EP0706591B1 - Multi-layered tissue paper web comprising biodegradable chemical softening compositions and binders - Google Patents

Multi-layered tissue paper web comprising biodegradable chemical softening compositions and binders Download PDF

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Publication number
EP0706591B1
EP0706591B1 EP94920271A EP94920271A EP0706591B1 EP 0706591 B1 EP0706591 B1 EP 0706591B1 EP 94920271 A EP94920271 A EP 94920271A EP 94920271 A EP94920271 A EP 94920271A EP 0706591 B1 EP0706591 B1 EP 0706591B1
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Prior art keywords
tissue paper
fibers
web
layered tissue
layered
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EP94920271A
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German (de)
English (en)
French (fr)
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EP0706591A1 (en
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Dean Van Phan
Paul Dennis Trokhan
Bart Steven Hersko
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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
    • 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
    • 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
    • D21H17/00—Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
    • D21H17/20—Macromolecular organic compounds
    • D21H17/33—Synthetic macromolecular compounds
    • D21H17/46—Synthetic macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • D21H17/54—Synthetic macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H21/00—Non-fibrous material added to the pulp, characterised by its function, form or properties; Paper-impregnating or coating material, characterised by its function, form or properties
    • D21H21/14—Non-fibrous material added to the pulp, characterised by its function, form or properties; Paper-impregnating or coating material, characterised by its function, form or properties characterised by function or properties in or on the paper
    • D21H21/22—Agents rendering paper porous, absorbent or bulky
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H27/00—Special paper not otherwise provided for, e.g. made by multi-step processes
    • D21H27/30—Multi-ply
    • D21H27/38—Multi-ply at least one of the sheets having a fibrous composition differing from that of other sheets

Definitions

  • This invention relates to multi-layered tissue paper web. More particularly, it relates to multi-layered tissue paper web comprising biodegradable chemical softener compositions and binder materials.
  • the treated tissue webs can be used to make soft, absorbent and lint resistance paper products such as 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 facial and toilet tissues are staple items of commerce. It has long been recognized that four important physical attributes of these products are their strength, their softness, their absorbency, particularly their absorbency for aqueous systems; and their lint resistance, particularly their lint resistance 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.
  • 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.
  • 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.
  • 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 multi-layered tissue paper will absorb at saturation as well as the rate at which the mass absorbs the liquid.
  • Lint resistance is the ability of the fibrous product, and its constituent webs, to bind together under use conditions, particularly when wet. In other words, the higher the lint resistance is, the lower the propensity of the web to lint will be.
  • 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. in US-A- 3,755,220 issued August 28, 1973 mention that certain chemical additives known as debonding agents interfere with the natural fiber-to-fiber bonding that occurs during sheet formation in paper making processes. This reduction in bonding leads to a softer, or less harsh, sheet of paper.
  • 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 US-A- 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.
  • dialkyl dimethyl ammonium salts e.g. ditallow dimethyl ammonium chloride, ditallow dimethyl ammonium methyl sulfate, di(hydrogenated)tallow dimethyl ammonium chloride etc .
  • these quaternary ammonium compounds are hydrophobic and not biodegradable, and can adversely affect the absorbency of the treated paper webs..
  • biodegradable quaternary ammonium compound with a polyhdroxy compound (e.g., glycerol, sorbitols, polyglycerols or polyoxyethylene glycols) will enhance both softness and absorbency rate of fibrous cellulose materials.
  • a polyhdroxy compound e.g., glycerol, sorbitols, polyglycerols or polyoxyethylene glycols
  • biodegradable chemical softening compositions comprising a biodegradable quaternary ammonium compound and a polyhydroxy compound can decrease the lint resistance of the treated paper webs.
  • the lint resistance can be improved through the use of suitable binder materials such as wet and dry strength resins and retention aid resins known in the paper making art.
  • WO-A-93/09287 and WO-A-93/09288 both disclose a tissue paper web comprising paper making Fibers, a quaternary ammonium compound, a polyhydroxy compound and a permanent and/or temporary wet strenght resin. Applicants have discovered that selectively adding the majority of the quaternary ammonium compound and the polyhydroxy compound to the outer layers or plies of a multilayered or multiply tissue paper enhances its effectiveness.
  • the present invention is applicable to tissue paper in general, but particularily applicable to multi-layered tissue tissue paper products such as those described in US-A- 3,994,771, issued to Morgan Jr. et al. on November 30, 1976.
  • the present invention provides soft, absorbent, lint resistant multi-layered tissue paper products comprising paper making fibers, biodegradable chemical softening compositions and binder materials.
  • the biodegradable chemical softening composition comprises a mixture of:
  • the multi-layered web comprises an inner layer and at least an outer layer, said inner layer being located inside said at least one outer layer in case of combining two multilayered webs to a two-ply web, wherein the majority of the biodegradable quaternary ammonium compound and the polyhydroxy compound is contained in at least one outer layer.
