AU734408B2 - Multi-layered tissue paper web comprising biodegradable chemical softening compositions and binder materials and process for making the same - Google Patents

Description

P/00/011 28/5/91 Regulation 3.2(2)

AUSTRALIA

Patents Act 1990

ORIGINAL

COMPLETE SPECIFICATION STANDARD PATENT Application Number: Lodged: Invention Title: MULTI-LAYERED TISSUE PAPER WEB COMPRISING BIODEGRADABLE CHEMICAL SOFTENING COMPOSITIONS AND BINDER MATERIALS AND PROCESS FOR MAKING THE SAME.

The following statement is a full description of this invention, including the best method of performing it known to us MULTI-LAYERED TISSUE PAPER WEB COMPRISING BIODEGRADABLE CHEMICAL SOFTENING COMPOSITIONS AND BINDER MATERIALS AND PROCESS FOR MAKING THE SAME FIELD OF THE INVENTION 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.

BACKGROUND OF THE INVENTION 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.

Lnt 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.

The use of wet strength resins to enhance the strength of a paper web is widely known. For example, Wesffelt 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 U.S. Pat. No. 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.

Shaw, in U.S. Pat. No. 3,821,068, issued June 28, 1974, also teaches that chemical debonders can be used to reduce the stiffness, and thus enhance the softness, of a tissue paper web.

Chemical debonding agents have been disclosed in various references such as U.S. Pat. No. 3,554,862, issued to Hervey et al. on January 12, 1971.

These materials include quaternary ammonium salts such as cocotrimethylammonium chloride, oleyltrimethylammonium chloride, di(hydrogenated)tallow dimethyl ammonium chloride and stearyltrimethyl ammonium chloride.

Emanuelsson et al., in U.S. Pat. No. 4,144,122, issued March 13, 1979, teach the use of complex quaternary ammonium compounds such as bis(alkoxy(2hydroxy)propylene) quaternary ammonium chlorides to soften webs. These authors also attempt to overcome any decrease in absorbency caused by the debonders through the use of nonionic surfaciants such as ethylene oxide and propylene oxide adducts of fatty alcohols.

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.

One exemplary result of research directed toward improved paper webs is described in U.S. Pat. No. 3,301,746, issued to Sanford and Sisson on January 31, 1967. Despite the high quality of paper webs made by the process described in this patent, and despite the commercial success of products formed from these webs, research efforts directed to finding improved products have continued.

For example, Becker et al. in U.S. Pat. No. 4,158,594, issued January 19, 1979, describe a method they contend will form a strong, soft, fibrous sheet. More specifically, they teach that the strength of a tissue paper web (which may have been softened by the addition of chemical debonding agents) can be enhanced by adhering, during processing, one surface of the web to a creping surface in a fine patterned arrangement by a bonding material (such as an acrylic latex rubber emulsion, a water soluble resin, or an elastomeric bonding material) which has been adhered to one surface of the web and to the creping surface in the fine patterned arrangement, and creping the web from the creping surface to form a sheet material.

Conventional quaternary ammonium compounds such as the well known dialkyl dimethyl ammonium salts ditallow dimethyl ammonium chloride, ditallow dimethyl ammonium methyl sulfate, di(hydrogenated)tallow dimethyl Sammonium chloride etc are effective chemical debonding agents. However, Sthese quaternary ammonium compounds are hydrophobic and not biodegradable, and can adversely affect the absorbency of the treated paper webs.. Applicants have discovered that mixing the biodegradable quaternary ammonium compound with a polyhdroxy compound glycerol, sorbitols, polyglycerols or polyoxyethylene glycols) will enhance both softness and absorbency rate of fibrous cellulose materials.

Unfortunately the use of biodegradable chemical softening compositions comprising a biodegradable quaternary ammonium compound and a polyhydroxy compound can decrease the lint resistance of the treated paper webs. Applicants have discovered that 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.

6. AP R.2001-17:31 WATERMARK PATENT 613 98196010 NO. 0867 P. 4/10 4 The present invention is applicable to tissue paper in general, but particularly applicable to multi-layered tissue paper products such as those described in U.S. Patent 3,994,771, issued to Morgan Jr. et. al, on November 1976, and incorporated herein by reference, It is an object of this invention to provide soft, absorbent and lint resistance multi-layered tissue paper products.

It is also a further object of this invention to provide a process for making soft, absorbent, line resistance multi-layered tissue paper products.

These and other objects are obtained using the present invention, as will become readily apparent from a reading of the following disclosure.

