CA2142605A1 - Tissue paper treated with nonionic softeners that are biodegradable - Google Patents

Tissue paper treated with nonionic softeners that are biodegradable

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Publication number
CA2142605A1
CA2142605A1 CA 2142605 CA2142605A CA2142605A1 CA 2142605 A1 CA2142605 A1 CA 2142605A1 CA 2142605 CA2142605 CA 2142605 CA 2142605 A CA2142605 A CA 2142605A CA 2142605 A1 CA2142605 A1 CA 2142605A1
Authority
CA
Canada
Prior art keywords
sorbitan
ethoxylated
softener
paper
esters
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Abandoned
Application number
CA 2142605
Other languages
French (fr)
Inventor
Saeed Fereshtehkhou
Larry N. Mackey
Dean V. Phan
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Procter and Gamble Co
Original Assignee
Individual
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Individual filed Critical Individual
Priority to CA002254257A priority Critical patent/CA2254257C/en
Publication of CA2142605A1 publication Critical patent/CA2142605A1/en
Abandoned legal-status Critical Current

Links

Classifications

    • DTEXTILES; PAPER
    • D21PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21HPULP 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
    • D21H21/00Non-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
    • D21H21/14Non-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
    • D21H21/22Agents rendering paper porous, absorbent or bulky
    • DTEXTILES; PAPER
    • D21PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21HPULP 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
    • D21H21/00Non-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
    • D21H21/14Non-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
    • D21H21/22Agents rendering paper porous, absorbent or bulky
    • D21H21/24Surfactants
    • DTEXTILES; PAPER
    • D21PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21HPULP 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
    • D21H19/00Coated paper; Coating material
    • D21H19/10Coatings without pigments
    • D21H19/14Coatings without pigments applied in a form other than the aqueous solution defined in group D21H19/12
    • DTEXTILES; PAPER
    • D21PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21HPULP 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
    • D21H25/00After-treatment of paper not provided for in groups D21H17/00 - D21H23/00
    • D21H25/02Chemical or biochemical treatment
    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10TTECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00Stock material or miscellaneous articles
    • Y10T428/24Structurally defined web or sheet [e.g., overall dimension, etc.]
    • Y10T428/24355Continuous and nonuniform or irregular surface on layer or component [e.g., roofing, etc.]
    • Y10T428/24446Wrinkled, creased, crinkled or creped
    • Y10T428/24455Paper
    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10TTECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00Stock material or miscellaneous articles
    • Y10T428/24Structurally defined web or sheet [e.g., overall dimension, etc.]
    • Y10T428/24802Discontinuous or differential coating, impregnation or bond [e.g., artwork, printing, retouched photograph, etc.]
    • Y10T428/24934Discontinuous or differential coating, impregnation or bond [e.g., artwork, printing, retouched photograph, etc.] including paper layer
    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10TTECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00Stock material or miscellaneous articles
    • Y10T428/249921Web or sheet containing structurally defined element or component
    • Y10T428/249953Composite having voids in a component [e.g., porous, cellular, etc.]
    • Y10T428/249955Void-containing component partially impregnated with adjacent component
    • Y10T428/249959Void-containing component is wood or paper
    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10TTECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00Stock material or miscellaneous articles
    • Y10T428/249921Web or sheet containing structurally defined element or component
    • Y10T428/249953Composite having voids in a component [e.g., porous, cellular, etc.]
    • Y10T428/249962Void-containing component has a continuous matrix of fibers only [e.g., porous paper, etc.]
    • Y10T428/249964Fibers of defined composition
    • Y10T428/249965Cellulosic
    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10TTECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00Stock material or miscellaneous articles
    • Y10T428/31504Composite [nonstructural laminate]
    • Y10T428/31971Of carbohydrate

Abstract

Tissue papers, in particular pattern densified tissue papers, having an enhanced tactile sense of softness when treated with certain nonionic softeners are disclosed. These nonionic softeners are biodegradable and comprise sorbitan esters, ethoxylated/propoxylated versions of these sorbitan esters, or mixtures thereof. The softener is typically applied from an aqueous dispersion or solution thereof to at least one surface of the dry tissue paper web.

Description

94/0s856 2 1 ~ 2 6 0 ~ ~CT/US~3/076S0 ~1`

~, -1- i TISSUE PAPER TREATED WITH NONIONIC , SOFTENERS THAT ARE BIO~EGRADABLE

. !~

, TECHNICAL FIELD
This application relates to tissue papers, in particular pattern densified tissue papers, having an enhanced tactile sense of so~tness. This application particularly relates to s tissue papers ~reated with certain nonionic softeners that arD
biodegradable.
: BACKGROUND OF T~E INVENTION
Paper webs or sheets, so~etimes called tissue or paper ti~sue~webs or sheets, find extensiYe us~ ln modern socie~y.
: These include such staple items as paper ~towels, facial tissues and sanitary~ (or toilet) tissues. These paper products can h~aYe:Yarious desirabl~e properties,; including wet and~dry tensile strength, absorbency for aqueous fluids ~(e.g., : .
wettability~5 low ~lint propertles, desirab1e bulk,:: and 5~ softness~: The;particular challenge ~in papermaking has been to appropriately balance these various~proper~ies to provide :superior tissue~paper.
Although~somewhat desirable for ~towel products, softness ~.
- is:a particularly important property for facial and toilet 2Q~ tissu~s.~ So~tness lis1the tact;ile sensation pe~ceivDdi'by the consumer who holds: a particular paper product, rubs i:t across .
: the skln, and; crumples it within the :hand. Such t~ctile ;~ : perceivable: softness can be characterized by, but is not limited to,~ friction, ~lexibility, and smo~othness, as well as s~ubjectlve descriptors, such as a feeling like~velvet,~ silk or : flannel. This tactile sensation is a combination of se~eral physical properties, including the flexibility or stiffness of ~ ' f~ ~

w 0 94/0s856 ~ 1 ~ 2 6 ~ 3 P ~ /US93~076 the sheet of paper, as well as the texture of the surrac~ of the paper.
Stiffness of paper is typically affected by efforts to increase the dry and/or we~ tensile strength of the web.
Incre~ses in dry tensile strenglh can be achieved either by mechanical process~s to insure adequate rormation of hydrogen bonding between the hydroxyl groups o~ adjacent papermak~ng fibers, or by ~he inclusion of certain dry strength additives.
Wet strength is typlcally enhanced by the inclusion of certain wel strengtn r sins, ~ha~, being typically cationtc, ~re easily deposited on and retained by the anionic carboxyl :: groups of the papermaking fibers. However, ~he use of both mechanical and chemical means to improve dry and wet tensi?e strength can also result in stiffer, harsher f~eling, less lS soft tissue papYrs.
Certain chemical additives, commonly referred to as debonding agents, can be added to papermaklng fibers to interfere with the natural fiber-to-fiber bonding that occurs : during sheet formation and drying, and thus lea~ to softer Z0 ~papers.~ These debonding agents are typically cationic and have certain disadvantages associated with their US@ in softening tissue:papers. Some luw molecular w~ight cationio debonding agents can cause e%cessive irritatisn upon contact with hu~an skin. Higher molecular weight cationic debonding agents can be more difficult to apply at low level~ to tissue : paper, and also tend to have unde~irable hydrophobic effeets ~ n the tissue~pap~r, e.g., result in decreased absorbency and ;~ particularly wettabi~ity. Since ~hese cati3nic debonding ~: ag~nts operate by disrupting interfiber bsnding, th2y can a~so : : :30 ~ decrease tensite strength to such an ~xtent that resins, atRxt or other~dry strength ad~itives ean be required to : . provide acceptable leYels of tensil2 strength. These dry: strength additives not only increase the cost of ~he tissue : : paper but can also have other, deleterious effQcts on tissue : 3~ softness. In addition, many cationic debonding agents are n4t .~ O 94/~5856 2 iL 4 2 6 !) PCr/VS93/07650 biodegradable, and therefore can adversely impact on environmental quality.
Mechanical pressing operations are typically applied to tissue paper webs to dewater them and/or increase their tensile s~rengLh. Mechanic~l pressing can occur over the entire area of the paper web, such as in the case of conventio~l felt-pressed paper. More pr~f2rably, dewatering is carried out in such a way that the paper 1s pattern : densified. Pattern densi~ied paper has certain densified ar~as or relatively high riberdensity, as well as relatively low fiber density, high bulk areas. Such high bulk pattern densified papers are typically formed from 2 partially dried paper web that has densified areas imparted to it by a : foraminous fabric having a patterned dlsplacement of knuckles.
See, for example~ U.S. Patent 3,301,746 (Sanfnrd et al), isssled January 31t 1967; U.S. Patent 3,994,771 (Morgan et al), issued November 30, 1976; and U.S. patent 4,529,480 (Trokhan3, i ssued July 16, 1~85 .
Besides tensile strength and bulk, another advantage of 20 ~ such patterned densification processes ~s that ornamental :patterns can be imprinted on the tissue paper. However, an i:nherent problem o~ patterned densification processes is that the:fabrk side o~ the tissue paper, i.e~. the pape~ sur~ace in h ~ contact w~th the ~oraminous fabric during papermaking, i s ;Z5~ sensed as rough~r: than the side not in :tontact with the abric. This is due to the high bulk fields that form, in essence, protrusions outward from the surface of the:paper.
It is these protrusions that can impart a ta~tile sensation of roughnèss.
30 ~ The softness of these ~ompressed, and par~ieularly . ~. .
: patterned d~nsifi~d tissue papers, ~can be improved by treatm~nt with YariouS agents such as vegetable, animal:or synthetic hydrocarbon oils, and especially polysiloxane ma~erials typically referred to as silicone 0il5. See 35~ ~ Co1umn 1, lines 30-45 of U.S. Patent 4,959,125 (Spendel), ` ~' ` ' W094/0~856 21,~?60~ PCT/US93/07~5~
., . .. , , ~. , issued Se,otemh~r 2;, 1930. Ihese silicone oils impart a silky, soft feeling to the tissue paper. However, some silicone oils are hydrophobic and can adversely affect the surface wettability of the treated tissue paper, i.e. the S tre~ted tissue papen can float, thus causing dispusal problems in sewer system~ when flushed. Indeed, some silicone softened papers can r~quire trDatment with other surf~ctants ~o ofrset this reduction in wettabillty caused by the sllicone. See U~S. Patent 5,059,282 (Ampulski et al), issued October 22, 15~1.
Besides silicones, tissue paper has been treated with cationic, as well as non~ationic, surfactants to enhance softness. See, for example, U.S. Patent 4,959,12~ (Sp~ndel~, issued Saptember 25, 199Q; and U.S. patent 4,940,513 ~:~ 15 (Sp,endel), issued July 10, I990, tha~ disclase proeesses for ~:~ enhancing the softness o~ tissue paper by treating it with noncationic, preferably nonionic, surfaGtants. However, the '125 patent teaches ~hat greater softness benefits are obtainable by the addition of the noncationic surfactants to ZO ~ the we~ paper web, the '513 patent only disc~oses the addition of noncationic surfactants to a h~et web. In such "wet webl' methods of addition, the nonc tionic surfactant can potentially migrat~ to the interior of the paper web and compl~etely coat.the fibers. This can cause~a variety of :25 ~ pro~lems9 including fiber debonding:that:leads to a reduction : in tensile strength of the paper, as well as adverse affects on paper; wettability if the noncationic surfactant is : hydrophobie or not very hydrophilic.
Tissue ~paper has aiso beén treà~ed with softeners by "dry 30~ web" addition ~ethods. One such method invol~es moYing the ~ .
dry :pap~r a ross one face of a shaped block of wax-like softsner that i s then deposited on the paper surface by a rubbing action. See U.S. Pa~ent 3,305,39~ ~Bri~), issued : February 21, 1967 ( softeners i ncl u~e stearate soaps such as 3 -5 zinc stearate, stearic acid esters, stearyl akohal, '~i:, ;
.~0 94/058$6 2 1 4 2 6 0 ~ PC~/US93/07650 polyethylene glycols such as Carbowax, and poly~thylene glycol esters of stearic and lauric acids). Another such method involves dipping the dry paper in a solution or em~lsion containing the softening agent. See U.S. Patent 3,296,06 (O'Brien et al), issued Janu~ry ~, 1967 (aliphat,o asters sr certain aliphatic or aromatic carboxylic acids as the s~ftening agent). A pot@ntial proble~ of these prior "dry web" additiQn methods is that the softening agent can be ~pplied less effec~ively, or in a manner that could potentially afrect the absor~ency of the tissu~ paper.
: Indeed, the '392 patent teaches as desirable modi~ication with certain cationic materials to avoid the tendency of the softener to migrate. Application of so~teners by either a rubbing action or by dipping the paper would also be difficult to adapt ~o commercial papermaking systems that run at high ;~ speeds. Furthermore, some of the softeners (Q.g., the pyrumellitate esters af the '06S patent), as well ~s some of the co-additives ~e.g., dimethyl distEaryl ammonium chloride of the '532 patent), ~aught to be useful in these prior "dry ~ web'l methods are not biodegradable.
Accordingly, it would be desirable to be able to soften :
tissue paper, in particular high bulk, pattern densified tissue papers, by a process that: (1) uses a i'dry web" method or~ a~ding the softening agent; (2~ can be carried out in a 5 :~ comme~cial papermaking system without significantly i~npacting on machine operability; (3) uses softeners that are nontoxic and biodegradable; and (4) can be carried out in a manner so as to maintain desi~able tensile strength, absorbency and low lint plroperties of~the tissue paper.
:30 ~ ~
ISCLOSURE OF TH INVENTIQN
: The present inventian relates to softened tissue:paper having a nonionic softener on at lYast one surface thereof.
Suitable~nanionic softeners comprise a nonionic surfactant selected from sorbitan esters, ethoxylated sorbitan esters, ~ .