  • the weight ratio of the biodegradable quaternary ammonium compound to the polyhydroxy compound ranges from about 1.0 : 0.1 to 0.1 : 1.0. It has been discovered that the biodegradable chemical softening composition is more effective when the polyhydroxy compound is mixed with said biodegradable quaternary ammonium compound at a temperature wherein said biodegradable quaternary ammonium compound and said polyhydroxy compound are miscible.
  • ester-functional quaternary ammonium compounds suitable for use in the present invention include compounds having the formulas: and and and wherein each R 2 substituent is a C 1 -C 6 alkyl or hydroxyalkyl group, benzyl group or mixtures thereof; each R 1 substituent is a C 12 - C 22 hydrocarbyl group, or substituted hydrocarbyl group or mixtures thereof; each R 3 substituent is a C 11 -C 21 hydrocarbyl group, or substituted hydrocarbyl or mixtures thereof.
  • 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, sorbitols, 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.
  • binder refers to the various wet and dry strength additives, and retention aids known in the art. These materials improve the lint resistance of the tissue paper webs of the present invention as well as counteracting any decrease in tensile strength caused by biodegradable chemical softening compositions.
  • suitable binder materials include permanent wet strength resins (i.e. Kymene ® 557H marketed by Hercules Incorporated of Wilmington, DE), temporary wet strength resins (i.e. National starch 78-0080 marketed by National Starch and Chemical corporation of New-York, NY), dry strength resins (i.e. Acco ® 514, Acco ® 711 marketed by American Cyanamid company of Wayne, New Jersey) and retention aid resins (i.e. Percol ®175 marketed by Allied Colloids of Sulfolk, Virginia).
  • the process for making the multi-layered tissue paper webs of the present invention comprises the steps of formation of a multi-layered paper making furnish from the aforementioned components, deposition of the multi-layered paper making furnish onto a foraminous surface such as a Fourdrinier wire, and removal of the water from the deposited furnish.
  • the term "lint resistance" is the ability of the fibrous product, and its constituent webs, to bind together under use conditions, particularly when wet. In other words, the higher the lint resistance is, the lower the propensity of the web to lint will be.
  • binder refers to the various wet and dry strength resins and retention aid resins known In the paper making art.
  • water soluble refers to materials that are soluble in water to at least 3% at 25 °C.
  • 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 fumish as by gravity or vacuum-assisted drainage, with or without pressing, and by evaporation.
  • an "aqueous paper making furnish” is an aqueous slurry of paper making fibers and the chemicals described hereinafter.
  • multi-layered tissue paper web, multi-layered paper web, multi-layered web, multi-layered paper sheet and multi-layered paper product all refer to sheets of paper prepared from two or more layers of aqueous paper making furnish which are preferably comprised of different fiber types, the fibers typically being relatively long softwood and relatively short hardwood fibers as used in tissue paper making.
  • the layers are preferably formed from the deposition of separate streams of dilute fiber slurries upon one or more endless foraminous screens. If the indidual layers are initially formed on separate wires, the layers are subsequently combined when wet to form a layered composite web.
  • the first step in the process of this invention is the forming of an aqueous paper making furnish.
  • the furnish comprises paper making fibers (hereinafter sometimes referred to as wood pulp), and a mixture of at least one biodegradable quaternary ammonium compound, a polyhydroxy compound and binder materials all of which will be hereinafter described.
  • wood pulp in all its varieties will normally comprise the paper making 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 Chemi-ThermoMechanical Pulp (CTMP). Pulps derived from both deciduous and coniferous trees can be used.
  • CMP Chemi-ThermoMechanical Pulp
  • hardwood pulps refers to fibrous pulp derived from the woody substance of deciduous trees (angiosperms): wherein softwood pulps are fibrous pulps derived from the woody substance of coniferous trees (gymnosperms).
  • Hardwood pulps such as eucalyptus are particularily suitable for the outer layers of the multi-layered tissue webs described hereinafter, whereas northern softwood Kraft pulps are preferrred for the inner layer(s) or ply(s).
  • 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 paper making.
  • the present invention contains as an essential component a mixture of a biodegradable quaternary ammonium compound and a polyhydroxy compound.
  • the ratio of the biodegradable quaternary ammonium compound to the polyhydroxy compound ranges from about 1.0 : 0.1 to 0.1 : 1.0; preferably, the weight ratio of the biodegradable quaternary ammonium compound to the polyhydroxy compound is about 1.0 : 0.3 to 0.3 : 1.0; more preferably, the weight ratio of the biodegradable quaternary ammonium compound to the polyhydroxy compound is about 1.0 : 0.7 to 0.7 : 1.0, although this ratio will vary depending upon the molecular weight of the particular polyhydroxy compound and/or biodegradable quaternary ammonium compound used.