SUMMARY OF THE INVENTION The present invention provides soft, absorbent, line resistant multilayered tissue paper products comprising paper making fibers, biodegradable chemical softening compositions and binder materials. Briefly, the biodegradable chemical softening composition comprises a mixture of: from about 0,01% to about 3.0% of a biodegradable quaternary ammonium compound, having the formula:

R

2

(CH

2 )n-Y-R 3

XX_

R

2

(CH

2 3

R

2

(CH

2 )n-Y-R 3

R

2

R,

and

R

3

-Y-CH

2

CH-CH

2

-N-(R

2

X-

R3-Y 06/04 '01 FRI 17:34 [TX/RX NO 9016] 6-APR.2001 17:31 WATERMARK PATENT 613 98196010 NO. 0867 P. 5/10 wherein each R 2 substituent is a C,-Ca alkyl or hydroxyalkyl group, benzyl group or mixtures thereof; each R, substituent is a C 12 hydrocarbyl group, or substituted hydrocarbyl group or mixtures thereof; each R, substituent is a C,1-C21 hydrocarbyl group, or substituted hydrocarbyl or mixtures thereof; Y is or or -NH-C(O) or and mixtures thereof; n is 1 to 4 and X" is a suitable anion, for example, chloride, bromide, methylsulfate, ethylsulfate, nitrate and the like; and from about 0.01% to about 3.0% of a polyhydroxy compound; preferably selected from the group consisting of 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 from about 200 to 4000; and from 0.01% to 3.0% of a binder material.

Preferably 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.

Examples of preferred ester-functional quaternary ammonium compounds suitable for use in the present invention include compounds having the formulas: 0

(CH

3 2 N- ((CH 2 2 R)2 Cl- 06/04 '01 FRI 17:34 [TX/RX NO 9016] and 0

(CH

3 2

(CH

2 2 C R 3 C1-

R

1 and 0

(OH

3

(HO-(CH

2 2 N+ N- ((OH 2 2 0 C R 3 2

CH

3

SO

4 and 0 R3 -C 0 CH 2 CH CH 2

-N+(R

2 3 Cl' R3 -C0 0 wherein each R 2 substituent is a C1 C6 alkyl or hydroxyalkyl group, benzyl group or mixtures thereof; each RI substituent is a 012 022 hydrocarbyl group, or substituted hydrocarbyl group or mixtures thereof; each R 3 substituent is a C1i1i C21 hydrocarbyl group, or substituted hydrocarbyl or mixtures thereof.

These compounds can be considered to be mono or diester variations of the well-known dialkyldimethylammonium safts such as diester ditallow dimethyl ammonium chloride, dliester 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 (hydrogen ated)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 (Hydrog enated)Taflow DiMethyl Ammonium Chloride (DEDHTDMAC), and mixtures thereof being preferred. 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).

Without being bound by theory, it is believed that the ester moiety(ies) lends biodegradability to these compounds. Importantly, the ester-functional quatemary ammonium compounds used herein biodegrade more rapidly than do conventional dialkyl dimethyl ammonium chemical softeners.

Examples of 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.

The term 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.

Examples of suitable binder materials include permanent wet strength resins (i.e.

Kymene 557H marketed by Hercules Incorporated of Wilmington, DE), temporary wet strength resins National starch 78-0080 marketed by National Starch and Chemical corporation of New-York, NY), dry strength resins Acco 514, Acco 711 marketed by American Cyanamid company of Wayne, New Jersey) and retention aid resins Percol ®175 marketed by Allied Colloids of Sulfolk, Virginia).

Briefly, 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 fumish 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.

All percentages, ratios and proportions herein are by weight unless otherwise specified.

BRIEF DESCRIPTION OF THE DRAWINGS While the Specification concludes with claims particularly pointing out and distinctly claiming the present invention, it is believed the invention is better (o C.

8 understood from the following description taken in conjunction with the associated drawings, in which Figure 1 is a schematic cross-sectional view of a three-layered single ply toilet tissue in accordance with the present invention.

Figure 2 is a schematic cross-sectional view of a two-layered two-ply facial tissue in accordance with the present invention.

The present invention is described in more detail below.

DETAILED DESCRIPTION OF THE INVENTION While this specification concludes with claims particularly pointing out and distinctly claiming the subject matter regarded as the invention, it Is believed that the invention can be better understood from a reading of the following detailed description and of the appended examples.

As used herein, the term "lint resistance' is the ability of the fibrous product, o.o* 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.

As used herein, the term "binder" refers to the various wet and dry strength resins and retention aid resins known In the paper making an.

As used herein, the term "water soluble' refers to materials that are soluble ••in water to at least 3% at 25 (C.

As used herein, the terms '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.

As used herein, an 'aqueous paper making furnish" is an aqueous slurry of paper making fibers and the chemicals described hereinafter.

As used herein, the term "'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 fumish 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.

It is anticipated that wood pulp in all its varieties will normally comprise the paper making fibers used in this invention. However, other cellulose fibrous pulps, such as cotton liners, bagasse, rayon, etc., can be used and none are disclaimed.

Wood pulps useful herein include chemical pulps such as Kraft, sulfite and surfate 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.

Both hardwood pulps and softwood pulps as well as blends of the two may be employed. The terms hardwood pulps as used herein 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 norther softwood Kraft pulps are preferrred for the inner layer(s) or ply(s). Also applicable to the present invention are fibers derived from recycled paper, which may contain any or all of the above categories as well as other nonfibrous materials such as fillers and adhesives used to facilitate the original paper making.