WO 94/058~6 P~/U!~i93/076~v 1 ~ 2 1 91 2 6 0 ~

propoxylated sorbit~n esters, mixed ethoxylated/propoxylatad sorbitan esters, and mixtures thereof. The softener is present in an amount of from about O.l to about 3% by weight of the dried tissue paper.
The present invention fur~her relat~s to a proc~s; for m~king these sortened tissue papers. This process com~rtses the step ~f treating at le-st one surface of a dri~d tissue paper ~eb with the softener. In other words, the process sf the present invention is a "dry web" addition method. This process is carried out in a manner such that from about 0.1 to about 3~0 of the softener by weight of the dry ~issue paper web is app1ied to the surface thereof. _-Tissue paper softened according to the present invention has a soft and velvet-like feel. It is especially useful in lS softening high bulk, pattenn densi~ied tissue papers, inclwding tissue papers having patterned designs.
Surprisingly, even when the softener is applied only to the smoother (i.e. wire) side of such pattern densified papers, ; the treated paper is still perc~ived as soft.
~;~ The present invention can be carried out in a commercial papermaking~system without signif k antly impacting on machine operability, including speed. The softeners used in the présent invention also ha~e environmental safety (i.e. are nontoxic an~- blodegradable) and cost;~advantage~,~ especially 25~ compared to prior softening agents used to tre~at tissue pap~er.
The improved softness benefits of the present invention can also~ be achieved while maintaining the desirable~ tensile ~; ~ str~ngth, absorbency ~e.g., wettability), and low lint propereies of t~e paper.
Figure~l is a DSC thermogram oF a preferred softener system use~ul in the present invention.

- -T~0 94/05~6 ?1l260~ PC~r/US93tO76~0 Figure 2 is a schem~tic representation illustrating a preferred embodiment ~f the process for softening tissue webs ;~according to the present invention.

OETATlFD DESCRIPTION OF ThE INVENTION
A.
The present invention is useful with tissue paper i-n general, including but not llmited ~o conventiona11y :felt pressed ti~ssue paper; high bulk pattern densified tissue paper; and high bulk, uncompacted tissue paper.~ The tissue paper can be o~ a homogenous or multi-layered construction;
and ~issue paper products made thereFrom can be of a sing~e-ply or multi-ply construction. The tissue paper preferably has a basis weigh~ of between about 10 g/m2 and about 65: g/m2, and density of: about 0.6 g/cc or less. Mo~e p~ef~rably, the basis weight will be about qO g/m2 or les:s and the density will; be about 0.3 g/cc or le:ss. Most preferably, the~ density will be:betwe~n about 0.~4 g/ce and ab~ut 0.2 9 k c- See Co1umn 13, lines 61-67, of U.5.~ Patent S,059,282 :; 20 ~ Ampulski et:a:~j:, issued October 22, 1991~ wh~ch d~scribes:how he~ density of tissue paper is ~easured. (Unless otherwise .
specified,~all amounts and weights relative to the paper: are on~a~dry basis.~
Conventionally pressed tissue paper and ~e~hods ~for Z5~ maki~ng such~paper ar~ well known in:the~art. ;Such ~paper is typ1cal1y :made by ~depositing a papermaking furnish on a foraminous fnrming~wire, nften referred to in thb ar~ as a Fourdrini~r wire. Once the furnish is deposited on the formin~ wi`re, i~ ~is re~er!re~ t~ as i~web. The ~web is dewatered by pressi:ng the web and drying at e1evated emperature.: The particular techniques and typical~equipment for ~aking webs according ~o the process jU5t des~ribed are : well known to those skilled in the art. In a typ k al process, a low ~onsistency pulp furnish is provided from a pressurized :: : 3~ ~ headbox. The headbsx has an opening for delivering a ~hin :~;::: : : :

W O 94/~58~6 P ~ /US93/076~ :
2 1~2BO~

depos,t of pulp furnish onto the Four~rinier 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 dried by ; pressing operat,ons wherein the w~b is subjact~d to presiure deYelopeiid by opposing mechanical members, for example, cylindrical rolls. The dewatered web is then further pressed and dried by a steam drum apparatus known in the art as a Yankee dryer. Pressure can be developed at the Yankee dryer by me~hanical: means such as an opposins cylindrical drum pressing against the web~ Multiple Yankee dryer drums can be employed, whereby additional preissing is optionally incurred between the drums. The tissue paper structures which are formed are referreid to hereafter as conYentlonal, pressed, ~;~ 15 tissue paper structures. Such sheets are considered ~o be compacted si:nce the entire web is subjected to substantial mechanical compressional forces while the fibers are moist and are~then dried while:in a compressed state : Patt~rn densified tiss~e paper is charac~erized by having a relatively high bulk field of relatively low:fiber density ;~ and~ an ar~ay of densified zones o~ relatively high:~flber ;~ density. Th~ high~ bulk field is alternatively characterized as a fi~ld of pillow regions. The densified zones aræ
alternatiuely re~erred to as knuckle regians. The densi~ied ZS~ zones~can be d~scretely spaced wtthin the high bulk fleld or . ~ can:be interconnected, either fully or partially, :within the : h~l:gh :bulk field.~ The patterns can :be formed in a nonornamental configuration or can be formed sa as to provide an orniamentàl d~isign(s)' ln the tissue paper.i Preferred ' i processes for making pattern densified tissue webs are - disclosed in U.S. Patent No. 3,301,746 (Sanford et al), issued anuary 31, 1967; U.S. Patent No. 3,974,025 (hyers), issu@d Au~ust 10, 19769 and U.S. Patent No. 4,1~1,609 lTrokhan) issued March 4, 1980; and U.S. Patent 4,637,85g (Trokhan) ;.

~s~

,~O 9~1/0~856 2 1 ~ 2 6 o ~ PCr/llS93/076~0 g issued January 20~ 1987; all of wnich are incorporated by refereMce .
In general, pattern densified webs are preferably prepared by depositing a papermaking furnish on a foraminsus forming wire ;uch as a Fourdrinier wirs to for~ a wet web and then juxtaposing the web against an array of supports. The web is pressed against the array of supports, th~reby resulting in densified zones in the web at the locations geo~raphically corresponding to the points of contact between the array of supports and tne wet web. The remainder or tha web not compressed durrbng this operation is referred to as the : hlgh bu?k field. This high bulk field can be further dedensified by application of ~luid pressure, such as with a vacuum typ~ device or a blow-through dryer, or by mechanically ~ pressing the web agains~ the array of supports. The web is dewatered, and op~ionally predried, in:such a manner so as to subskantially avoid compression of the high bulk field. This s preferably accomplished by fluid pressure, such as with a vacuum type ~evice or blow-through dryer, or ~lternately by mechanically pressing the web against an~ array of supports wherein the high bulk field is not: compressed.~ The operations ~ : ~
n ~- ~ of` dewaterin~, optional predrying and formation of the densified zones can be integrated or partial1y integrated ~o reduce the total number of processing steps performed.
: Subse~uant to formation of the densified zones, dewatering, and optional predrying, the web is dried to completian, preferably still avoiding ~echanical pressing. Preferably, : from about 8% to about 55X of ths tissue paper surface co~pri`ses`densi~ied knuckles haYing a relative'density of at least 1257~ of the density of the high bulk field.
: The array of supports is preferably an imprinting carrier fabric having:a patterned displacement of k~uckles which : operate a~ the array of supp~rts which faoilitate theforma~ion of ~he densified zones upon application of pressure.
: : 35 The pattern:of knuckles constitutes the array of supports '~