  • the biodegradable chemical softening composition contains as an essential component from about 0.01% to about 3.00% by weight, preferably from about 0.01% to about 1.00% by weight of a biodegradable quaternary ammonium compound, preferably biodegradable quaternary ammonium compounds having the formula: or or wherein each R 2 substituent is a C1 - C6 alkyl or hydroxyalkyl group, benzyl group or mixtures thereof; each R 1 substituent is a C 12 - C 22 hydrocarbyl group, or substituted hydrocarbyl group or mixtures thereof; each R 3 substituent is a C 11 -C 21 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
  • tallow is a naturally occurring material having a variable composition.
  • Table 6.13 in the above-identified reference edited by Swem indicates that typically 78% or more of the fatty adds of tallow contain 16 or 18 carbon atoms.
  • 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.
  • 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 12 - C 18 alkyl and / or alkenyl, most preferably each R 1 is straight-chain C 16 - C 18 alkyl and / or alkenyl.
  • each R 2 is methyl or hydroxyethyl.
  • R 3 is C 13 - C 17 alkyl and / or alkenyl, most preferably R 3 is straight chain C 15 - C 17 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 1 - C 6 alkyl or hydroxyalkyl group
  • R 3 is C 11 -C 21 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 13 -C 17 alkyl and / or alkenyl, most preferably each R 3 is straight-chain C 15 -C 17 alkyl and / or alkenyl, and R 2 is a methyl.
  • the biodegradable chemical softening composition contains as an essential component from about 0.01% to about 3.00% by weight, preferably from about 0.01% to about 1.00% by weight of a polyhydroxy compound.
  • polyhydroxy compounds useful in the present invention include glycerol, sorbitols, 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 biodegradable chemical softening composition described above i.e. mixture of a biodegradable 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 paper making fibers, or furnish, in the wet end of the paper making machine at some suitable point ahead of the Fourdrinier wire or sheet forming stage.
  • applications of the above described biodegradable 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.
  • biodegradable chemical softening composition is more effective when the biodegradable quaternary ammonium compound and the polyhydroxy compound are first pre-mixed together before being added to the paper making furnish.
  • a preferred method consists of first heating the polyhydroxy compound to a temperature of about 66 °C (150°F), and then adding the biodegradable quatemary 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 : 0.1 to 0.1 : 1.0; preferably, the weight ratio of the biodegradable quaternary ammonium compound to the polyhydroxy compound is about 1.0 : 0.3 to 0.3 : 1.0; more preferably, the weight ratio of the biodegradable quaternary ammonium compound to the polyhydroxy compound is about 1.0 : 0.7 to 0.7 : 1.0, although this ratio will vary depending upon the molecular weight of the polyhydroxy compound and/or biodegradable quaternary ammonium compound used.
  • the adsorption of the potyhydroxy compound onto paper is significantly enhanced when it is premixed with the biodegradable quaternary ammonium compound and added to the paper by the above described process.
  • at least 20% of the polyhydroxy compound and the biodegradable quatemary ammonium compound added to the fibrous cellulose are retained; preferably, the retention level of biodegradable 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 biodegradable chemical softening compositions described herein are used before the equilibrium state has been attained.
  • the vesicles containing biodegradable 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 biodegradable quats component stays on the surface of the cellulose fiber, where it enhances the surface feel and softness of the paper product.
  • the present invention contains as an essential component from about 0.01% to about 3.0%, preferably from about 0.01% to about 1% by weight of a binder material selected from the group consisting of permanent wet strength resins, temporary wet strength resins, dry strength resins, retention aid resins and mixtures thereof.
  • the binder materials act to control linting and also to offset the loss in tensile strength, if any, resulting from the biodegradable chemical softener compositions.
  • the binder materials can be chosen from the following group of chemicals: polyamide-epichlorohydrin, polyacrylamides, styrene-butadiene latexes; insolubilized polyvinyl alcohol; ureaformaldehyde; polyethyleneimine; chitosan polymers and mixtures thereof.
  • Polyamide-epichlorohydrin resins are cationic wet strength resins which have been found to be of particular utility.
  • Polyacrylamide resins have also been found to be of utility as wet strength resins or retention aids. These resins are described in US-A-3,556,932, issued on January 19, 1971, to Coscia, et al. and 3,556,933, issued on January 19, 1971, to Williams et al.,
  • One commercial source of polyacrylamide resins is American Cyanamid Co. of Stanford, Connecticut, which markets one such resin under the mark Parez ® 631 NC.
  • Other commercial sources of cationic polyacrylamide resins are Allied Colloids of Sulfolk, Virginia, and Hercules, Inc. of Wilmington, Delaware, which markets such resins under the marks Percol ® 175 and Reten ® 1232.
  • Still other water-soluble cationic resins finding utility in this invention are urea formaldehyde and melamine formaldehyde resins.
