CA1071360A - Fabric treating articles with improved conditioning properties - Google Patents

Abstract

ABSTRACT OF THE DISCLOSURE
Softening articles with improved fabric conditioning properties comprising fabric shortener, certain substantially water-insoluble particulate materials and a dispensing means especially adapted for use in an automatic clothes dryer are described. The articles simultaneously provide softness, ease of ironing, anti-wrinkling and improved appearance and aesthetic benefits to fabrics treated therewith.

Description

B_C~GROU~ 0~ T~ INVE~ N
~ his in~ention relztes to faDric treating articles which comprise a su~stantially water~insoluble particulate material releasably com~ined with a dispe~sing mean~.
T~e articles also preferably contain one or more ~abric lS softeners. These articles are especi211y adap~ed or use in an automatic clothes dryer to im~art anti-wrinkling, e2se of ironin~, sof~ne~s, folding ease, enhar.ced drapabil-ity, and appearance bene~its to fabrl'cs concurlently with a fabric dr~ing operation.

' ~

~i!L6~7~L3~0 Treating fabrics in an automatic clothes dryer has recently been shown to be an effective means for conditioning and imparting desirable tactile properties ~hereto. In particular, it is becoming common to soften fabrics in an automatic clothes dryer rather than during the rinse cycle of a laundering operation.
~reating fabrics in the dryer, rather than in the wash, enables the formulator of fabric conditioners to develop and use materials~which may not be compatible with detergen s. ~oreover~ the user of dryer-added conditioners is not compelled to make the special effort to add the product during the rinse cycle in the manner required with many rinse-added products.
While signi'icant advances in the art of softening fabrics in the dryer have been made, it has now been discovered that softness is but one of , several important benefits which can be imparted to ~brics in this manner. ~s noted hereinabove, the present invention provides a means whereby many desirable properties can be impar~ed to fabrics con-' currently with a standard drying operation in any automatic dryer.
It is an object of the present invention to cond.ition fabrics in an automatic clothe~ dryer.
It is another object herein to provide articles which can be added to a clothes dryer to condition ~abrics concurrently with a drying operation.

.
; - 2 -.

107~3GO .

These and other objects are obtained herein as will be seen from the following disclosure.

DESCRIPTION OF T~E PRIOR ART
U~SO Patent 3,822,145, Liebowitz, et alO, FABRIC
S~FTENING, issued July 2, 1974, relates to the use of : spherical materials as fabric so~tening agents~ U.S.
Paten~ 3,743,534, Zamora, et al., PROCESS F3R S~FTE~I~G
' F~BRICS IN A DR~ER, issued July 3, 1973; 3,69g,095, Grand, et al., FIBER CON3~TIONING ARTICLE, issued October 17, 1972; 3,686,025, Morton, TEXTILE SOFTENING
PGENTS IMPREGN~TED INTO ABSORBENT MATERI~LS, issued . August 22, 1972; 3,676,199, Hewitt, et al., F~BRIC
; CONDITIONING ARTICLE A~D USE THEREOF, issued July 11, ~ 1972; 3,633,538,: Hoefli~, SPHERIC~L D~VICE FOR CONDI-- 15 TIONING FABRICS IN DRYER, issued January 11, 1972;
3.634,947, Furgal, COATING APP~RATUS, issued January 18, 1972; 3,632,~96, Zamora, DRYER-ADDED FPBRIC-SOFTENING
COMPOSITIONS, issued January 4, 1972; and 3,442,692, Gaiser, METHOD OF CONDITIONING FABRICS, issued May 6, 1969, each relate to articles and methods for conditioning f~brics in automatic dryers. U.S. Patents 3,033,699, . Aarons, et al., ANTISTATIC COMPOSITION, issued May 8, 1962; 3,063,128, Etchison, PROCESS FOR CONTROLLING
STATIC PROPERTIES OF SYNTHETIC TEXTILE FIBERS, issued November 13, 1962;~3,766,062, Wixoni 1,2-ALK~NEDIOL
CONTAINING FABRIC SOFTENING COMPOSITIONS, issued O~tober 1~, 1973; 3,785,973, Bernholz, et al., TF~TILE

.
. .