,j `

W09~/05~56 21~26~0~a Pcr/us93/o765lJ ~

previously r~ferred to. Suitable imprinti~g carrier fabrics are disclosed in U.S. Patent No. 3,301,746 (Sanford et al), issued January 31, 1967; U.S. Patent No. 3,821,068 (Salvucoi et al ), issued May 21, 1974; U.S. Patent No. 3,974,025 (Ayers), issued August 10, 1976; U.S. Pat2nt No. 3,i73.164 ~Friedberg et al.~, issued March 30, 1971; U.S. Patent No.
3,473,576 (Amneus), issued Ortober 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 ~ 85, all of which are incorporated by reference.
Pre~erably, the furnish is first for~ed 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 can alternately be initially deposited on a foraminous support~ng: oarrier which als~ operat~s as an imprinting fabric. Once formed, the wet web is dewa~ered and, pre:ferably,~ thermal~ly predriQd to a selécted fiber consiste:ncy of between about 40% and about 8~X. ~ Dewatering is preferably performed~with ~suc~ion boxes or othar vaouum devices or with b1ow-through ~ryerc. The knuckle imprint of thQ imprinting fabric is impresscd in the web as discussed above9 prior to , ~ , dry:ing th~ web to completion. One methad for accompl ishing this is through application of meohanlcal pressure. This can b~:done, for example, by pressing a nip roll wh1ch supports 5 ~ thelimprinting fabric against the faoe of a drying d~um, sueh as a Yankee :dryer, wherein the web is disposed between the nip roll and drying drum. Also, preferably, the web is molded agairst the~ imprinting fabric prior to completion of drying by application 3f fluid pressure with a vacuum de~ice suoh as a suction box, or with a blow-through dryer. Fluid pressure can : be applied::to induce impression of ~ens1fied zon~s during : initial dewatering, in a separate, subsequent proeess stage, ~; or a combinaticn thereof.
:~ Uncompacted, nonpattern-densified tissue pap~r s~ruc~ures 35~ are described in UOS. Patent No. 3,812,000 (S~lvurei et al), ,'li: :

i ~3 ~.0 94/0~856 2 1 A~ ~ 6 o; Pcr/us93/o76so '~

issued May 217 1974 and U.S. Patent No. 4,2û8,459 (Becker et al ~, issued June 17, 198a, both of which are incorporated by reference. Xn general, uncompacted, nonpattern-densified ~ ;tissue paper structures are prepared by depositing a paper~aking furnish on a foraminous forming wire such as Fourdrinier wire to form a wet web, draining the web ~nd removing additional water without mechanical compression until the web has a fiber c~nsistency of at least about 80X7 and crepi ng the web . Water i s removed from the web by vacuum dewatering and thermal dryin~. The resulting structure is a soft but weak, high bulk sheet of relatively uncompacted fibers. Bnnding material is preferably applied to portions of the web prior to creping.
Compacted non-pattern-densified tissue structures are oommonly known in the art as conventicn~l tissue struetures.
In general, compacted, non-pattern-dens~fied tlssue paper structur~s are prepared by d~epos~ting a papermaking furnish on : a foraminous wire sueh as a Fourdrinier wire to form a wet `: web9 draining tbe web and removing additional water with the o aid of a uniform mechanical compaction (pressing) until the web has a consistency of 25-50%, transferrins the web to a thermal dryer such as a Yank~e and creping the web. Overall, ~ wa~er is re~ov@d from the web by vacuu~, mechanical pressing : ~: and thermal meaRs . The resulting structure is strong and ~9enerally of singu~ar density, but very low in bulk~
: absorbency and softness.
The paper~aking fibers utilized for the present invention ; i ! will, normally include fibers derivedf ~rom wood pulp. ;Other ~ cellulosic fibrous pulp fibers, such as cotton linters, :: : 30 . bagasse, etc., can be utilized and are intended to be within : : the scope of this invention. Synthetie fibers, such as rayon, polyethylene and polypropylene fibers, can also be u~ilized in I co~bination with natural cellulosic ~ibers. One exemplary polyethylene fiber which can be utilized is PulpexTM, , avaitable from Hercules, Inc. (Wilmington, Delaware3.

':

..........

W 0 94/OSB56 P~r~U593/07650 2 1 4 ~ 6 0 ~J -12-Applicable wood pulps include chemical pulps, such as Kraft, sulfite, and sulfate pulps, as well as mechanieal pulps including, for example, groundwaod, thermomechanical pulp and chemieally modified thermomechanical pulp. Chemical pulps, howeYer, are preferred sinc- they imparl a superior tac~
sense or softness to tissue sheets made therefrom. Pulps derived from both declduous trees ~hereafter, also referred to as "hardwood~) and coniferous trees (hereafter, also referred to as "softwood") can be utilized. Also useful in the present invention are fibers deriYed rrom recycled paper, which can sontain any or all vf the above categories ~s well as other non-fi!brous materials such as fillers and adhesives used to -facilitate the original papermaking.
In addition to papermaking fibers, the p~permaking furnish ~sed to make tissue paper structures can have sther components or m~terials added thereto as can be or later become known in the art. The types of addi~ives desirable wilt be dependent upon the particular end use of the tissue sheet contemplated. For example, in products such as toilet 2~0 papert paper towels, facial tissues and other similar product~s, high wet str~ngth is a desirable attribute. Thus, it is often desirable to add to the papermaking furnish chem k al;subs~ances known in the art as "wet strengthl' resins.
A general dissertation on the types of wet strength ~ ~resins utilized in the paper art can be~ found in TAPPI;
; monograph series No. 29, Wet Strength in Paper and Paperboard, Technical Associ~tion of the Pulp and Paper Industry ~(New York, 1965). The most u$eful wet strength resins have generally been cationic in character. Potyamide-~pichlorohydrin resins are eationic wet strength resins which have~ bQen ~sund to be of particular utility. Suitable types of such resins a~e described in U.S. Patent No. 3,700,523 Keim~, issued Oc~ober 24, 1972, and U.S. Patent Nu. 3,772,076 Keimj, -issued NoYember 13, 1913, both of whieh are ~ncorporated by reference. One commercial souree of a useful , ~" ~ :

~ 94/0~56 2 1 ~ ~ 6 ~ ~ P~r/US93/~7650 polyamiae-epicnlorohydrin re~ins is Hercules, Inc. of Wilmington, Delaware, which markets such resins under the mark Kymeme~ 557H.
Polyacryl2mide resins have also been found to be of util ity as wet str~ngth r~sins. These r~sins ar~ described in U.S. Patent N~s. 3,5~6,932 (Co;c,a et al), issue~ January 13, 1971, and ~,556,~33 (Williams et al), issued January 1~, 1971, both of which are incorpor~ted herein by reference. One commeroial source of polyacrylamide resins is American Cyanamid Co. af Stanford, Connecticut, which mar~et; one such resin under the mark Parez~ 631 NC.
Still other water-soluble cationic resins finding utility in this invention are urea ~ormaldehyde and melamine formald~hyde resins.~ The more common functi4nal groups of ~ 15 these polyfunctional resins ~re nitrogen containing groups ;~: such as amino groups and methylol groups attached to nitro~en.
Polye~hylenimine type resins can also find ut~lity in the ;: pres2nt inYention. In addition9 temporany wet strength resins such as Caldas 10 (~anufac~ured by Japan Carlit3 and CoBond 100a ~manufactured by National Starch and Ch~mical Company) : can be us~d in the present invention. It i5 to be understood that the additinn of chem k al compounds such as the wet strength and t~mporary wet strength resins discussed above to the pulp furnish is optional and is not necessary for the :practice of:the present invention.
In addition to wet strength additiYes, it can also be ~:~ desirable to include in the papermaking fibers cer~ain dry strength and lint control additives knnwn in the art. In this regard,~starch bind~rs ~ave been found tn be p'articularly suitable. In addition to reducin~ linting of the finished ~^~ tissu~ paper product, low leYels of starch binders al50 impart . a modest improvement in the dry tensile strength without imparting stiffness that could result from the addition of high ~evels of starch. Typically the starch binder is included in an amsunt such that it is retained at a level of :j j , W 0 94/05$56 PCT/US93tO765~ ~
21~0S

from about 0.01 to about 2%, pref~rably from about 0.1 ~o about 1%, by weight of the tissue paper.
In generalS, suitable starch binders for the present invention are characterized by water solubility, and hydro~hilicity. Al~houqh it is not intended to limit the scope of suit~ble starch binders, representativ~ s;arch materials include corn starch and potato starch, with waxy corn starch known industrially as amioca starch being part1cularly preferred. Amioca s~arch differs from common oorn stareh in that it is en~ir ly amylopeetin, wher~; co,~mon corr. starch contains both amylopectin and ~mylose. Yarious : unique characteristics of amioca st~rch are further described in "Amioca - The Starch From Waxy Corn", H. H. Sschopmeyer, Food Industries, December 1945, pp. 106-108 (Vol. pp.
: 15 1476-~7 : The starch binder can be in granu~ar or disp~rsed form~
: ~ the granular form being especially preferred. The starch binder is preferably sufficiently cooked to induce:swelllng of : the granules.: More preferably, the starch granules are ` 20 : swol~en7 as by cooking, to a point just prioSr to dispersion of the:starsh granule. Such highly swollen starch granules shall ;be referred to~as being "fully cooked." The conditions for di~persion in gseneral can vary dependsing upon th~ size of the staroh granules, the degree of crystallinity of the granules, : and the amount of amylose present. Fully cooked amSioca st~rch, for examplse, can be prepared by heating an aqueous ~ slurry of abnut 4Z consistency of starch granules at about :~ 190-F (about 88s~) for between about 30 and about 40 minu~es.
Other exemplary'starch binders which can be us~d ir.clude modified cationic starches such as those modi~ied to have nltrogen ontaining groups, including amino groups ~and methylol groups attached tQ nitrogen, available from Natlonal . Starch and Chemiral ComFSany, (Sridgewater, New Jersey), that haYe heretofore been used as pulp furnish additives to ~ 35 increase wet and/or dry strength.

s `
,, ~
.

.qO 94/05856 2 1 ~L ~ 6 ~ ~ PCI/US93/07650 .. ..