  • the more common functional groups of these polyfunctional resins are nitrogen containing groups such as amino groups and methylol groups attached to nitrogen.
  • Polyethylenimine type resins may also find utility in the present invention.
  • the binder materials can be chosen from the following group of starch-based temporary wet strength resins: cationic dialdehyde starch-based resin (such as Caldas produced by Japan Carlet or Cobond 1000 produced by National Starch); dialdehyde starch; and/or the resin described in US-A-4,981,557 issued on January 1, 1991, to Bjorkquist
  • the binder materials can be chosen from the following group of materials: polyacrylamide (such as combinations of Cypro 514 and Accostrength 711 produced by American cyanamid of Wayne, N.J.); starch (such as corn starch or potato starch); polyvinyl alcohol (such as Airvol 540 produced by Air Products Inc of Allentown, PA); guar or locust bean gums; polyacrylate latexes; and/or carboxymethyl cellulose (such as Aqualon CMC-T from Aqualon Co., Wilmington, DE).
  • suitable starch for practicing the present Invention is characterized by water solubility, and hydrophilicity.
  • Exemplary starch materials include corn starch and potato starch, albeit it is not intended to thereby limit the scope of suitable starch materials; and waxy corn starch that is known industrially as amioca starch is particularly preferred.
  • Amioca starch differs from common corn starch in that it is entirely amylopectin, whereas common corn starch contains both amplopectin and amylose.
  • Various unique characteristics of amioca starch are further described in 'Amioca - The Starch from Waxy Corn", H. H. Schopmeyer, food Industries, December 1945, pp. 106-108 (Vol. pp. 1476-1478).
  • the starch can be in granular or dispersed fom albeit granular form is preferred.
  • the starch is preferably sufficiently cooked to induce swelling of the granules. More preferably, the starch granules are swollen, as by cooking, to a point just prior to dispersion of the starch granule. Such highly swollen starch granules shall be referred to as being "fully cooked".
  • the conditions for dispersion in general can vary depending upon the size of the starch granules, the degree of crystallinity of the granules, and the amount of amylose present.
  • Fully cooked amioca starch for example, can be prepared by heating an aqueous slurry of about 4X consistency of starch granules at about 190 °F (about 88 °C) for between about 30 and about 40 minutes.
  • Other exemplary starch materials which may be used include modified cationic starches such as those modified to have nitrogen containing groups such as amino groups and methylol groups attached to nitrogen, available from National Starch and Chemical Company, (Bridgewater, New Jersey). Such modified starch materials are used primarily as a pulp furnish additive to increase wet and/or dry strength. Considering that such modified starch materials are more expensive than unmodified starches, the latter have generally been preferred.
  • Methods of application include, the same previously described with reference to application of other chemical additives preferably by wet end addition, spraying; and, less preferably, by printing.
  • the binder may be applied to the tissue paper web alone, simultaneously with, prior to, or subsequent to the addition of softener, absorbency, and/or aesthetic additives.
  • At least an effective amount of a binder, preferably starch, to provide lint control and concomitant strength increase upon drying relative to a non-binder treated but otherwise identical sheet is preferably applied to the sheet.
  • a binder is retained in the dried sheet, calculated on a dry fiber weight basis; and, more preferably, between about 0.1% and about 1.0% of a binder material, preferably starch-based, is retained.
  • the second step in the process of this invention is the depositing of the multi-layered paper making furnish using the above described chemical softener composition and binder materials as additives 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 paper making art.
  • Preferred mutti-layered tissue paper embodiments of the present invention contain from about 0.01% to about 3.0%, more preferably from about 0.1% to 1.0% by weight, on a dry fiber basis of the biodegradable chemical softening composition and binder materials described herein.
  • the present invention is applicable to multi-layered tissue paper in general, including but not limited to conventionally felt-pressed multi-layered tissue paper; high bulk pattern densified multi-layered tissue paper; and high bulk, uncompacted multi-layered tissue paper.
  • the multi-layered 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 multi-layered tissue paper making, upon one or more endless foraminous screens. If the individual layers are initially formed on separate wires, the layers are subsequently combined when wet 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 paper making 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 multi-layered 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/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 3 or less.
  • density will be between 0.04 g/cm 3 and 0.20 g/cm 3 .
  • the multi-layered tissue paper webs of the present invention comprise at least two superposed layers, a first layer and at least one second layer contiguous with the first layer.
  • the multi-layered tissue papers comprise three superposed layers, an inner or center layer, and two outer layers, with the inner layer located between the two outer layers.
  • the two outer layers preferably comprise a primary filamentary constituent of about 60% or more by weight of relatively short paper making fibers having an average fiber between about 0.2 and about 1.5 mm. These short paper making fibers are typically hardwood fibers, preferably, eucalyptus fibers.