Biodegradable chemical softener compositions 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.

Each of these types of compounds will be described in detail below.

A. Biodegradable quaternary ammonlum compound 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: R2 (CH 2 )n Y R 3

R

2

(CH

2 )n Y R 3 or

(CH

2 CY-0 *5 0 whri eahR usiun saC 6akl.rhdoyly rubny ru or mitrsteef ahR usiun i 1 2 yrcr ruo susiue yroa..gopo.mxue hrof ahR usiteti l 18-AFR.2001 13:56 WATERMARK PATENT 613 98196010 NO. 1335 P. 3 11 C,2 hydrocarbyl group, or substituted hydrocarbyl or mixtures thereof; Y is or or 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.

As discussed in Swern, Ed. in Bailey's Industrial Oil and Fat Products, Third Edition, John Wiley and Sons (New York 1964), tallow is a naturally occurring material having a variable composition. Table 6.13 in the aboveidentified 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 the above-described levels of saturations are expressly meant to be included within the scope of the present invention.

It will be understood that substituents 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. Preferably, each R, is C,1-Ci, alkyl and/or alkenyl, most preferably each R, is straight-chain alkyl and/or alkenyl. Preferably, each R 2 is methyl or hydroxyethyl. Preferably R, is C,1-C17 alkyl and/or alkenyl, most preferably R 3 is straight chain C,1-C17 alkyl and/or alkenyl, and X- is chloride or methyl sulfate. Furthermore, the ester-functional quaternary ammonium compounds can optionally contain up to about 10% of the mono(long chain alkyl) derivatives, 2

OH)((CH

2 )OC(O)Ra)X' as minor ingredients. These minor ingredients can act as emulsifiers and are useful in the present invention.

Specific examples of ester-functional quaternary ammonium compounds having the structures named above and suitable for use in the present invention include the well-known diester dialkyl dimethyl ammonium salts such as diester 18/04 '01 WED 13:59 [TX/RX NO 9177] 18-APR-2001 13:56 18. PR. 001 3:56WATERMARK PATENT 613 98196010N.135 P 4 NO. 1335 P. 4 11a ditallow dimethyl ammonium chloride, monoester ditallow dimethyl ammonium chloride, diester ditallow dimethyl ammonium methyl sulfate, diester di(hyd rogenated)tallow dimethyl ammoniu m methyl sulfate, diester di(hyd rogenated)tallow dimethyl ammoniu m chloride, and mixtures thereof.

Diester ditallow dimethyl ammonium chloride and diester di(hydrogenated)tallow dimethyl ammonium chloride are particularly preferred. These particular materials are available commercially from Sherex Chemical Company Inc. of Dublin, Ohio under the tradename "ADOG EN DDMVC 18/04 '01 WED 13:59 [TX/RX NO 9177] Di-quat variations of the 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: 0 (R 2 2

(R

2 2 0 II I II

R

3 C 0 (CH2)2 N (CH 2 N (CH 2 2 0- C R 3 2 X- In the structure named above each R 2 is a Ci C6 alkyl or hydroxyalkyl group, R 3 is C11-C21 hydrocarbyl group, n is 2 to 4 and X' is a suitable anion, such as an halide chloride or bromide) or methyl sulfate. Preferably, each

R

3 is C13-C17 alkyl and or alkenyl, most preferably each R 3 is straight-chain Ci5 C17 alkyl and or alkenyl, and R 2 is a methyl.

B. Polyhydroxy Compound S: 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.

Examples of polyhydroxy compounds useful in the present invention include glycerol, sorbitols, polyglycerols having a weight average molecular weight of from S. 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. For example, 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. Preferably, the weight ratio of glycerol to polyoxyethylene glycol ranges from about 10 1 to 1: 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.

However, 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.

It has been discovered that the 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, as will be described in greater detail hereinafter in Example 1, consists of first heating the polyhydroxy compound to a temperature of about 66 °C (150 0 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 :i 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 although this ratio will vary depending upon the molecular weight of the polyhydroxy compound and/or biodegradable quatemary ammonium compound used.

It has unexpectedly been found that the adsorption of the polyhydroxy 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. In fact, at least 20% of the polyhydroxy compound and S. the biodegradable quatemary ammonium compound added to the fibrous cellulose o are retained; preferably, the retention level of biodegradable quaternary ammonium compound and the polyhydroxy compound is from about 50% to about of the added levels.

Importantly, adsorption occurs at a concentration and within a time frame that are practical for use during paper making. In an effort to better understand the surprisingly high retention rate of polyhydroxy compound onto the paper, the physical science of the melted solution and the aqueous dispersion of a DiEster Di(Touch Hardened)Tallow DiMethyl Ammonium Chloride (DEDTHTDMAC), and polyoxyethylene glycol 400 were studied.