B. BiQde~radabl~ Nonlonic Soft~ners Su~table nonionic softeners for use in the present inven~ion are biodegradable. As used herein, the term "biodegradability" ref0rs to the complete breakdown of a substance by microorganisms to car~on dioxide, water, biomass, and inorganic materials. The biodegradation potential can be estimated by measuring carbon dioxide evolution and dissolved organ k carbon removal ~rom a medium containing the substance being tested as the sole carbon and energy source and a dilute bacteri~l inoculum obtained from th~ supernatant Ot homogenized activated sludge. See Larson, "Estimation of Biodegradation Potential of Xenobiotic Organic Chemicals,"
ADD1 jed and Environmental MicrobioloqY, Yolume 38 (1979), pages 11~3-~1, which describes a suitable method for estimating biodegradability. Using this method, a substance is said ~o be readily biodegradable if it has greater than 70Y~
c:arbon dioxide evolution and greater than 90Y~ dissclved organic carbon removal within 28 days. The softeners used in ~: the present invention meet such biodegradability criteria.
Another important aspect nf the so~teners used in the pres~nt invention is their melting propQr~ies. It is believed : tha~ the operative mechanism by which softeners used in the present inventioR work is as a result of surface lubrication of:the tissue paper. Such surface lubrication is believed to 25~ ~require the:so M ener active to begin melt;ing at or below about body temperature, l~e. at abnut 37-C. Accordingly9 suitable ;:softeners for use in the present inYention typically h~aYe, as easured by Differential Scanning Calorimetry (DSCJ, an onset oF melting at dt ~ below! aiboùt~ 37-C. Preferably, thèse : 30 sof$eners have an onset of melting a~ or below about 35'C.
As used herein, the term Nonset of melting" refers`to thQ
- : point at which the ~oftener begins to change from a solid to a : liquid state. As measured by DSC, onse~ of melting occurs at the point of intersection of: (a~ the tangent drawn at the point of greatest slope on the leading edge of the peak, and WO g4/05856 ` PCl`/US93/07631) ~14~60~

(b) the extrapolated base line ~f the DSC thermogram. See pages 807-808 of Wendlandt, Thermal AnalYsis, (3rd edition, 1986), which defines this point of intersection as the ~'extrapolated onset." What constitutes an onset of melting of the soft~ner oan be best understood by ref rence to Figure 1.
Figure 1 represents a DSC thermogram of a preferred softener system comprising mixed sorbitan stearate esters (GLYCOMUL-S
CG) and an ethoxylated aliphatic alcohol (NEODOL 23-6.5T) in about a 4:1 weight ratio. Referring to Figure 1, the DSC
thermogram identified by the letter T has tws endotnermic peaks P-1 and P~2 that represent the melting of two different phases of the softener system. The peak mett point (i.e.,---the highest poin~ on the peak) is 9.92-C (PM-1) and 49.74-C (PM-2 : for P 1 an~ P-2, respectively. The onset of melting for each ; 15 of these peaks is -1.94-C (OM-1) and 32.36-C (OM-2), respectively:. Ths onset of melting represent~d by OM-2 is the most imp~rtant since P-2 represents the largest, predominant : melting phase of the softener system. Indeed9 for the purposes of the present invention, the onse~ of melting usually re~ers to that of the predominant melting phase, i.e.
: ~ that phase having the largest peak area.
The onset of ~elting of softener systems used in the present ~nvention can be determined by DC as foltows: A TA
instruments DSC, Model 2910 (Controller 2000 with TA Operating : System S~ftware 8.5C) made by TA Instruments, Newcastle, DE is : used. The softener sample is placed in an open aluminum pan with an invQrted lid and the weight recorded. The soft@ner sample pan and a ref@rence pan are then placed in the DSC
cell. The cell ccnt~ining the softener sampla is caoled to ~ -50C, allowed to equilibrate, and then scanned from -50~ to ; 2259C at a rate o~ 20-C per minute. A nitrogen purge flow of ; 0.0037 l./min is applied to the cell. The resulting DSC
thermogram records the onset of mel~ing point, the peak melt psint, and h~at of fusion for each of the endathermic peaks, as is shown in ~igure- 1.

, ~ ~ 94/0~56 2 1 ~ 2 6 0 :~ PCT/US93/~7650 Nonionic softPners suitable for use in the present invention comprise certain nonionic surfactants. These nonionic surfactants include the sorbitan esters, preferably the sorbitan esters of the C12-C~2 fatty acids~ most pr~rerably the sorDitan esters of Cl2-C22 saturated fatty acids. Because of the manner in which they are typically manufactured, these sorbitan esters usually comprise mixtures of mono-9 di-, tri-, etc. esters. Representativ~ examples of suitable sorbitan esters include the sorbitan laurates (e.g., SPAN Z0~, sorbitan myrtstat~s, sorbitan palmitates (e.g., SPAN
40), surbitan stearates (e.g., SPAN 60), and sorbitan behenates, that oomprise one or more of the mono-, di-- an~
tri-ester versions of these sorbitan esters, e.g., sorbitan.
mono-, di- and ~ri-laurate, sorbitan mono-, di- and ` tri-myris~ate, sorbitan mono-, di- and tri-palmitate, sorbitan ~` : : mono-, di- ~ and tri-stearate, sorbitan :mono~, di and tri-behenate, as well as mixed coconut fatty acid sorbitan : mons-, di- and ~ri-esters, and mixed:tallow fatty acid sorbitan mono-, di- and tri-esters. Mixtures of different 20~ ~ sorbi:tan esters can also be used, such as sorbitan palmitates with sorbit2ln stearates. Particularly prePerred sorbitan es~ers~ are~the sorbitan stearates, typical1y as~a ~ixture of mono-, di- and tri-esters (plus some tetraester) such as SPAN~ 60? and sorbitan stearates sold under the trade name 2S~ 6LYCOMUL-S by Lon~a, Inc. : ~ ~
Nonionic surfactants suitable in the softener systems of the presen~ invention oan also include ethoxy7a$ed, propoxylated, and mixed ethoxylated/propoxylated versions of : these sorbitan esters. The ethoxylated/propuxy1ated versions 30: ~ of these sorbitan esters have 1 to 3 oxyethylene/oxypropylene moi~ties and typically an average degree of ethox~fla~ion/
propoxyla~ion sf from 1 to about 20. Representative examples of :suitable ethoxylated/propoxylated sorbitan es~ers include ethQxylated/propoxylated sorbitan laurates, e~hoxylated/-~ 35 ~ propoxyla~ed sorbitan myristates, ethoxyl~ted/propoxylated ! :

21 ~ 2 6 05 .?~
6 . PCr/U593/07651J
.

sorbitan palmitatest ethoxylated/propoxylated sorbitan stearates, and ethoxylated/propoxylated sorbitan behenates.
where the average degree of ethoxylation/propoxylation per sorbitan ester is preferably from about 2 to about 20. more i pr~ferably from about 2 to about 10, mos~ pref~5bly ,~rom about ~ to about 6. Ethoxylated versions or these sorbitan esters are especially prererred and are commeroially available under th~ trade name TWEENS. A particularly preferred vers;on of these sorbitan esters is ethoxylated sorbitan stearate having an average degrss Ot ethoxylation per sorDitan est r or about ~, sold under the trade name TWEEN 61.
Besides the nonionic surfactant, softeners used in the present invention can additionally comprise other components.
These other components typically aid in dispersing (or dissolving) the surfactant in water, modify the melting : properties o~ the surfactant, or both. In particular, : unethoxylated/unpropoxylated sorbitan esters, such as the sor~itar.:stearates, are not Yery hydrophilic, and can have mel:t point propert;es such that the onset of melting is above 0`~:~ about 37-C. In the ~ase of such less hydrophilic, higher melting surfactants, it is usually desirable that the softener comprise one or more components that aid in tispersing:the sur~actant in watert as well as lower :the melting~point of the surfactant.
: :25 :~ : In the case of sorbitan ester surfactants, suitabl~e i:spersion and~melt point additives include condensation products of aliphatic alcohols with ~rom about 1 to about 25 ~ moles of ethylene oxide. The alkyl chain of the aliphatic `~ ~ alcohol is typ~cally `in a ~straight chain (linear) 30: configuration and contains from about 8 to ~bout 22 carbon : atoms. Particutarly preferred are the condensatiQn products of alcshols having an alkyl gro~p containing from abo~t:11 to ; about 15 car~on atoms with from about 3 to about 15 moles, preferably from about 3 to about 8 moles, of ethylene oxide 35 : per mole of alcohol. Examples of suoh ethoxylated alcohols 1: .

~ ~;

v~o 94~0~8S6 PC~r/~'S93/0765~ 21~2605 include the condensation products of myristyl alcohol with 7 moles of ethylene oxide per mole of alcohol, the condensaticn products of coconut alcohol (a mixture of ~atty alcohols haYing alkyl chains varying in length from 10 to 14 carbon atoms) with about 5 moles of ~thyl~ne oxide. A number of suitable ethoxylated alcohols are commercially available, including TE~GITOL l;-S-9 (the condensation product of C11-C1s linear alcohols with 9 moles of ethylen~ oxide), marketed by ~ Un1on Carbide Corporation; KYRO EOB (condensation product of ;~ 10 C13-C1s linear a1cohols with 9 moles of ethylene oxide~, marketed by The Procter & Gamble C0.1 and especially the NEODOL brand name surfactants marketed by Shell Chemical Co., in particular NEODOL 25-12 ~condensation product of C12-C1s linear alcohols with 12 moles of ethylene oxide), NEOOOL
: 15 23^6.5T (condensation product of cl~-el3 linear alcohols with 6~5 moles of ethylene ox~de that has been dist;lled ~topped) : to remove certain impurities), and NEO~OL Z3-3 (condensation produet of C12-C13 linear alcohols with 3 moles of ethylene oxide).
20 : A particularly preferred softener system for use in the present invention co~prises a mixture ~o~ sorbitan stearate és~ters9 such as~6LYCOMUL-S, ~nd an ethoxy1~ted C}1-C1s linear alcohol surfac~ant, such as NEODOL 25-12, and preferably NEODOL~ 23~6.5T. These preferred so~teners comprise a weight 25~:~: :ratio of sarbitan stearate esters to ethoxylated alcohol surfactant in the range of from about 1:1 to about 10~
` ; Preferably,~these softeners comprise a weight :ratio of sorbitan stearate esters ~o e~hoxylated alcahol surfactant in the rahge of`~from about 3:1 to about 6:1. Besides dispersinlg th~ sorbitan steardte esters in water, the ethoxylated alcohol surfactant is also believed to lower the onset o~ melting of he sorbitan stearat~ esters to well~below body tempera~ure7 e.g., the onset of ~elting is about 32-C or less. ~In the absence of the Neodol surfactant, sorbitan stearate ~sters 3S typically have an onset of melting of about 37~ - 39-C~

W O 9~/05856 ~ 21~ ~ 6 0 a P ~ /US93/0765~i -In the case of the ethoxylate-;~propoxylated versions of the sorbitan esters, the nonionic surfactant does not typically require an additional dispersing aid. Also? the etho%ylat~d/propoxylated versions of the sorbitan esters are usually suffioiently low melting, e.g., some sueh as the TWE~N 60 are par~ially liquid at room temperature (20--25-C).
Aceordlngly, melting point aids are not typically required for su~h surfactants.