  • low cost sources of short fibers such as sulfite fibers, thermomechanical pulp fibers, cheml-thermomechanlcal pulp fibers, recycled fibers including fibers fractionated from recycled fibers, and mixtures thereof can be used in one or both of the outer layers or blended in the inner layer, if desired.
  • the inner layer preferably comprises a primary filamentary constituent of about 60% or more by weight of relatively long paper making fibers having an average fiber length of least about 2.0 mm. These long paper making fibers are typically softwood fibers, preferably, northern softwood Kraft fibers.
  • Figure 1 is a schematic cross-sectional view of a three-layered single ply toilet tissue in accordance with the present invention.
  • the three layered single ply web 10 comprises three superposed layers, inner layer 12 , and two outer layers 11. Outer layers 11 are comprised primarily of short paper making fibers 16; whereas inner layer 12 is comprised primarily of long paper making fibers 17 .
  • multi-ply tissue paper products are formed by placing at least two multi-layered tissue paper webs in juxtaposed relation.
  • a two-ply tissue paper product can be made comprising a first two-layered tissue paper web and a second two-layered tissue paper web in juxtaposed relation.
  • each ply is a two-layer tissue sheet comprising a first layer and a second layer.
  • the first layer preferably comprises the short hardwood fibers and the second layer preferably comprises the long softwood fibers.
  • the two plys are combined in a manner such that the short hardwood fibers of each ply face outwardly, and the layers containing the long softwood fibers face inwardly.
  • FIG. 2 is a schematic cross-sectional view of a two-layered two-ply facial tissue in accordance with the present invention.
  • the two-layered two- ply web 20 is comprised of two plies 15 in juxtaposed relation.
  • Each ply 15 is comprised of inner layer 19 , and outer layer 18.
  • Outer layers 18 are comprised primarily of short paper making fibers 16; whereas inner layers 19 are comprised primarily of long paper making fibers 17 .
  • three-ply tissue paper products can be made by placing three multi-layered tissue paper webs in juxtaposed relation.
  • tissue paper products comprising three-layers -- single ply or two-plys -- two layers, etc.
  • Tissue paper products consisting of three or more plys in combination with each ply consisting of one or more layers are also expressly meant to be included within the scope of the present invention.
  • the majority of the biodegradable quaternary ammonium compound and the polyhydroxy compound is contained in at least one of the outer layers of the multi-layered tissue paper web of the present invention. More preferably, the majority of the biodegradable quaternary ammonium compound and the polyhydroxy compound is contained in both of the outer layers. It has been discovered that the biodegradable chemical softening composition is most effective when added to the outer layers or plies of the tissue paper products. There, the mixture of the biodegradable quaternary compound and polyhdroxy compound act to enhance both the softness and the absorbency of the multi-layered tissue products of the present invention.
  • the biodegradable chemical softening composition comprising a mixture of the biodegradable quaternary ammonium compound and the polyhdroxy compound is schematically represented by dark circles 14 . It can be seen in figures 1 and 2 that the majority of the biodegradable chemical softening composition 14 is contained in outer layers 11 and 18 , respectively.
  • binder materials are used for linting control and to increase the tensile strength.
  • the binder is contained in the inner layer and at least one of the outer layers of the multi-layered tissue paper webs of the present invention. More preferably, the binder is contained throughout the multi-layered product, i.e., in the inner and outer layers.
  • the binder materials are schematically represented by white circles 13 . It can be seen in figures 1 and 2 that the majority of the binder materials 13 are contained in inner layers 12 and 19 respectively. In an alternate preferred embodiment (not shown), the majority of the binder is contained in at least one of the outer layers, more preferably both of the two outer layers of the multi-layered product.
  • biodegradable chemical softening composition comprising a biodegradable quaternary ammonium compound and a polyhydroxy compound in conjunction with a binder material results in a tissue paper product having superior softness, absorbency, and lint resistance properties.
  • a tissue paper product having superior softness, absorbency, and lint resistance properties.
  • Selectively adding the majority of the biodegradable chemical softening composition to the outer layers or plys of the tissue paper enhances its effectiveness.
  • the binder materials are dispersed throughout the tissue sheet to control linting. However, like the biodegradable chemical softening composition, the binder materials can be selectively added where most needed.
  • Such paper is typically made by depositing paper making 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 multi-layered tissue paper structures which are formed are referred to hereinafter as conventional, pressed, multi-layered 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 multi-layered 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 paper making 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 multi-layered 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 multi-layered 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 multi-layered tissue paper structures are prepared by depositing a paper making 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.
  • the multi-layered tissue paper web of this invention can be used in any application where soft, absorbent multi-layered tissue paper webs are required. Particularly advantageous uses of the multi-layered tissue paper web of this invention are in toilet tissue and facial tissue products.