Without wishing to be bound by theory, or to otherwise limit the present invention, the following discussion is offered for explaining how the ester-functional quaternary ammonium compound promotes the adsorption of the polyhydroxy compound onto paper.

DEDTHTDMAC (DiEster Di(Touch Hardened)Tallow DiMethyl Ammonium Chloride) exist as a mixture of liquid crystalline and crystalline phases, at equilibrium. X-ray data indicate that commercial DEDTHTDMAC is, in fact, a liquid crystalline phase showing no evidence of crystalline states.

Mixtures of DEDTHTDMAC with PEG-400.

Phase studies of these two materials using the step-wise dilution method demonstrate that their physical behavior is similar to that of di(hydrogenated)tallow dimethyl ammonium chloride. These compounds are miscible over a wide range of temperatures (2 50 which indicates that dispersions may be prepared from these mixtures over a comparable range of temperatures. No upper temperature limit of miscibility exists. The X-ray data show that a mixture of crystal and liquid phases do, in fact, exist in DEDTHTDMAC PEG-400 mixtures.

Mixtures of DEDTHTDMAC with glycerol.

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.

Mixtures of DEDHTDMAC with PEG-400.

Phase studies of these two materials using the step-wise dilution method S. demonstrate that their physical behavior is similar to that of DEDTHTDMAC.

These compounds are miscible over a wide range of temperatures 67 which indicates that dispersions may be prepared from these mixtures over a comparable range of temperatures. No upper temperature limit of miscibility exists.

SPhysical state of mixtures of quats polyhydroxy compounds I water.

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. 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 addition of mixtures of about equal parts of DEDTHTDMAC and polyhydroxy compounds glycerol, PEG-400 etc. to water, so as to form a mixture containing about 1% of DEDTHTDMAC will precipitate the DEDTHTDMAC. Most likely, the DEDTHTDMAC phase near room temperature will be the lamellar liquid crystal.

Colloidal structure of dispersions.

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.

State of the dispersions.

When the above described dispersions are cooled, the partial crystallization of the material within the colloidal particles may occur. However, it is likely that 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. Preferably, the biodegradable chemical softening compositions described herein are used before the equilibrium state has been attained.

It is believed that the vesicles containing biodegradable quats and polyhydroxy compounds glycerol, PEG-400 etc. break apart upon drying of the fibrous cellulosic material. Once the vesicle is broken, the majority of the PEG component may penetrate into the interior of the cellulose fibers where it enhances the fiber flexibility. Importantly, some of the PEG is retained on the surface of the fiber where it acts to enhance the absorbency rate of the cellulose fibers. Due to ionic 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.

Binder materials The present invention contains as an essential component from about 0.01% to about 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.

If permanent wet strength is desired, 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.

S: Polyamide-epichlorohydrin resins are cationic wet strength resins which have been found to be of particular utility. Suitable types of such resins are described in U.S. Patent No. 3,700,623, issued on October 24. 1972, and 3,772,076, issued on November 13, 1973, both issued to Keim and both being hereby incorporated by reference. One commercial source of a useful potyamide-epichlorohydrfn resins is Hercules, Inc. of Wilmington, Delaware, which markets such resin under the mark Kymeme 557H.

Polyacrylamide resins have also been found to be of utility as wet strength resins or retention aids. These resins are described in U.S. Patent No. 3,556,932, issued on January 19, 1971, to Cosda, et al. and 3,556,933, issued on January 19, 1971, to Williams et al., both patents being incorporated herein by reference.

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.

17 If temporary wet strength is desired, 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 U.S. Patent No. 4,981,557 issued on January 1, 1991, to Bjorkquist and incorporated herein by reference.

If dry strength is desired, 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, 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). In general, 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 :i 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 tom 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 OC) 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. Preferably, between about 0.01% and about of 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 multilayered tissue paper embodiments of the present invention contain from about 0.01% to about 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 U.S. Patent 3,994,771, Morgan, Jr. et al. issued November 30, 1976, and incorporated herein by reference. In general, 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 g/m 2 and about 65 g/m 2 and density of about 0.60 g/cm 3 or less. Preferably, basis weight will be below about 35 g/m 2 or less; and density will be about 0.30 g/ cm 3 or less. Most preferably, 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. Preferably, 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. Alternatively, low cost sources of short fibers such as sulfite fibers, thermomechanical pulp fibers, chemi-thermomechanical 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. Referring to figure 1, 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.

In an alternate preferred embodiment of the present invention, multi-ply tissue paper products are formed by placing at least two multi-layered tissue paper webs in juxtaposed relation. For example, a two-ply tissue paper product can be made comprising a first two-layered tissue paper web and a second twolayered tissue paper web in juxtaposed relation. In this example, 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. Figure 2 is a schematic crosssectional view of a two-layered two-ply facial tissue in accordance with the present invention. Referring to figure 2, 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. Similarly three-ply tissue paper products can be made by placing three multi-layered tissue paper webs in juxtaposed relation.