~ 10 C. Tr~atinq Tissue PaDer With Softener Svstem : In the process according to the present invention, at leas~ one surface of the dried tissue paper web is treated with the softener. Any method suitable for applying additives to the surfaces o~ paper webs can be used. Suitable me~hods : ~:inc~lude spraying, printing (e.g., flexographic printing), oating ~e.g., gravure coating~, or com~inations o~ appli-cation:techniques, e.g. s~raying the softener on a rot~ting surface, such as a catender roll, that then transfers the softener to the surface of ghe paper:web. The softener~ean be 20 :~ app~ ed either:to one surface of the dried ~issue paper web, or~both sur~aces. for example, in the ease of pattern dens;fied tissue papers, the softener can:be~applied to the rougher, fabrîe~side, the smoother, wlre side,~or both: sides of:the tis:sue~paper web. Surprisingly,~even when the softener zs~ is~applied only to the s~oother, wire side of the: tissue paper d~ eb, the treated paper is still perceived~as so~t.
: In the process of the present invention, ~he softener is typieally ~pplied from an aqu~ous dispersion or solution.
These aqueous systems typically comprise just wa~r and the ;: :30~ softQner, but cao~ include other optional;components. As ~ previously noted, certain softPner surfactants can be `~ H~ dispersed: or dissolved in water without dispersing aids.
: However~ in the case of other s~rfactants, such as the sorbitan stearates, the softener usually eomprises a dispersing aid, as previously desoribed. The aqueous sys~em , ~,O 9~/0~856 ~ 93/07~0 21~1260S

can additionally comprise a minor amount (e.g., up to about 0.~% ~y weight) of a salt, such as sodium sulfate, to lower the viscosity of the aqueous system at higher concentrations of softeners, especially those containing sorbitan stearates.
In formul~ting such aquesus systems, the sortener is dispersed or dissolved in the water in an effective amount.
: What constitutes "an eftective amount" or the sofkener in the aqueous system depends upon a number of factors~ ino~uding the type of softener used, the softening effects desired, the manner of application and li~e ractor;. :8asically, the :~ softener needs to be present in amount sufficient to provide effective softening without adversely affecting the ability to apply the softener from the aqueous system to the tissue paper web. For example, relatively high concentrations of softener can make the~dispersion/solution so VlSCOUS ~S to be difficult, or impossible, to zpply the softener to the tissue paper~ web by conventional spray, printing: or coating equl;pment.
In :the case of sorbitan esters, such as sorbi~tan ~
zo ~ ~stearate, that require dispçrsing aids, the soft~ner usually comprises from about 9 to:about 30% by weight of the aque~us : system. Preferably, sorbitan ester-containing s~fteners omprise from ~about 12 to about 20%, most p~eferably from~
about 12 to about 16%,~by wei~ht of the aqueous system.~ Where : spray:appli~ca~ions are contemplatedt ~the ~aqueous system of sorbitan ester-~containing softener should be formulated to have a viscosi~y of about 700 ~entipoise or less, and : typically within the range of fro~ about 200 to absut 700 cent~poise, when'meas~ured at the temperàture oflapplication, e.g., pr~ferably from about 50- to about 81-F (from about 10-to about 27-C). Preferred aqueous systems of sorbitan ester softeners accordihg to the present invention have vi:scosities in the range of from about 300 to about 5Q0 centipoise, when measured a~ a temperature of- from about 50- to about 81CF
~from about 10 ~o about 27'C).

, ~

W O 94/05XS6 PC~r/US~3~076~ ' 2 1 4 2 6 0 ~ 2~ ;

The effect of softener concentration and temperature on the viscosity of aqueous dispersions of sorbitan ester-containing softeners is particularly illustrated by a preferred softener system used in the present invention. This i preterred softener comprtses a 4:1 wPight ratio or GLYCOMUL-S
CG (a mixed sorbitan stearate ester) to NEODOL 23-6.;T ~an ethoxylated C12-~13 linear alcohol). Viscosity measurements (at 24-C) with varying concentrations of this preferred softener system are shown in Table 1 below:
~ 10 ~ Table I
:~ So~tener Conc. Viscosity (% GLYCOMUL-S CG) l__~tiDoise !
5. 1;9 : 11 . 320 : : 14 : 890 : 17 : 2~80 ; ~ ~ 3390 ~ :
: As Gan be seen ln Table I above, the viscosity o~ aqueous ~, ~
dispersions o:f: this preferred softener system rise 20~ : dramatically:~at concentrations~abovelabout 11% GLYCOMUL-S CG.
The optimum concentration af GLYCOMUL-S CG in such aqueous d1spersions is~lltypically about 12%~ at 24~C~. This~:
concentrati:on is consi:dered "opti~um" in that: Ia) :the concentr~t~ion::~of softener active is as high as practical to 5~ mi~nlmize the amount of water added~to the tissue paper~web during:treatment with the softener; (b)~yet is not s:o high so : as to make~the aqueous dispersion too v~iscous to be suitable : for pray ap~lications. IIf highe,r,lconcentrations iof: ;j 6LYCOMUL-S CG are desired, a minor amount (e.g.l about 0.3% by 130~ weight) of a salt, such as sodium~ sulf~te~ is ~prefærably - :included in the aqueous dispersion ~o keep it at:or~:below ~a visoosity of about 700 centipoise when measured~within the previously :ind k ated temperature range.

3S:

2 ~ P~T/U~93tO7 -23- :

The effect or varying temperatures on the viscosity o;
aqueous dispersions of this preferred softener system ~GLYCOMVL-S CG concentration of about 12%) are shown in Table 2 below:

Table TemDerature (-C~ viscositY (centiPoise~

$00 16 ~80 ~ 38 2 90 5~ ~
~: As can be seen in Table 2 above, varying the temperature of the aqueous dispersion of this preferred softener system can also haYe a significant effect on its viscosity. the viscosity is fairly eonstant at temperatures of ~rom about 10-: : to about 27~C, then rises dramatically at a ~emperature o~
about 33UC, and then falls equally dramatically at a temperaSur~ of about 49-C due to phase separation o~ the : GLYCaMULS ~G and water. Accordingly, for spray ~pplicatians, 25 ~ ~ ~t:he :temperatur@ of the aqueous dispersion of this preferred soft~ne~ syste~q at its optimum so~tener 2ctive conrentration, is pr@~rably between about lQ~C and about 27-Co ~: In the case:of ethoxylated/propoxylated sorbitan es~ers, such as.TWEN 619, thjat can;be~dispersed ar disso,lved in water ; ~ 3a : without oth~r a1ds, the softener usually comprises from about 10 to about 50% by weight of the aqueous system. The preferred ethoxylated sorbitan ester-containing so~teners : (e.g. T~EEN 61) pref@rably comprise from about 20 to about 4~%
by weight, most preferably from about 25 to abou~ 35% by wei~ht, of the aqueous system, typically as an aqueous , ~ , WO 94/058~6 PCr/US93/1)76~1) .
~ 60'~ -24-solution. Where spray applic~tions are contemplated, th~
aqueous systems comprising these preferred ethoxylated sorbitan ester so~teflers should be formulated to have a viscosity of about 7no centipoise or less, and typically in the range of from about 20 to about 700 cent~poise, as measured ~t the temperature of application, e.g., prererasly from about 130- to about lS0-F (from about ~4.4~ to about 6;.6 : C), such as in the case of TWEEN 61 which melts and dissolves in ~ater within this temperature range. Preferred aqueous sys~ms of thes prererred ethoxylated sorDitan ester softeners have viscosities in the range of from about 20 to about 500 centipoise, when measured at a temperature of from about 130~ to about 150F (fro~ about 54.4~ to about 65.69C)~
:: In the process of the present invention, the softener is applied to the tissue paper web after it has been dried, i.e.
the~application of softener is a "dry web" additi~n method When dri:ed, the tissue paper usually has a mo:istur~ content of about 10% ;or less, prefe~ably about 6% or less, most preferably about 3% or l ess . In commercial papermaking 20:~: systems, treatment with the softener usually occurs af~er the tissue paper web has been dried by,~ and then creped from, a Yankee dryer. As previously noted, if added to a wet paper web,-nonionic surfactants, such as the ~orbitan stearates, have~a greater potefltial to migrate to~the interior of the web 25 :~ and: completeiy ~oa~:the fibers. This can cause :inereas:ed fiber debonding that could lead to a further reduction in tensile strength 2~ the paper, as w~ll as affect paper ettab~lity if the surfactant is a less hydrophilic one, as are! sorbltanistearates. ' :: 30 ~- Addition of such nonionic sur~actants to wet webs is parS k ularly not desirable in commercial papermaki~ng systems.
: Such addition can interfere with the glue coating on a Yankee dryer, and can also cause skip crepe and loss in sheet ; : control. Accordingly, treatment of the tissue paper web with- 35 the $oftener after it has been dried,~as in the present ,j:
~!~

~O 9~/05~s6 P ~ /US93/07650 214~6U~;

invention, avoids these potential problems Ot wet web addition, particularly in commercial papermaking systems.
In the proeess o~ the present invention7 the softener is applied in an amount o~ from about 0.1 to about 3% by weigh~
of the tissue paper web. Preferably~ the softener is applied in an amount of from about 0.2 to about 008% by weight o~ the tissue paper web. Such rela~ively low levels of soft~ner are adequate to impart enhanced softness to the tissue paper, yet do not coat the surface of the tissue paper web to such an extent that strength, absorbency, and particularly wettability, are substantially affected. The softener is also : typically applied to the surface of the tissue paper web in a nonuniform manner. By "nonuniform" is meant ~hat the amount, pattern of dis~ribution, etc. of the softener ean vary over the surface o~ the paper. For example, some portions of th~
: sur~ace of the tissue paper web can have yre3ter or lesser amounts of softener, including portions of the surface that do not have any softener on i~.
his typical:non~niformity of the softener on the tixsu2 paper web is believed to be due, in lar~e part, to the manner : in which the softener is applied~to the~surfaee thereof. For example, in preferred treatment methods wh~re aQueous : dispersions or solutions of the softener are spray~d, the :soften~r is applied as a regular, or typically irregular, .
pattern of softensr droplets on the surface o~ the tissue paper web. This nonuniform application of sof~ener is also beli~ved to avoid subs~antial adverse effects on the s~rength ~:: and absorbency of the tissue paper, and in particular its wetta~ility, `as': well as reducing the levet of softener re~uired to provide effective ~oftening o~ the tissue paper.
The benefits o~ nonuniform appl k ation are believed to be : especially i~portant when the softener comprises 1ess hydrophilic nonionic surfactants, in particular sorbitan esters such as the sorbitan stearates.
: 35 ' :` ~ : :