  • two multi-layered tissue paper webs of this invention can be ply-bonded to form 2-ply facial or toilet tissue products.
  • 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 multi-layered tissue paper refers, in general, to the propensity of the multi-layered tissue paper to be wetted with water. Hydrophilicity of multi-layered tissue paper may be somewhat quantified by determining the period of time required for dry multi-layered 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.
  • approximately 4-3/8 inch x 4-3/4 inch (about 11.1 cm x 12 cm) of multi-layered 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 multi-layered 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 multi-layered 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. See Larson, "Estimation of Biodegradation Potential of Xenobiotic Organic Chemicals," Applied and Environmental Microbiology.
  • the density of multi-layered 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 multi-layered tissue paper is the thickness of the paper when subjected to a compressive load of 95 g/in 2 (15.5 g/cm 2 ).
  • Dry lint can be measured using a Sutherland Rub Tester, a piece of black felt, a four pound weight and a Hunter Color meter.
  • the Sutherland tester is a motor-driven instrument which can stroke a weighted sample back and forth across a stationary sample.
  • the piece of black felt is attached to the four pound weight.
  • the tester then rubs or moves the weighted felt over a stationary issue sample for five strokes.
  • the Hunter Color L value of the black felt is determined before and after rubbing. The difference in the two Hunter Color readings constitutes a measurement of dry linting.
  • Other methods known in the prior arts for measuring dry lint also can be used.
  • biodegradable chemical softening composition described herein, or to the paper making furnish so long as they do not significantly and adversely affect the softening, absorbency of the fibrous material, and enhancing actions of the biodegradable chemical softening composition.
  • surfactants may be used to treat the multi-layered 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 multi-layered 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.
  • 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 biodegradable 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 biodegradable 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 blow through drying and layered paper making techniques to make soft, absorbent and lint resistance toilet multi-layered tissue paper treated with a chemical softener composition comprising DiEster Di(Touch Hardened)Tallow DiMethyl Ammonium Chloride (DEDTHTDMAC) and a Polyoxyethylene Glycol 400 (PEG-400) and a temporary wet strength resin.
  • a chemical softener composition comprising DiEster Di(Touch Hardened)Tallow DiMethyl Ammonium Chloride (DEDTHTDMAC) and a Polyoxyethylene Glycol 400 (PEG-400) and a temporary wet strength resin.
  • DEDTHTDMAC DiEster Di(Touch Hardened)Tallow DiMethyl Ammonium Chloride
  • PEG-400 Polyoxyethylene Glycol 400
  • a pilot scale Fourdrinier paper making machine is used in the practice of the present invention.
  • the 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.
  • 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 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
  • National starch 78-0080 marketed by National Starch and Chemical corporation of New-York, NY
  • a 1% solution of the biodegradable chemical softener mixture is added to the Eucalyptus stock pipe before the in-line mixer at a rate of 0.2% by weight of the dry fibers.
  • 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 8.7 ⁇ 10 5 Linear Idaho cells (per square meter 56.2 per square inch) 40 percent knuckle area and 0.023 cm (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) (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 multi-layered tissue paper product.
  • the multi-layered tissue paper has about 3.2g/m 2 (18 #/3M Sq Ft)basis weight, contains about 0.2% of the biodegradable chemical softener mixture and about 0.3% of the temporary wet strength resin.
  • the resulting multi-layered tissue paper is soft, absorbent, has good lint resistance 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 paper making technique to make soft, absorbent and lint resistance toilet multi-layered tissue paper treated with a chemical softener composition comprising DiEster Di(Touch Hardened)Tallow DiMethyl Ammonium Chloride (DEDTHTDMAC) and a mixture of polyhydroxy compound (Glycerol / PEG-400) and a dry strength additive resin.
  • a chemical softener composition comprising DiEster Di(Touch Hardened)Tallow DiMethyl Ammonium Chloride (DEDTHTDMAC) and a mixture of polyhydroxy compound (Glycerol / PEG-400) and a dry strength additive resin.
  • a pilot scale Fourdrinier paper making machine is used in the practice of the present invention.
  • the 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.
  • 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 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 2% solution of the dry strength resin i.e. Acco ® 514, Acco ® 711 marketed by American Cyanamid company of Fairfield, OH
  • Acco ® 514, Acco ® 711 marketed by American Cyanamid company of Fairfield, OH
  • a 1% solution of the biodegradable chemical softener mixture is added to the Eucalyptus stock pipe before the in-line mixer at a rate of 0.2% by weight of the dry fibers.
  • 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 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 3360 (84) machine-direction and 3040 (76) cross-machine-direction monofilaments per m (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 8.7 ⁇ 10 5 Linear Idaho cells per square meter (562 per square inch ), 40 percent knuckle area and 0.023cm (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) (about 244 meters per minute).
  • the dry web is formed into roll at a speed of 700 fpm ( 214 meters per minutes).