It should not be inferred from the above discussion that the present invention is limited to 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.

Preferably, 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 0effective 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 multilayered tissue products of the present invention. Referring to figures 1 and 2, the biodegradable chemical softening composition comprising a mixture of the biodegradable quaternary ammonium compound and the potyhdroxy 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.

However, it has also been discovered that the lint resistance of the multilayered tissue paper products decreases with the inclusion of the biodegradable quaternary ammonium compound and the polyhdroxy compound.

Therefore, binder materials are used for linting control and to increase the tensile strength. Preferably, 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. Referring to figures 1 and 2, 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.

The combination of the biodegradable chemical softening composition comprising a biodegradable quaternary ammonium compound and a polyhdroxy compound in conjunction with a binder material results in a tissue paper product having superior softness, absorbency, and lint resistance properties. Selectively adding the majority of the biodegradable chemical softening composition to the ."eo outer layers or plys of the tissue paper, enhances its effectiveness. Typically 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.

Conventionally pressed multi-layered tissue paper and methods for making such paper are known in the art. 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. Once 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. In a typical process, 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 U.S. Patent No. 3,301,746, issued to Sanford and Sisson on January 31, 1967, U.S. Patent No. 3,974,025, issued to Peter G. Ayers on August 1976, and U.S. Patent No. 4,191,609, issued to Paul D. Trokhan on March 4, 1980, and U.S. Patent 4,637,859, issued to Paul D. Trokhan on January 20, 1987; all of which are incorporated herein by reference.

In general, 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 predred, in such a manner so as to substantially avoid compression of the high bulk field. This is preferably accomplished by fluid pressure, such as with a vacuum type device or blow-through dryer, or alternately by mechanically pressing the web against an array of supports wherein the high bulk field is not compressed. The operations of dewatering, optional predrying and formation of the densified zones may be integrated or partially integrated to reduce the total number of processing steps performed. Subsequent to formation of the densified zones, dewatering, and optional predrying, the web is dried to completion, preferably still avoiding mechanical pressing. Preferably, from about 8% to about of 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 U.S. Patent No. 3,301,746, Sanford and Sisson, issued January 31, 1967, U.S. Patent No. 3,821,068, Salvucci, Jr. et al., issued May 21, 1974, U.S. Patent No. 3,974,025, Ayers, issued August 10, 1976, U.S. Patent No. 3,573,164, Friedberg et al issued March 30, 1971, U.S. Patent No. 3,473,576, Amneus, issued October 21, 1969, U.S. Patent No. 4.239,065, Trokhan, issued December 16, 1980, and U.S. Patent No. 4,528,239, Trokhan, issued July 9, 1985, all of which are incorporated herein by reference.

Preferably, 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. Once formed, 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. This can be done, for example, by pressing a 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. Also, preferably, 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 U.S. Patent No. 3,812,000 issued to Joseph L Salvucci, Jr. and Peter N. Yiannos on May 21, 1974 and U.S. Patent No. 4,208,459, issued to Henry E. Becker, Albert L. McConnell, and Richard Schutte on June 17, 1980, both of which are incorporated herein by reference. In general, uncompacted, non pattern densified mutti-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 24 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 facal tissue products. For example, two multilayered tissue paper webs of this invention can be ply-bonded to form 2-ply facial or toilet tissue products.

Molecular Weight Determination A. Introduction The essential distinguishing characteristic of polymeric materials is their molecular size. The properties which have enabled polymers to be used in a diversity of applications derive almost entirely from their macro-molecular nature.

In order to characterize fully these materials it is essential to have some means of defining and determining their molecular weights and molecular weight Sdistributions. It is more correct to use the term relative molecular mass rather the molecular weight, but the latter is used more generally in polymer technology. It is not always practical to determine molecular weight distributions. However, this is becoming more common practice using chromatographic techniques. Rather.

recourse is made to expressing molecular size in terms of molecular weight averages.

B. Molecular weight averages If we consider a simple molecular weight distribution which represents the weight fraction (wj) of molecules having relative molecular mass it is possible to define several useful average values. Averaging carried out on the basis of the number of molecules (Ni) of a particular size (Mi) gives the Number Average Molecular Weight n ,_Mi 1 Ni An important consequence of this definition is that the Number Average Molecular Weight in grams contains Avogadro's Number of molecules.

This definition of molecular weight is consistent with that of monodisperse molecular species, i.e. molecules having the same molecular weight. Of more significance is the recognition that if the number of molecules in a given mass of a polydisperse polymer can be determined in some way then Mn, can be calculated readily. This is the basis of colligative property measurements.

Averaging on the basis of the weight fractions (Wi) of molecules of a given mass (Mi) leads to the definition of Weight Average Molecular Weights Mw WiNi_. NiMi2 E Wi E Ni Mi Mw is a more useful means for expressing polymer molecular weights than in since it reflects more accurately such properties as melt viscosity and mechanical properties of polymers and is therefor used in the present invention.