Wl:~ 94/~5856 PCr/US93/0765~J
21~260a The softener can be appl ied to the tissue paper web at any point after it has been dried. For example, the softener can be appl ied to the tissue paper web after it has been creped from a Yankee dryer, but prior to calendering, l.e., before being~ passed through calender rolls. The sott~ner can also be applied to the paper web atter it has passed ~hrough such calender rolls and prior to being wound up on a parent roll. Although not usually preferred, the softener c~n also be applied to the tlssue paper as it is being unwound from a parent roll and prior to being wound up on a smaller, ;inished : paper produet roll.
Figure 2 illustrates a preferred method of applying the : aqueous dispersions or solutions of softener to the dry tissue paper.web. Referring to Figure 2, wet tissue web 1 is carriéd lS on imprinting fabric 14 past turning roll~ 2 and then ran5ferred to a Yankee dryer 5 (rotating in the direction indicated~by~arrow 5a) by th~ action of pressure roll 3 while imprinting fabric~::14 traYels past turning roll 16. The paper : web i:s: adhesively secured to the cylindrical s~rface of dryer :20 ~ 5 by:~an adhesive~ suppl:ied from spray appllcator 4.~ Drying is comp1~t~d by~steam~heating dryer ~ and by~hot air heated and~
circulated through dry:ing hood 6 by means not shown. The web is~;then dry~creped~from dryer S by doetor blade 7, after which it~`becomes;designated as dried creped paper sheet 15.~ : :
25 ~ :: Paper:sheet }5 then passes between a pair of ca~lender rol;ls 10 and; 11. An aque~us dispersion or solutio:n of :softener is sprayed ~onto upper calender roll I9 and/or 1ower : cal~ender roll 11: by spray applicators 8 and 9, respectively, : depending ~n wh~ther:dn~:~or both sideis o~ p~per,she~et 15 is to 30~ be ~reated with softener. The aqueous dispersion or solution of softener i~s::applied by sprayers 8 and~ to the surface of upper calender rol~l 10 andlor lower calender roll l l as a :
: pattern of droplets. These droplets containing the softener -: are then transferred by upper calender roll 10 andlor lower 35~ ~ calender roll 11, (rotating in the direction indicated by .10 94/05856 2 1 ~ 2 6 0 !i PCT/US93/076s0 arrows lOa and llai~ to the upper and/or lower sur~ace of paper sheet 15. In the case of pattern~densified papers, the upper surface of paper sheet 15 usually corresponds to the rougher, fabric side of the paper, while the lawer surface corresponds to the smoother, wire side of the pape~. The upper cal~nder roll 10 and/or lower calender rotl 11 applies this pattern of so~tener droplets to the upper and/or lower surface of paper sheet ~5. Softener-treated paper sheet 15 then passes over a circumferential portion of reel 12, and is then wound up onto parent roll 13.
One particular advantage of the embodiment shown in figure 2 is the ability to heat upper calender roll 10 and~r lower calender roll 11. By heating calender rolls 10 and/or ll, some of the water in the aqueous dispersion or solution of softeiner is evaporated. This means the pattern of droplets : contain ~cre concentrated amounts of the softener. As a result~ a par~icularly effective amount of the softener is applied to the~ surface(s) of the tissue paper, but tends not to migrate to the interior of the paper web because of the 20 ~ ~ reduced amount of water.

:: Ti~ssue paper softened according to the present invention, especially facial and toilet tissue, has a so~t: and~:
2~5 ~ ~ vel:vet-like~feel due~to the so~tener applied to one or~both ::
su~faces of the: paper. This softness~ can be eval~uated by subjective testing that obtains what are referred to as Panel S~ore Units (PSU) where a number of practiced :softness judges are ask~d-:~o raite~the r~lative so~tn~ss of a plurality of i~
30 ~ ~ paired samples. The data are analyzed by a statistical method known as a paired;comparison analysis. In this method, pairs of samples are first identified as such. Then, ~he ~pairs of : samples are iudged one pair at a time by each judge: one sample of each pair being designated X and the other Y.

WO 94/05856 P~r/US93/07~5~ :
~ 2~ 6Q~

Briefly, ~ach X sample is sr~ded against its paira~ Y sample as follows:
1. a grade of zero is given if X and Y are judged to ~e equally soft.
2. a ~rade of plus one is given if X is judged to maybe be a little softer than Y, and a grade o~ minus one is giYen if Y is judged to maybe be a little softer than X;
: ~ 3. a grade of plus two is given if X is judged to surely b~ a little softer t~an Y, and a grad~ of : : minus ~wo is given if Y is judged to surely be a little soft~r than X;
4. a grade of plus ~hree is given to X if it is judged to be a lot softer than Y, and a grade of minus three is given if Y is iudged to be a lot softer than X;~ and lastly, 5.~:~: a:grade of::plus four is given to: X if it is judged to be a; whole lot softer than Y, and a grade of minus ~ is given if Y is jud~ged to be a whole lo~
20~ softer than X.
T~e~re ulting~:data ~rom all-judges: and all sample pairs are then~pair-averaged and r:ank ordered accordiflg to thelr grades.
Then, the~rank:~is sh~fted up or down in value as required~to ;gi:ve~:a zero~PSU value:to whichever s~ample is chosen to~:be the~
25~ zero-base~standard. The other sampl:es then have plus:or minus a:~ values: as~d@termined by their rela~ive grades with respect: to::
thé:zero base:~s~tandard. A difference of about 0.2 PSU usually repres~nts a-significance difference in subjeetively perceived sd~tness. R~lative toilth'e unsoften~d tissue paper, ~tissue~
30 ~ : paper softened according tn the present invention typically is . .
about 0.5 PSU or:~greater in softness. :: ~:
An:importan~ aspect of the present invention is :that thi~s softness enhancement can be achieved while other deslred : properties in the tissue paper are maintained, such as by 3~ compens3ting mechanical processing (e.g. pulp refining) and/or ~ , .

~0 94/~5856 Pcr/us93/076~0 ~1~260.;

the use of chemical additives (e.g., starch binders). One such property is the total dry tensile strength of the tissue paper. As used herein, "total tensile stren~th" refers to the sum of the machine and cross-machine breaking strengths in grams per inch of the sample width. Tissue papers softened aecording to the present invention typically have total dry tensile strengths of at least about 360 g/in., with typical ranges of from about 360 :to about 450 g/in. for single-ply : facial/toilet tissues, from about 400 to about 500 g/in. for two-ply facial/toilet tissues, and fr~m about 1000 to 1800 g/in. ~or towel products.
Another property that is important for tissue paper softened according to the present invention is its absorbency : or wettability, as reflected by its hydrophilicity.
15 : ~ydroph~licity of tissue paper refersj ifl general, to the propensity of the tissue paper to be wettèd wi~h water.
Hydrophilicity of tissue paper can be quantified somewhat by s determining~ the period of time required for dry tissue ~aper o~b~come completely wetted with water. This period of time :
20 ~: is: re~ferred to as the "wetting" (or "sink~ng"3 time. In order to provide a consistent and repeatable test for wetting time, the fo~llowing procedure can be used ~for :wetting time determinations: first, a paper sample (the :environ~ental conditions for~testing of paper sdmpl@s are~ 23~+ I~-C and 50 +
25~ X~RH.: as specified in TAPPI Method T 402), àpproximately 2.5 nches x 3t~ ches (about 6.4 cm x 7.6 cm3 is cut from an 8 : sheet thick stack;Q~ conditioned paper~sheets; second, the cut 8 sheet thick paper sample is placed on the surfac~ o~ 2500 ml'.:of distill'ed wa~e~ ~at Z3 + 1~C and a~ltimer ~s ;
: 30 simultaneously started 3S the bottsm sheet of~the sam~le ` tous~5 the water; third, the timer is ~stopp~d and read when wetti~g of th~ paper sample is completed,:i.e. when the top sheet of the sample becomes completely wetted. Complete wetting is observed-visually.

~ - ~
.

W~ 94/05~6 . ,; PCr/lJS93/~7651/
214~6~
-30~

The preferred hydrophilicity of tissue paper depends upon its intended end use~ It is desirable for tissue paper used in a variety of applications, e.g., toilet paper, to completely wet in a relatîvely short period of time to prevent clo~ging once the toilet is flushed. Preferably, ~etting time is 2 minutes or less. More preferably, wet~ing time is 30 seconds or less. Most preferably, wetting time is 10 seconds or less.
The hydrophilicity of tissue paper can, of course, be determin~d immediately a~t~r manufacture. Howevsr, ~ubstantial increases in hydr~phobicity can occur during the :: first two weeks after the tissue paper is made: i.e. after - the paper has aged two (2) weeks following its manufacture.
Thus, the above stated wetting times are preferably measured at the end of such two week period. Aceordingly, wetting . ti~es measured at the end o~ a two week aging period at room temperature are referred to as "two week wetting:times.N
: Tissue papers:softened according to the present invention should also desir~ably have relatively low lint properties. As 20: used herein, "lint" typically refers to dust-like paper particles that: are either unadhered, or loosely adhered9 to th~:surface of the paper. The generation of lint is usually an~lndication of a certain amount of debonding of the paper ibers, as well as othèr factors such as fiber length~ head~ox ~ layering,~etc. In order to reduce~lint formati~on~ tissue paper softened according to the present invention typically :requires the sddition o~ starch binders to the pape~making : ~ibers, as preY1ous~y described in part A of this application.
'As previd~sly noteJ, the ~present invention is '! i~
30: particularly useful in enhan~ing the softness o~ paktern : densified tissue papers, in p~rticular those havin~ pattern . designs. These pattern -densified papers are ~typically characterized by a relatively low density ~grams/cc~ and a relatiYely low basis weight (g/cm2). Pattern densi~ied tis-sue papers according to the present invention typically have a , ' .~ ~

~ 0 94/05856 2 1 4 ~ 6 0 ~ PCT/US93/07650 density of aibout 0.60 g/cc or less, and a basis weight between about 10 g/m2 and about 65 g/m2. Preferably, these pattern densified papers have a density of about 0.3 g/co or less (most preferab7y betwe~n about 0.04 g/cc and about 0.2 g/cc), and a basis weight of about 40 g/m2 or 12s,. See Column 13, lines 61-67, of U.S. Patent 5,059,282 (Ampulski et al), issued October 22, 1991, which describes how the density of paper is measured.