~1~7~L3~i~

FI~ISH, issued January 15, 1974; and 3,793,196, Okazaki, et al., SOFTENING AC,ENT, issued Febnuaxy 19, 1974, relate to fabric softening agents of various types. U. S. Patent 3,594,212, Ditsch, TREATMENT OF FIBROUS MATERIALS WITH
MONTMORILLONITE CLAYS AND POLYAMINES AND POLYQUATERNARY
AM~IONIUM COMPOUNDS relates to the treatment of ibrous materials with clays and ~mine or ammonium compounds. Fatty alcohols are well-known "scrooping" agents for use on textiles.
Canadian Patent 1,029,15'1 of Edwards and Diehl entitled FABRIC SOFTENING COMPOSITIONS WITH IMPROVED CONDITIONING
PROPERTIES, granted April 11, 1978, discloses mixtures of fabric softeners and particwlate conditioners. Canadlan Patent 1,035,506 of Murphy et al, granted August 1, 1978;
U. S. Patent 4,127,694 of Murphy et al, granted November 28, 1978; Murp;y et al, Belgian Patent No. 825,361, granted August 11, 1975; U. S. Patent 4,085,052 of Murphy et al., granted April 18, 1978; and Zaki, U. S. Patent 4,022,938, granted May 10, 1977, each relate to dryer-added fabric 20 softeners and articles of various types.
The concurrently-filed Canadian application of Ned C.
Webb, et al. entitled FABRIC TREATING COMPOSITIONS AND
ARTICLES, Serial No. 237,530, filed October 14, 1975, relates to dryer-added particulate conditioners which provide a ` ~ desirable substantive odor to fabrics.

~' ~' ~7~3~0 SUMM~RY OF THE INVENTION
The instant invention is based on the disco~er~
that certain water-insoluble particulate materials can be appliea to clothing and fabrics in an automatir clothes dryer to provide anti-wrinkling and ease of ironing benefits thereto. The particulate materials also make t~e fabrics easier to fold and enhance their drapability, thereby resulting in an lmproved appear-~ ance.

The particulate materials employed in the practice of this invention are used in combination with a dis-pensins means to provide an article containing a pre-measured amount of said particulate ma~erial. The dispensing means is designed to dispense the particulate material evenly and ef~iciently onto fa~ric surfaces with the tumbling action of an automatic clothes dryer.
Preferred article~ here.in comprise the particula.e material, the-dispensing means, and one ~r more fabric softening compounds. Such articles can be formulated to distribute both the fabric softener and the par-ticulate material onto abric surfaces evenly and efficiently during a drying operation in-an automatic clothe~ dryer.

,~ " .
,~ _5_ ., .

~3 ,' ,.. ' , .. . . . . . . . . .

~7~36S) The present invention, in one aspect, resides in a fabric treating article especially adapted for use in an automatic dryer, comprising: (a~ a fabric conditioning amount of a water-insoluble particulate material characterized by: (i) an average particle size of from about 1.0 ~m to about 50 ~m;
(ii) a shape having an anisotropy of from about 5:1 to about 1:1; (iii) a hardness of less than about 5.5 on the Mohs scale;
(iv) a melting temperature above about 150C; and (v) sub- :
stantial freedom from exchangeable calcium and magnesium ions, said particulate material being in releasable combination :-with; (b) a water-insoluble dispensing means.
In another aspect this invention resides in an article adapted for concurrently softening and conditioning fabrics in an automatic clothes dryer, comprising: (a) a softening amount of a fabric softener characterized by a melting point : above about 38"C; (b) a fabric conditioning amount of a substantially water-insoluble particulate materi.al charac-terized by: (i) an average particle size of from about l.0 ~m to about 50 ~m; (ii) a shape having an anisctropy of from about 5:1 to about l:l; (iii) a hardness of less than about 5.5 on the Mohs scale; (iv) a melting temperature above about 150C; and (v) substantial freedom from exchangeable calcium and magnesium ions; said softener and said particulate material being in releasable combination with; (c) a water--insoluble dispensing means. ..
In its process aspect, this invention encompasses aprocess for conditioning fabrics comprising combining ~-:
'. '~'~
~5a- . :
,~ ' damp fabrics with an article of the type hereinabove disclosed in an automatic clothes dryer and operating said automatic dryer, with tumbling, in standard fashion.

