHTDMAC 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 (pH ⁇ 3; Temperature ⁇ 66°C) to form a sub-micrometer 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 micrometer.
  • Figure 5 illustrates a cryo-transmission photo-micrograph taken at X 63,000 of a 2% concentration of the vesicle dispersion of a 1 : 1 by weight ratio of a DEDTHTDMAC and polyhydroxy compounds system in the liquid state.
  • 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 711 marketed by American Cyanamid company of Fairfield, OH) is added to the NSK stock pipe at a rate of about 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 about 0.2% by weight of the dry fibers.
  • the adsorption of the substantially waterless self-emulsifiable biodegradable 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 3.31 machine direction and 2.99 cross-machine direction monofilaments per mm (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 0.87 cells per mm 2 (562 Linear Idaho cells per square inch), 40 percent knuckle area and 0.23 mm (9 mils) of photo-polymer depth. 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 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) 244 meters per minute.
  • the dry web is formed into roll at a speed of about (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 37 g/m 2 (23 #/3M Sq Ft) basis weight, contains about 0.1% of the substantially waterless self-emulsifiable biodegradable 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 biodegradable chemical softener composition
  • a substantially waterless self-emulsifiable biodegradable chemical softener composition comprising a premix of DiEster Di(Touch Hardened)Tallow DiMethyl Ammonium Chloride (DEDTHTDMAC) and a Polyoxyethylene Glycol 400 (PEG-400) in solid state and a dry strength additive resin.
  • DEDTHTDMAC DiEster Di(Touch Hardened)Tallow DiMethyl Ammonium Chloride
  • 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 biodegradable chemical softener composition is prepared according to the procedure in Example 1 wherein the homogenous premix of DEDTHTDMAC and PEG-400 in solid state is dispersed in a conditioned water tank (pH ⁇ 3; Temperature ⁇ 66°C) to form a sub-micrometer 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 micrometer.
  • Figure 3 illustrates a cryo-transmission photo-micrograph taken at X 63,000 of a 2% concentration of the vesicle dispersion of a 1 : 1 by weight ratio of a DEDTHTDMAC 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 711 marketed by American Cyanamid company of Wayne, New Jersey) is added to the NSK stock pipe at a rate of about 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 3.31 machine direction and 2.99 cross-machine monofilaments per mm (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) 244 meters per minute.
  • the dry web is formed into roll at a speed of about (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 37 g/m 2 (23 #/3M Sq Ft) basis weight, contains about 0.1% of the substantially waterless self-emulsifiable biodegradable 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.

Landscapes

  • Paper (AREA)
  • Biological Depolymerization Polymers (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
  • Polysaccharides And Polysaccharide Derivatives (AREA)
  • Cosmetics (AREA)
EP94920030A 1993-06-03 1994-05-23 Waterless self-emulsifiable biodegradable chemical softening composition useful in fibrous cellulosic materials Expired - Lifetime EP0702736B1 (en)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
US7229793A 1993-06-03 1993-06-03
US72297 1993-06-03
PCT/US1994/005778 WO1994029521A1 (en) 1993-06-03 1994-05-23 Waterless self-emulsifiable biodegradable chemical softening composition useful in fibrous cellulosic materials

Publications (2)

Publication Number Publication Date
EP0702736A1 EP0702736A1 (en) 1996-03-27
EP0702736B1 true EP0702736B1 (en) 2000-03-08

Family

ID=22106731

Family Applications (1)

Application Number Title Priority Date Filing Date
EP94920030A Expired - Lifetime EP0702736B1 (en) 1993-06-03 1994-05-23 Waterless self-emulsifiable biodegradable chemical softening composition useful in fibrous cellulosic materials

Country Status (26)