~: 10 SDeC;fjC_ lustra.tlon _ f the preDaratlon o; So;t~ned T~ssue PaQer Accordinq_to the Present Invention The following are specific illustrations of the softening of tissue paper in accordance with the present invention:

A. ~
An aqueous dispersion of softener is prepared from GLYCOMUL-S CG (a mixed sorbitan stearate ester surfactant made 20 ~ by~ Lonza, Inc.j, NEODOL 23-6.ST (a 20% solution of an ` Qthoxylat~d :C12-C13 linear alicshol dispersi:ng surfactant and wetting ag~nt:made ~y Shell Chemical Co~pany), DOW 65 Additive (a silicone polymer ~foam suppressant made~ by Dow Cornlng Corpo:ration), and distilled water. The composition of 25 ~ ~GLYCOMUL-S CG is shown in Table 3 below:

Table 3 .
C~mpQsi~n 30 ~ Monoester 22 . 6 Diester 39,3 ri~st:er 22.9 Tetraester 7 .1 Fztty ~cid (total~ 3.1 :: Polyol 4.3 Other 0 . 5 ~::

~.
; ~ ..

WO 9q/0585~ ~CI`/US93/û765li ~
21~260~

In preparing the aqueous dispersion o~ softener, the components are added to a stainless steel reactor equipped with te~perature controlled heating and mechanical stirring in the fsllowing weight percentages shown in Table 4 below:
; 5 Tab~e 4 ComDonent ~h~
NEO W L 23.-6.5T* 3.2 GLYCOMUL-S CG 11 . 9 DOW 65 Additive 0.8 Water 84.1 *surfactant active only The contents of the reactor are heated to 75-C with slow stirring and then allowed to cool to 49C or below with ~ lS continuous, moderate stirring. (Two visually distinct Phases : will form if the stirring is stopped while the dispersian is ``~ above 49'C.) The viscosity o~ the resulting aqueous dispersion of softener, when measured at 24C after vigorous s:tirring, should be between 200 and 700 centipoise. If the viscosity of the dispersion is higher, distilled water can be added in small increments un~il the viscosity is within the ; : appropriate range.

: B. ~ ~ ~
~: . : z5 : : A pilot scale Fourdrinier papermaking machine is used.
The ma~hine has a layered headbox with a top ohamber, a center chamber, and a bottom chamber. A first fibrous~slurry comprised pr~marily of short papermaking fibers (Eucalyptus Hardwood-Kraft),~is pumped;through the tsp and bottom headbox chambers. -Simultaneously~ a second fibrous slurry compris~d primarily of 19ng papermaking fib~rs:(Northern Softwood Kraft) is pumped through the center headbox chamber and delivered in a superposed relationship onto the Fourdrinier wire to form a 3-layer embryonic web. Th2 first slurry has a fiber consisteney of about O.llYo, while the second slur;ry has a ~ ' . ,, : `
~; ~ ' '' " ' '.

r ~,O 9~/0~856 2 1 ~ 2 6 0 ~ P ~ /US93t~765~

fiber consistency of about 0.15%. The emb~yonic web is dewatered through the Fourdrinier wire (5-shed, satin weave configuration having 84 machine-direction and 76 cross-machine-direction monofilaments per inch, respectively~, the .
dewatering bein~ assisted by deflector and vacuum boxes.
: The wet embryonic web is transferred from the Fourdrinier wire ~o a carrier fabric similar to that shown in Figure 10 o~
U.S. Patent 4,637,859, but with an aesthetically pleasing macropattern of rose petals superimposed on the regular micro-pattern of the carrier fabric. At the point of transfer to the carrier fabric, the web has a fiber consistency of about : 22%. The wet web is moved by the carrier fabric past a vacuum dewatering box, through blow-through predryers, and then t~ansferred onto a Yankee dryer. The web has a fiber consistency o~ about 27% after the vacuum dewatering box, and about 6~% after the predryers and prior to transfer onto the Yankee dryer.:
The web is adher~d to the surfaee of the Yankee dryer by a creping adhesive comprising a 0.25% a~ueous solution of 2 a ~olyvinyl alcohol that is applied to the sur~ace of the dryer.
The Yank~e dryer is operated at a temperature of about 177~C
and:a s~rface spced of about 244 meters per minute. The dried : web i:s then creped frQm the Yankee dryer with a doctor blade; : havlng a bevel angle of about 24 and positioned with respect : 25~ t~ the dryer to provide an impact angle of about 83~. Prior: to creping, the fiber consistency of the dried web is increas~d to an estimated 99X.
: The dried~ creped web (moisture eontent of 1%) is then . passed.betw~en a, pair o~ calender rolls biased,tog~th`er at roll weight and opera~ed at surface speeds of 201 meters per : minute. The lower, hard rubber ealender roll is sprayed with : the previously prepared aqueous dispersioR of softener by four : 0.71 mm diameter spray nozzles aligned :in a linear fashionwith a~spacing of about lQ cm between nozzles. The vol:umetric flow rat~ of the aqueous dispersion of scftener through each ~ ~ .
~: :
~, ~
, ~ ~

WO ~4/058~6 2 i 4 2 6 0 ~ PCl/US93/~76~'~j `

noz~le is about 0.37 1 iters per minute per oross-direction meter. The aqueous dispersion of softener is sprayed onto this lower calendar roll as a pattern of droplets that are then transfer~ed to the smoother, wire side of the dried, creped web by direct pressure transfer. The retention rate of the saft2ner on the dried web is~ in general, ab~ut 57%. The resulting softened tissue paper has a basis weight of about 30 grams/m~, a density of about O.lO grams/cc, and about 0.6%
softener (80~/~ GLYCOMUL-S CG) by weight of the dry paper.

ExamDle 2 Tissue papers were treated with varying levels of softener using the procedure described in Example l. The properties of these softened papers are shown in Table below:
Table S
Softener* ~ Softness Tota1 Sink Levell~ (PSU~ Tensiletq~in ~ ~
0 0 : 402 0 . 8 2~ 0.46 : 1.1 408 1.7 o ~3 ~ 1 .3 3~5 3.3 : 1 . 2 428 2 . 4 : :
*80~. GLYCOMUL-5 CG
ExamQ~e_3 2~ : A. ~ ~
~ : An aqueous solution of softener is prepared ~rom TWEEN 61 : ~ ~ (a mixed sorbitan stearate ester having an average degree:o~ -~: ethoxylation of 4 made by ICI Americas9 Inc.~, DOW 65 Addi~ve; and; ~istille~ water. Inipreparing the aqueous~
3~ solution of softener, the components are added to a stainless steel reactor equipped with tempera~ure~oontrolled~heating and mechanical stirring in the following weight percentages shown ; in Table 6 below:

, ~ ~
, , , ~,~ 94/058~6 2 1 ~ 2 6 Q ~ P~/vs93/07650 Table 6 Component _e~ o DOW 65 Additive . 0.4 Distilled Water 59.5 The contents of the reactor are heated to 7;'C with slow stirring and then allowed to cool to 60~C ~ S-C with maderate stirring. The viscosity of the resulting aqueous solution of softener, meas~red at 60~C, should be between 20 and 700 cengipoise. If ~hei viscosity of the solution is higher, distilled water can be added in small increments until the viscosi~y is wi~hin ~he appropriate range.

B. ~
A dried, creped paper web is prepared si~ilar to Example 1. As thîs dried, crep~d web passes between the pair~of calender rolls, the lower, hard rubber calender roll: is sprayed with the aqueous solution of snftener at a flow rate 20 : adjusted~to provide a pattern of TWEEN 61 softener droplets that are then transferred to the smoother, wire side o~ the dried ~reped web. ~bout 0.5% TWEEN ~1 by weight nf the dry :paper is retained. The resulting softened tissue paper has a velvety, flannel-like feel with enhanced tactile softness.
~; 25 : ~ ~
: ~

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i~ .
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7~

':

,:
i .

Claims (55)