  • the multi-layered tissue paper has about 40.g/m 2 (23 #/3M Sq Ft) basis weight, contains about 0.1% of the biodegradable chemical softener mixture and about 0.2% of the dry strength resin.
  • the resulting multi-layered tissue paper is soft, absorbent, has good lint resistance 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 paper making technique to make soft, absorbent and lint resistance toilet multi-layered tissue paper treated with a chemical softener composition comprising DiEster Di(Touch Hardened)Tallow DiMethyl Ammonium Chloride (DEDTHTDMAC) and a Polyoxyethylene Glycol 400 (PEG-400), a dry strength additive and a cationic polyacrylamide additive resin (Percol ® 175) as retention aid.
  • a chemical softener composition comprising DiEster Di(Touch Hardened)Tallow DiMethyl Ammonium Chloride (DEDTHTDMAC) and a Polyoxyethylene Glycol 400 (PEG-400), a dry strength additive and a cationic polyacrylamide additive resin (Percol ® 175) as retention aid.
  • DEDTHTDMAC DiEster Di(Touch Hardened)Tallow DiMethyl Ammonium Chloride
  • PEG-400 Polyoxyethylene Glycol 400
  • a pilot scale Fourdrinier paper making machine is used in the practice of the present invention.
  • the 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.
  • 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 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 biodegradable 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; and a 0.05% solution of Percol ® 175 is added to the Eucalyptus layers before the fan pump at a rate of 0.05% by weight of the dry fibers.
  • the adsorption of the 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 3360 (84) machine-direction and 3040 (76) cross-machine-direction monofilaments per m (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).
  • the multi-layered tissue paper has about 40g/m 2 (23 #/3M Sq. Ft.) basis weight, contains about 0.1% of the biodegradable chemical softener mixture, about 0.1% of the dry strength resin and about 0.05% of the retention aid resin.
  • the resulting multi-layered tissue paper is soft, absorbent, has good lint resistance and is suitable for use as a facial and/or toilet tissues.
  • the purpose of this example is to illustrate a method using a blow through drying and layered paper making techniques to make soft, absorbent and lint resistance facial multi-layered tissue paper treated with a chemical softener composition comprising DiEster Di(Touch Hardened)Tallow DiMethyl Ammonium Chloride (DEDTHTDMAC) and a Polyoxyethylene Glycol 400 (PEG-400), a permanent wet strength resin and a retention aid (Percol® 175).
  • DEDTHTDMAC DiEster Di(Touch Hardened)Tallow DiMethyl Ammonium Chloride
  • PEG-400 Polyoxyethylene Glycol 400
  • Percol® 175 a retention aid
  • a pilot scale Fourdrinier paper making machine is used in the practice of the present invention.
  • the 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.
  • 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 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.
  • 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 biodegradable chemical softener mixture is added to the Eucalyptus stock pipe before the in-line mixer at a rate of 0.2% by weight of the dry fibers; and a 0.5% solution of Percol® 175 is added to the Eucalyptus layers before the fan pump at a rate of 0.05% by weight of the dry fibers.
  • the Eucalyptus slurry is diluted to about 0.2% consistency at the fan pump.
  • the treated fumish mixture (50% of NSK / 50% 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 3360 (84) machine-direction and 3040 (76) cross-machine-direction monofilaments per m (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 11 ⁇ 10 5 Linear Idaho cells per square (711 Linear Idaho cells per square m), 40 percent knuckle area and 0.023cm (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) (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 two ply multi-layered facial tissue paper.
  • the multi-layered tissue paper has about 37g/m 2 (21 #/3M Sq Ft)basis weight, contains about 1% of the permanent wet strength resin, about 0.2% of the biodegradable chemical softener mixture and about 0.05% of the retention aid resin.
  • the resulting multi-layered tissue paper is soft, absorbent, has good lint resistance and is suitable for use as facial tissues.