Analytical and Testing Procedures Analysis of the amount of biodegradable treatment chemicals used herein S. or retained on tissue paper webs can be performed by any method accepted in the applicable art.

A. Quantitative analysis for ester-functional quaternary ammonium and polyhydroxy compounds For example, the level of the ester-functional quaternary ammonium compound, such as DiEster Di(Hydrogenated)Tallow DiMethyl Ammonium Chloride (DEDHTDMAC) 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.

B. Hydrophillcity (absorbency) 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 26 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 0 C and 50+2% R.H. as specified in TAPPI Method T 402), 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; second, the sheet is folded into four 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; third, the balled sheet is placed on the surface of a body of distilled water at 23 1 0 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: after the paper has aged two weeks following its manufacture. Thus, the wetting times are preferably S. 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'.

C. Biodegradable Suitable substantially waterless self-emulsifiable biodegradable chemical softening composition for use in the present invention are biodegradable. As used herein, the term '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," ADolied and Environmental Microbiology. Volume 38 (1979), pages 1153-61, which describes a suitable method for estimating biodegradability. Using this method, a substance is said to be readily biodegradable if it has greater than carbon dioxide evolution and greater than 90% dissolved organic carbon removal within 28 days. The softeners used in the present invention meet such biodegradability criteria.

27 C. Density The density of multi-layered tissue paper, as that term is used herein, 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 multilayered tissue paper, as used herein, is the thickness of the paper when subjected to a compressive load of 95 g/in 2 (15.5 g/cm 2 D. Lint Dry lint 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.

Wet lint A suitable procedure for measuring the wet linting property of tissue samples is described in U.S. Patent No. 4,950,545; issued to Walter et al., on August 21, 1990, and incorporated herein by reference. The procedure essentially involves passing a tissue sample through two steel rolls, one of which is partially submerged in a water bath. Unt from the tissue sample is transferred to the steel roll which is moistened by the water bath. The continued rotation of the steel roll deposits the lint into the water bath. The lint is recovered and then counted. See col. 5, line 45 col. 6, line 27 of the Walter et al. patent. Other methods known in the prior art for measuring wet lint also can be used.

Optional Ingredients Other chemicals commonly used in paper making can be added to the 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.

For example, 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. (New York. NY); alkylglycoside ethers as described in U.S. Patent 4.011,389. issued to W. K. Langdon, et al. on March 8, 1977; and alkylpolyethoxylated esters such as Pegosperse 200 ML available from Glyco Chemicals, Inc. (Greenwich, CT) and IGEPAL RC-520 available from Rhone Poulenc Corporation (Cranbury, The above listings of optional chemical additives is intended to be merely exemplary in nature, and are not meant to limit the scope of the invention.

The following examples illustrate the practice of the present invention but are not intended to be limiting thereof.

EXAMPLE 1 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 comprising a mixture of DiEster Di(Touch Hardened)Tallow DiMethyl Ammonium Chloride (DEDTHTDMAC) and Polyoxyethylene Glycol 400 (PEG-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 3. DEDTHTDMAC is dissolved in the PEG to form a melted solution at about 66 °C (150 4. Adequate mixing is provided to form a homogenous mixture of DEDTHTDMAC in PEG; 5. The homogenous mixture of is cooled down to a solid form at room temperature.

The substantially waterless self-emulsifiable biodegradable chemical softener composition of can be pre-mixed (steps 1-5 above) at the chemical supplier 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.

29 EXAMPLE 2 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.

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 are weighted separately; 3.

Mixture of is heated up to about 66 °C (150 4. DEDTHTDMAC is dissolved in to form a melted solution at 66 °C (150 5. Adequate mixing is provided to form a homogenous mixture of DEDTHTDMAC in 6. The homogenous mixture of is cooled down to a solid form at room temperature.

The substantially waterless self-emulsifiable biodegradable chemical softener composition of can be pre-mixed (steps 1-6 above) at the chemical supplier 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.

EXAMPLE 3 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 pilot scale Fourdrnier paper making machine is used in the practice of the present invention. First, 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 0 The melted mixture is then dispersed in a conditioned water tank (pH 3, Temperature 66 to form a sub-micron vesicle dispersion. The particle size of the vesicle dispersion is determined using an optical microscopic technique. The particle size range is from about 0.1 to 1.0 micron.

Second, 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 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 0 diluted to about 0.2% consistency at the fan pump.

Third, 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) is added to the Eucalyptus stock pipe before the stock pump at a rate of 0.1% by weight of the dry fibers; and 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 S* 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 photopolymer fabric having 562 Lnear Idaho cells per square inch, 40 percent knuckle area and 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 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). 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 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 mufti-layered tissue paper has about 18 #/3M Sq Ft basis weight, contains about 0.2% of the biodegradable chemical softener mixture and about 0.3% of the 31 temporary wet strength resin. Importantly, the resulting multi-layered tissue paper is soft, absorbent, has good lint resistance and is suitable for use as facial and/or toilet tissues.