THE EMBODIMENTS OF THE INVENTION IN WHICH AN EXCLUSIVE
PROPERTY OR PRIVILEGE IS CLAIMED ARE DEFINED AS FOLLOWS:
1. A process for softening a tissue paper web which comprises the step of treating at least one surface of a dry tissue paper web with a nonionic softener comprising a nonionic surfactant selected from the group consisting of sorbitan esters, ethoxylated sorbitan esters, propoxylated sorbitan esters, mixed ethoxylated/propoxylated sorbitan esters, and mixtures thereof, in a manner such that the softener is applied to said at least one surface in an amount of from about 0.1 to about 3% by weight of the dry tissue paper web.
2. The process of Claim 1 wherein the dry tissue paper web has a moisture content of about 10% or less and wherein the softener is applied nonuniformly to said at least one surface.
3. The process of Claim 2 wherein the softener is applied from an aqueous system thereof as a pattern of softener droplets to said at least one surface.
4. The process of Claim 3 wherein the softener is applied to said at least one surface in an amount of from about 0.2 to about 0.8% by weight of the dry tissue paper web.
5. The process of Claim 2 wherein the softener is applied to said at least one surface after creping and prior to calendering of the dry tissue paper web.
6. The process of Claim 2 wherein the dry tissue paper web is a pattern densified tissue paper having 2 moisture content of about 6% or less, a basis weight between about 10 g/m2 and about 65 g/m2 and a density of about 0.6 g/cc or less.
7. The process of Claim 6 wherein said at least one surface is the smoother side of the pattern densified tissue paper.
8. The process of Claim 1 wherein the predominant melting phase of the softener has an onset of melting of about 37°C or less.
9. The process of Claim 8 wherein the nonionic surfactant is a sorbitan ester of a C12-C22 fatty acid.
10, The process of Claim 9 wherein the sorbitan ester is selected from the group consisting of sorbitan laurates, sorbitan myristates, sorbitan palmitates, sorbitan stearates, sorbitan behenates and mixtures thereof.
11. The process of Claim 10 wherein the softener further comprises an ethoxylated alcohol having a straight alkyl chain of from about 8 to about 22 carbon atoms and from about 1 to about 25 moles of ethylene oxide.
12. The process of Claim 11 wherein the softener comprises a mixture of sorbitan stearate esters and an ethoxylated alcohol having a straight alkyl chain of from about 11 to about 15 carbon atoms and from about 3 to about 15 moles of ethylene oxide, in a weight ratio of sorbitan stearate esters to ethoxylated alcohol of from about 1:1 to about 10.
13. The process of Claim 12 wherein the weight ratio of sorbitan stearate esters to ethoxylated alcohol is from about 3:1 to about 6:1 and wherein the ethoxylated alcohol has a degree of ethoxylation of from about 3 to about 8.
14. The process of Claim a wherein the nonionic surfactant is an ethoxylated sorbitan ester of a C12-C22 fatty acid having an average degree of ethoxylation of from 1 to about 20.
15. The process of Claim 11 wherein the ethoxylated sorbitan ester is selected from the group consisting of ethoxylated sorbitan laurates, ethoxylated sorbitan myristates, ethoxylated sorbitan palmitates, ethoxylated sorbitan stearates, ethoxylated sorbitan behenates and mixtures thereof, the ethoxylated sorbitan ester having an average degree of ethoxylation of from about 2 to about 10.
16. The process of Claim 15 wherein the ethoxylated sorbitan ester is selected from the group consisting of ethoxylated sorbitan stearates having an average degree of ethoxylation of from about 2 to about 6.
17. A softened tissue paper having on at least one surface thereof a nonionic softener comprising a nonionic surfactant selected from the group: consisting of sorbitan esters, ethoxylated sorbitan esters, propoxylated sorbitan esters, mixed ethoxylated/propoxylated sorbitan esters and mixtures thereof, the softener being in an amount from about 0.1 to about 3% by weight of the dry tissue paper.
18. The paper of Claim 17 wherein said softener is applied nonuniformly to said at least one surface.
19. The paper of claim 18 wherein said softener is applied to said at least one surface as a pattern of softener droplets.
20. The paper of Claim 19 wherein said softener is in an amount from about 0.2 to about 0.8% weight of the dry paper.
21. The paper of Claim 18 which is a pattern densified tissue paper having a basis weight between about 10 g/m2 and about 65 g/m2 and a density of about 0.6g/cc or less.
22. The paper of Claim 21 wherein said at least one surface is the smoother side of the paper.
23. The paper of Claim 17 wherein the predominant melting phase of said softener has an onset of melting of about 37°C or less.
24. The paper of Claim 23 wherein said nonionic surfactant is a sorbitan ester of a C12-C22 fatty acid.
25. The paper of Claim 24 wherein said sorbitan ester is selected from the group consisting of sorbitan laurates, sorbitan myristates, sorbitan palmitates, sorbitan stearates, sorbitan behenates and mixtures thereof.
26. The paper of Claim 25 wherein said softener further comprises an ethoxylated alcohol having a straight alkyl chain of from about 8 to about 22 carbon atoms and from about 1 to about 25 moles of ethaylene oxide.
27. The paper of Claim 26 wherein said softener comprises a mixture of sorbitan stearate esters and an ethoxylated alcohol having a straight alkyl chain of from about 11 to about 15 carbon atoms and from about 3 to about 15 moles of ethylene oxide, in a weight ratio of sorbitan stearate esters to ethoxylated alcohol of from about 1:1 to about 10:1.
28. The paper of Claim 27 wherein the weight ratio of sorbitan stearate esters to ethoxylated alcohol is from about 3:1 to about 6:1 and wherein the ethoxylated alcohol has a degree of ethoxytation of from about 3 to about 8.
29. The process of Claim 23 wherein said nonionic surfactant is an ethoxylated sorbitan ester of a C12-C22 fatty acid having an average degree of ethoxylation of from 1 to about 20.
30. The paper of Claim 29 wherein said ethoxylated sorbitan ester selected from. the group consisting of ethoxylated sorbitan laurates, ethoxylated sorbitan myristates, ethoxylated sorbitan palmitates, ethoxylated sorbitan stearates, ethoxylated sorbitan behenates and mixtures thereof, the ethoxylated sorbitan ester having an average degree of ethoxylation of from about 2 to about 10.
31. The paper of Claim 30 wherein said ethoxylated sorbitan ester is selected from the group consisting of ethoxylated sorbitan stearates having an average degree of ethoxylation of from about 2 to about 6.
32. A process for softening a pattern densified tissue paper web, which comprises the steps of:
(a) providing a patterned densified tissue paper web having:
(1) a moisture content of about 6% or less;
(2) a basis weight between about 10 g/m2 and about 65 g/m2; and (3) a density of about 0.6 g/cc or less; and (4) from about 0.01 to about 2% starch binder by weight of the paper web;
(b) providing an aqueous system comprising an effective amount of a nonionic softener comprising a nonionic surfactant selected from the group consisting of sorbitan esters of C12-C22 saturated fatty acids, ethoxylated sorbitan esters of said fatty acids having an average degree of ethoxylation of from about 2 to about 10, and mixtures thereof, the predominant melting phase of the softener having an onset of melting at or below about 35°C; and (c) applying the softener from the aqueous system thereof to at least one surface of the paper web in an amount of from about 0.1 to about 3% by weight of the paper web.
33. The process of Claim 32 wherein the softener is applied to said at least one surface after creping and prior to calendering of the paper web.
34. The process of Claim 33 wherein the aqueous system is sprayed as a pattern of softener droplets onto the surface of a rotating calender roll that then transfers the softener droplets to said at least one surface.
35. The process of Claim 34 wherein the softener is applied to said at least one surface in an amount of from about 0.2 to about 0.8% by weight of the paper web.
36. The process of Claim 35 wherein the paper web of step (a) has a moisture content of about 3% or less, a basis weight of about 40 g/m2 or less and a density of about 0.3 g/cc or less.
37. The process of Claim 36 wherein said at least one surface is the smoother side of the paper web.
38. The process of Claim 32 wherein the nonionic surfactant is selected from the group consisting of sorbitan laurates, sorbitan myristates, sorbitan palmitates, sorbitan stearates, sorbitan behenates and mixtures thereof.
39. The process of Claim 38 wherein the aqueous system comprises from about 9 to about 30% by weight softener and has a viscosity of from about 200 to about 700 centipoise at a temperature from about 50° to about 81°F (from about 10° toabout 27°C).
40. The process of Claim 39 wherein the softener further comprises an ethoxylated alcohol having a straight alkyl chain of from about 8 to about 22 carbon atoms and from about 1 to about 25 moles of ethylene oxide.
41. The process of Claim 40 wherein the softener comprises a mixture of sorbitan stearate esters and an ethoxylated alcohol having a straight alkyl chain of from about 11 to about 15 carbon atoms and from about 3 to about 15 moles of ethylene oxide, in a weight ratio of sorbitan stearate esters to ethoxylated alcohol of from about 1:1 to about 10:1.
42. The process of Claim 41 wherein the weight ratio of sorbitan stearate esters to ethoxylated alcohol is from about 3:1 to about 6:1 and wherein the ethoxylated alcohol has a degree of ethoxylation of from about 3 to about 8.
43. The process of Claim 32 wherein the nonionic surfactant is an ethoxylated sorbitan ester selected from the group consisting of ethoxylated sorbitan laurates, ethoxylated sorbitan myristates, ethoxylated sorbitan palmitates, ethoxylated sorbitan stearates, ethoxylated sorbitan behenates and mixtures thereof.
44. The process of Claim 43 wherein the aqueous system comprises from about 10 to about 50% by weight softener and has a viscosity of from about 20 to about 700 centipoise at a temperature from about 130° to about 150°F (from about 54.4°
to about 65.6°C).
45. The process of Claim 44 wherein the ethoxylated sorbitan ester is selected from the group consisting of ethoxylated sorbitan stearates having an average degree of ethoxylation of from about 2 to about 6.
46. A softened patterned densified tissue paper, which has:
(1) a basis weight between about 10 g/m2 and about 65 g/m2;
(2) a density of about 0.6 g/cc or less;
(3) a total dry tensile strength of at least about 360 g/in; and (4) from about 0.1 to about 3% by weight nonionic softener comprising a nonionic surfactant selected from the group consisting of sorbitan esters of C12-C22 saturated fatty acids, ethoxylated sorbitan esters of said fatty acids having an average degree of ethoxylation of from about 2 to about 10, wherein said softener is applied to at least one surface of the tissue paper as a pattern of softener droplets, and wherein the predominant melting phase of said softener has an onset of melting at or below about 35°C.
47. The paper of Claim 45 which comprises from about 0.2 to about 0.8% of said softener by weight.
48. The paper of Claim 47 which has a basis weight of about 40 g/m2 or less and a density of about 0.3 g/cc or less.
49. The paper of Claim 48 wherein said at least one surface is the smoother side of the paper.
50. The paper of Claim 46 wherein said nonionic surfactant is selected from the group consisting of sorbitan 1aurates, sorbitan myristates, sorbitan palmitates, sorbitan stearates, sorbitan behenates and mixtures thereof.
51. The paper of Claim 50 wherein said softener further comprises an ethoxylated alcohol having a straight alkyl chain of from about 8 to about 22 carbon atoms and from about l to about 25 moles of ethylene oxide.
52. The paper of Claim 51 wherein said softener comprises a mixture of sorbitan stearate esters and an ethoxylated alcohol having a straight alkyl chain of from about 11 to about 15 carbon atoms and from about 3 to about 15 moles of ethylene oxide, in a weight ratio of sorbitan stearate esters to ethoxylated alcohol of from aboult 1:1 to about 10:1.
53. The paper of Claim 52 wherein the weight ratio of orbitan stearate esters to ethoxylated alcohol is from about 3:1 to about 6:1 and wherein the ethoxylated alcohol has a degree of ethoxylation of from about 3 to about 8.
54. The paper of Claim 53 wherein said nonionic surfactant is an ethoxylated sorbitan ester selected from the group consisting of ethoxylated sorbitan laurates, ethoxylated borbitan myristates, ethoxylated sorbitan palmitales, ethoxylated sorbitan stearates, ethoxylated sorbitan behenates and mixtures thereof.
55. The paper of Claim 54 wherein said ethoxylated sorbitan ester is selected from the group consisting of ethoxylated sorbitan stearates having an average degree of ethoxylation of from about 2 to about 6.
CA 2142605 1992-08-27 1993-08-12 Tissue paper treated with nonionic softeners that are biodegradable Abandoned CA2142605A1 (en)

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EP0656970A1 (en) 1995-06-14
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GR3023346T3 (en) 1997-08-29
JPH08500858A (en) 1996-01-30
FI950862A0 (en) 1995-02-24
ATE152793T1 (en) 1997-05-15
NZ255759A (en) 1997-02-24
AU5011093A (en) 1994-03-29
AU679189B2 (en) 1997-06-26
CA2254257A1 (en) 1994-03-17
ES2104168T3 (en) 1997-10-01
KR950703101A (en) 1995-08-23
EP0656970B1 (en) 1997-05-07
BR9306990A (en) 2002-12-24
DK0656970T3 (en) 1997-11-03
CA2254257C (en) 2005-01-25
US5494731A (en) 1996-02-27
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