Country Link
EP (1) EP0702736B1 (ko)
JP (1) JP3428650B2 (ko)
KR (1) KR100336445B1 (ko)
AT (1) ATE190369T1 (ko)
AU (1) AU694739B2 (ko)
BR (1) BR9406786A (ko)
CA (1) CA2162850A1 (ko)
CZ (1) CZ321295A3 (ko)
DE (1) DE69423353T2 (ko)
DK (1) DK0702736T3 (ko)
EG (1) EG20526A (ko)
ES (1) ES2142947T3 (ko)
FI (1) FI955790A (ko)
GR (1) GR3032823T3 (ko)
HK (1) HK1016022A1 (ko)
HU (1) HUT74117A (ko)
MY (1) MY111105A (ko)
NO (1) NO954869L (ko)
NZ (1) NZ268169A (ko)
PE (1) PE53794A1 (ko)
PH (1) PH31546A (ko)
PT (1) PT702736E (ko)
SG (1) SG66293A1 (ko)
TR (1) TR27810A (ko)
TW (1) TW251324B (ko)
WO (1) WO1994029521A1 (ko)

Families Citing this family (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5538595A (en) * 1995-05-17 1996-07-23 The Proctor & Gamble Company Chemically softened tissue paper products containing a ploysiloxane and an ester-functional ammonium compound
DE19711452A1 (de) 1997-03-19 1998-09-24 Sca Hygiene Paper Gmbh Feuchtigkeitsregulatoren enthaltende Zusammensetzung für Tissueprodukte, Verfahren zur Herstellung dieser Produkte, Verwendung der Zusammensetzung für die Behandlung von Tissueprodukten sowie Tissueprodukte in Form von wetlaid einschließlich TAD oder Airlaid (non-woven) auf Basis überwiegend Cellulosefasern enthaltender flächiger Trägermaterialien
US6607637B1 (en) * 1998-10-15 2003-08-19 The Procter & Gamble Company Soft tissue paper having a softening composition containing bilayer disrupter deposited thereon
AU753313B2 (en) * 1998-10-15 2002-10-17 Procter & Gamble Company, The Process for making soft tissue paper
US11286620B2 (en) 2019-01-11 2022-03-29 The Procter & Gamble Company Quaternary ammonium compound compositions and methods for making and using same

Family Cites Families (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5223096A (en) * 1991-11-01 1993-06-29 Procter & Gamble Company Soft absorbent tissue paper with high permanent wet strength
US5217576A (en) * 1991-11-01 1993-06-08 Dean Van Phan Soft absorbent tissue paper with high temporary wet strength
US5264082A (en) * 1992-04-09 1993-11-23 Procter & Gamble Company Soft absorbent tissue paper containing a biodegradable quaternized amine-ester softening compound and a permanent wet strength resin
US5262007A (en) * 1992-04-09 1993-11-16 Procter & Gamble Company Soft absorbent tissue paper containing a biodegradable quaternized amine-ester softening compound and a temporary wet strength resin

Also Published As

Publication number Publication date
CA2162850A1 (en) 1994-12-22
NZ268169A (en) 1997-11-24
ES2142947T3 (es) 2000-05-01
GR3032823T3 (en) 2000-06-30
TW251324B (ko) 1995-07-11
FI955790A (fi) 1996-01-23
KR960702878A (ko) 1996-05-23
CZ321295A3 (en) 1996-07-17
TR27810A (tr) 1995-08-29
PE53794A1 (es) 1995-01-02
KR100336445B1 (ko) 2002-10-04
DE69423353T2 (de) 2000-10-12
EG20526A (en) 1999-06-30
EP0702736A1 (en) 1996-03-27
JPH08511069A (ja) 1996-11-19
HK1016022A1 (en) 1999-10-22
DE69423353D1 (de) 2000-04-13
PH31546A (en) 1998-11-03
MY111105A (en) 1999-08-30
NO954869D0 (no) 1995-11-30
HUT74117A (en) 1996-11-28
HU9503465D0 (en) 1996-01-29
BR9406786A (pt) 1996-01-30
NO954869L (no) 1996-02-02
AU694739B2 (en) 1998-07-30
JP3428650B2 (ja) 2003-07-22
PT702736E (pt) 2000-08-31
FI955790A0 (fi) 1995-12-01
AU7095894A (en) 1995-01-03
WO1994029521A1 (en) 1994-12-22
DK0702736T3 (da) 2000-06-05
ATE190369T1 (de) 2000-03-15
SG66293A1 (en) 1999-07-20

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