EXAMPLE 4 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 pilot scale Fourdrinier paper making machine is used in the practice of the present invention. First, 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 The melted mixture is then dispersed in a conditioned water tank (pH Temperature 66 to form a sub-micron vesicle dispersion. The particle size of the vesicle dispersion is determined using an optical microscopic technique. The particle size range is from about 0.1 to micron.

Second, 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 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.

Third, 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 Acco 514, Acco 711 marketed by American Cyanamid company of Fairfield, OH) is added to the Eucalyptus stock pipe before the stock pump at a rate of 0.1% by weight of the dry fibers; and 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.

Dewaering 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 photopolymer fabric having 562 Lnear Idaho cells per square inch, 40 percent knuckle area and 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 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 S: (PVA). 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).

Two plies of the web are formed into multi-layered tissue paper products and laminating them together using ply bonded technique. The multi-layered tissue paper has about 23 #/3M Sq Ft basis weight, contains about 0.1% of the S. biodegradable chemical softener mixture and about 0.2% of the dry strength resin.

Importantly, the resulting multi-layered tissue paper is soft, absorbent, has good lint resistance and is suitable for use as facial and/or toilet tissues.

EXAMPLE 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 pilot scale Fourdrinier paper making machine is used in the practice of the present invention. First, 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 to form a sub-micron vesicle dispersion. The particle size of the vesicle dispersion is determined using an optical microscopic technique. The particle size range is from about 0.1 to 1.0 micron.

Second, 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 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.

Third, 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.

S Dewatering occurs through the Fourdrinier wire and is assisted by a deflector and vacuum boxes. The Fourdrinier wire is of a 5-shed, satin weave configuration having 84 machine-direction and 76 cross-machine-direction monofilaments per inch, respectively. The embryonic wet web is transferred from the Fourdrinier wire, at a fiber consistency of about 15% at the point of transfer, to a conventional felt. Further de-watering is accomplished by vacuum assisted drainage until the web has a fiber consistency of about 35%. The web is then adhered to the surface of a Yankee dryer. The fiber consistency is increased to an estimated 96% before the dry creping the web with a doctor blade. The doctor blade has a bevel angle of about 25 degrees and is positioned with respect to the Yankee dryer to provide an impact angle of about 81 degrees; the Yankee dryer is operated at about 800 fpm (feet per minute) (about 244 meters per minute). The dry web is formed into roll at a speed of 700 fpm (214 meters per minutes).

Two plies of the web are formed into multi-layered tissue paper products and laminating them together using ply bonded technique. The multi-layered tissue paper has about 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. Importantly, 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.

EXAMPLE 6 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).

A pilot scale Fourdrinier paper making machine is used in the practice of the .present invention. First, 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 0 The melted mixture is then dispersed in a conditioned water tank (pH 3, Temperature 66 to form a sub-micron vesicle dispersion. The particle size of the vesicle dispersion is determined using an optical microscopic technique. The particle size range is from about 0.1 to 1.0 micron.

Second, 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 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.

Third, 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 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 711 Linear Idaho cells per square inch, 40 percent knuckle area and 9 mils of photo-polymer depth. Further de-watering is accomplshed 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 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 Acohol (PVA). 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 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. Importantly, the resulting muti-layered tissue paper is soft, absorbent, has good int resistance and is suitable for use as faial tissues.

Claims (7)