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Paper (AREA)
  • Sanitary Thin Papers (AREA)
  • Materials For Medical Uses (AREA)
  • Laminated Bodies (AREA)
  • Biological Depolymerization Polymers (AREA)
EP94920271A 1993-06-30 1994-06-17 Multi-layered tissue paper web comprising biodegradable chemical softening compositions and binders Expired - Lifetime EP0706591B1 (en)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
US8585293A 1993-06-30 1993-06-30
US85852 1993-06-30
PCT/US1994/006916 WO1995001479A1 (en) 1993-06-30 1994-06-17 Multi-layered tissue paper web comprising biodegradable chemical softening compositions and binder materials and process for making the same

Publications (2)

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EP0706591A1 EP0706591A1 (en) 1996-04-17
EP0706591B1 true EP0706591B1 (en) 2001-08-29

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JP (1) JPH08512104A (tr)
KR (1) KR100333211B1 (tr)
AT (1) ATE204935T1 (tr)
AU (1) AU7112894A (tr)
BR (1) BR9406992A (tr)
CA (1) CA2165536A1 (tr)
CZ (1) CZ351495A3 (tr)
DE (1) DE69428118T2 (tr)
ES (1) ES2159561T3 (tr)
FI (1) FI956336A (tr)
HU (1) HUT74119A (tr)
MY (1) MY114367A (tr)
NO (1) NO308320B1 (tr)
NZ (1) NZ268281A (tr)
PE (1) PE28095A1 (tr)
SG (1) SG64312A1 (tr)
TR (1) TR27850A (tr)
TW (1) TW305001B (tr)
WO (1) WO1995001479A1 (tr)

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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
US5882743A (en) * 1997-04-21 1999-03-16 Kimberly-Clark Worldwide, Inc. Absorbent folded hand towel
US6423183B1 (en) 1997-12-24 2002-07-23 Kimberly-Clark Worldwide, Inc. Paper products and a method for applying a dye to cellulosic fibers
US6607637B1 (en) * 1998-10-15 2003-08-19 The Procter & Gamble Company Soft tissue paper having a softening composition containing bilayer disrupter deposited thereon
JP2002527641A (ja) * 1998-10-15 2002-08-27 ザ、プロクター、エンド、ギャンブル、カンパニー 柔らかいティッシュ・ペーパーを製造する方法
US6749721B2 (en) 2000-12-22 2004-06-15 Kimberly-Clark Worldwide, Inc. Process for incorporating poorly substantive paper modifying agents into a paper sheet via wet end addition
US6582560B2 (en) 2001-03-07 2003-06-24 Kimberly-Clark Worldwide, Inc. Method for using water insoluble chemical additives with pulp and products made by said method
US7749356B2 (en) 2001-03-07 2010-07-06 Kimberly-Clark Worldwide, Inc. Method for using water insoluble chemical additives with pulp and products made by said method
US20060070712A1 (en) * 2004-10-01 2006-04-06 Runge Troy M Absorbent articles comprising thermoplastic resin pretreated fibers
US7670459B2 (en) 2004-12-29 2010-03-02 Kimberly-Clark Worldwide, Inc. Soft and durable tissue products containing a softening agent
US8282776B2 (en) 2005-12-15 2012-10-09 Kimberly-Clark Worldwide, Inc. Wiping product having enhanced oil absorbency
US7807023B2 (en) 2005-12-15 2010-10-05 Kimberly-Clark Worldwide, Inc. Process for increasing the basis weight of sheet materials
US8444811B2 (en) 2005-12-15 2013-05-21 Kimberly-Clark Worldwide, Inc. Process for increasing the basis weight of sheet materials
US7879191B2 (en) 2005-12-15 2011-02-01 Kimberly-Clark Worldwide, Inc. Wiping products having enhanced cleaning abilities
US7879189B2 (en) 2005-12-15 2011-02-01 Kimberly-Clark Worldwide, Inc. Additive compositions for treating various base sheets
US7820010B2 (en) 2005-12-15 2010-10-26 Kimberly-Clark Worldwide, Inc. Treated tissue products having increased strength
US7785443B2 (en) 2006-12-07 2010-08-31 Kimberly-Clark Worldwide, Inc. Process for producing tissue products
ES2367748B1 (es) * 2009-01-19 2012-06-07 Hilaturas Ferre, S.A. Procedimiento para la obtención de hilos con propiedades biocidas.
US8105463B2 (en) 2009-03-20 2012-01-31 Kimberly-Clark Worldwide, Inc. Creped tissue sheets treated with an additive composition according to a pattern

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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
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
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

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PE28095A1 (es) 1995-10-11
BR9406992A (pt) 1996-09-10
CZ351495A3 (en) 1996-07-17
TR27850A (tr) 1995-09-04
TW305001B (tr) 1997-05-11
NO960002D0 (no) 1996-01-02
KR960703448A (ko) 1996-08-17
KR100333211B1 (ko) 2002-11-04
FI956336A0 (fi) 1995-12-29
AU7112894A (en) 1995-01-24
CA2165536A1 (en) 1995-01-12
FI956336A (fi) 1996-02-28
NO308320B1 (no) 2000-08-28
ES2159561T3 (es) 2001-10-16
DE69428118T2 (de) 2002-06-06
EP0706591A1 (en) 1996-04-17
ATE204935T1 (de) 2001-09-15
SG64312A1 (en) 1999-04-27
HU9503967D0 (en) 1996-03-28
WO1995001479A1 (en) 1995-01-12
NO960002L (no) 1996-02-29
MY114367A (en) 2002-10-31
JPH08512104A (ja) 1996-12-17
NZ268281A (en) 1998-03-25
HUT74119A (en) 1996-11-28
DE69428118D1 (de) 2001-10-04

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