1. 6-APR.2001 17:32 WATERMARK PATENT 613 98196010 NO. 0867 P. 6/10 36 THE CLAIMS DEFINING THE INVENTION ARE AS FOLLOWS: 1. A multi-layered tissue paper web characterised in that it includes at least two superposed layers, a first layer and at least one second layer contiguous said first layer, said multi-layered web including: a) paper making fibers; b) from 0.01% to 3.0% by weight of a biodegradable quaternary ammonium compound; c) from 0.1% to 3.0% of a water soluble polyhydroxy compound; and d) from 0.01% to 3.0% of a binder material; and wherein the biodegradable quaternary ammonium compound is chosen from the group comprising species of formula R 2 (CH 2 )n-Y-R 3 ~x-p N+ X~, R 2 (CH 2 )n-Y-R 3 R 2 (CH 2 )n-Y-R 3 R 2 RI and R3-Y-CH2 CH-CH2-N-(R 2 3 X R 3 -Y wherein each R, substituent is a C 1 -C 6 alkyl or hydroxyalkyl group, benzyl group or mixtures thereof; each R, substituent is a C 2 -C 22 hydrocarbyl group, or substituted hydrocarbyl group or mixtures thereof; each R, substituent is a 06/04 '01 FRI 17:34 [TX/RX NO 9016]
2. 18-APR.2001 13:57 WATERMARK PATENT 613 98196010 NO. 13 35 P. 37 C 11 -C, 2 hydrocarbyl group, or substituted hydrocarbyl or mixtures thereof; Y is or or and mixtures thereof; n is 1 to 4 and X- is a suitable anion. 2. A multi-layered tissue web according to claim 1 wherein each R 2 substituent is methyl. 3. A multi-layered tissue web according to claim 1 wherein each R, substituent is C 16 alkyl or alkenyl. 4. A multi-layered tissue web according to claim 1 wherein each R 3 substituent is Ci 5 -C 1 7 alkyl or alkenyl. A multi-layered tissue web according to claim 1 wherein X- is chloride or methyl sulphate. 6. A multi-layered tissue web according to claim 1 wherein said polyhydroxy compound is selected from the group comprising glycerol, sorbitols, polyglycerols having a weight average molecular weight of from 150 to 800, polyoxyethylene glycols and polyoxypropylene glycols having a weight average molecular weight from 200 to 4000, and mixtures thereof. 7. A multi-layered tissue web according to claim 6 wherein said polyhydroxy compound is a polyoxyethylene glycol or polyoxypropylene glycol having a weight average molecular weight of from 200 to 1000. 8. A multi-layered tissue web according to claim 7 wherein the weight average molecular weight of from 200 to 600. 18/04 '01 WED 13:59 [TX/RX NO 9177] 6.APR.2001 17:32 WATERMARK PATENT 613 98196010 NO. 0867 P. 8/10 38 9. A multi-layered tissue paper web according to claim 1 wherein the binder material is selected from the group comprising permanent wet strength resins, and mixtures thereof, temporary wet strength resins, dry strength resins, retention aid resins and mixtures thereof. A multi-layered tissue paper web according to claim 9 wherein the wet strength resin is a polyamide-epichlorohydrin or polyacrylamide wet strength resin. 11. A multi-layered tissue paper web according to claim 9 wherein the temporary wet strength resin is starch based, 12, The multi-layered tissue paper web of any one of the preceding claims wherein said multi-layered web includes three superposed layers, an inner layer and two outer layers, said inner layer being located between two said outer layers, wherein said biodegradable quaternary ammonium compound, said water soluble polyhydroxy compound, and said binder material are each contained in one or more of said layers of said multi-layered web. 13. A multi-layered tissue paper web according to claim 12 wherein said multi-layered web comprises a single ply. 14. The multi-layered tissue paper web of claim 12 or claim 13 wherein the majority of the biodegradable quatemary ammonium compound and the polyhydroxy compound is contained in at least one of said outer layers, preferably in both of said outer layers. The multi-layered tissue paper web of any one of claims 12 to 14 wherein the majority of the binder is contained in said inner layer. 06/04 '01 FRI 17:34 [TX/RX NO 9016] 6-APR.2001 17:32 WATERMARK PATENT 613 98196010 NO. 0867 P. 9/10 39 16. The multi-layered tissue paper web of any one of claims 12 to wherein said inner layer includes relatively long paper making fibers, said long paper making fibers having an average length of at least 2.0 mm and wherein each of two said outer layers includes relatively short paper making fibers, said short paper making fibers having an average length between 0.2 and mm. 17. A multi-layered tissue paper web according to claim 16 wherein the inner layer includes softwood fibers, 18. A multi-layered tissue paper web according to claim 16 wherein the outer layers include hardwood fibers.
3. 19. The multi-layered tissue paper web of any one of claims 16 to 18 wherein said inner layer comprises mixtures of softwood fibers and low cost fibers, and at least one of said outer layers comprises low cost fibers or mixtures of hardwood fibers and low cost fibers, wherein said low cost fibers are selected from sulfite fibers, thermomechanical pulp fibers, chemi- thermomechanical pulp fibers, recycled fibers, and mixtures thereof. The multi-layered tissue paper web of any one of claims 1 to 19 wherein the weight ratio of the quaternary ammonium to the polyhydroxy compound ranges from 1.0 0.3 to 0.3:
4. 21. The multi-layered tissue paper web of claim 20 wherein the weight ratio ranges from 1.0 0.7 to 0.7
5. 22. A multi-ply tissue paper product including at least two juxtaposed multi- layered tissue paper webs of claim 1, and wherein said binder materials are permanent wet strength resins or temporary wet resins, and wherein the majority of said biodegradable quatemary ammonium compound and said 06/04 '01 FRI 17:34 [TX/RX NO 9016] 6-APR.2001 17:32 WATERMARK PATENT 613 98196010 NO. 0867 P. 10/10 polyhydroxy compound are contained in at least one of said outer layers and wherein the majority of said binder material is contained in said inner layer.
6. 23. A multi-ply tissue paper product according to claim 22 comprising two plies.
7. 24. A multi-ply tissue paper product according to claim 23 wherein each of said plies comprises two superimposed layers DATED this 6 h day of April 2001 THE PROCTER GAMBLE COMPANY WATERMARK PATENT TRADEMARK ATTORNEYS 290 BURWOOD ROAD HAWTHORN VICTORIA 3122 AUSTRALIA P13076AU00 LCG/KMH/RES 06/04 '01 FRI 17:34 [TX/RX NO 9016]