DETAILh'D DESCRIPT}:ON OF T~ VENTION
The articles herein.comprise multiple components, each o~ which are discussed~ in turn, below.

Particulate Component ~. The substantially water-insoluble particulate material used in the articles of the instant invention is ~haracterized by: ~1) an average particle size from about 1.0 micrometers (~m) to about 50 ~m, preferably - rom about 5 ~m to about 30 ~m: (2) a shape having an anisotropy of from a~out S:l to about 1:1; ~3) a lS hardness of less than about 5.5 on the Mohs scale;
t4) a melting (~oftening) temperature above about 150C; and (Sj substantial freedom from exchangeable calcium and magnesium ions.
~ The average particle size limitation o~ the 20 substantially water-insoluble particulate material herein relates to the diameters of commercially avail-. able textile ~ibers, which, for the most part, fall within the range of about 10 ~m to about 30 ~m. For the reasons described more fully hereinafter, partic-ulate materials having an average diameter greater than about 50 micrometers do not provide the fabric :
. benefi~s enumerated hereinbefore. Likewise, particulate ~:.
; materials whose particle:size diameter is less than about 1 ~m do not provide the desired fabric conditioning benefits.
' ~ : - 6 - ~ :

~7~3~0 The particulate material herein is further characterized by an anisotropy (axial ratio) of about 5:1 to 1:1. The determination of particle size can be based on the measurement of the projection area o the water-insoluble particle, or on the linear measures of this projection areaO That is to say, for the loose particle, resting on its surface of maximum ~tability, the long and intermediate axes are normally horizontal and the short axis is ~erkical. In that 10 ~ context, the term "long axis" represents the maximum overall length of the pa~ticle: "intermediate axis"
~tands for the maximum dimension of a particle in a direction perpendicular to the long axis: and "short axis" represents the maximum dimension in a direction perpendicular to the plane containing the long and intermediate axes. The term "anisotropy" means the ratio of long axis to short axis for a specific ; particulate material. (See ~ADV~NCES IN OPTIC~L AND
ELECTRON MICROSCOPY~ Vol. 3, R. Barer and V. E. Cosslett, ACADEMIC PRESS 1969, London and New York~) Preferred ~or use in the compositions o~ this invention are particulate materials having an anisotropy within the range from about 3:1 to about 1.1:1.
The particulate material used herein is further characterized by a hardness of less than about 5.5 on the Mohs scale. The hardness is a measure of resistance to cru~hing, and is a good indication of the abrasive character of a solid material. Examples of materials ;~
- arranged in increased order of hardness according to .' _ 7 ~: 1 6~

the Mohs scale are as follows: h.(hardness)-l: talc, dried filter-press cakes, soap-stone, waxes, aggregated salt crystals h-2: gypsum, rock salt, crystalline salt in general; h~3: barytes, chalk, brimstone, calcite:
h-~: fluorite, soft phosphate, magnesite, Iimestone;
h-5: apatite, hard phosphate, hard limestone, chromite, bauxite; h 6: feldspar, ilmenite~. hornblendes; h-7:
quartz, granite h-8: topaz; h-9: corundum, emery;
`~ and h-10: diamond.
Suitable particulate materials have a hardness of less than about 5.5 on the Mohs scaleO Although some conditioning bene~its can be obtained with particulate materials having a Mohs hardness of up to about 7, overall benefits secured with such materials are not optimal, and such materials are not used in the instant articles. One reason for avoiding such high hardness materials is that they can cause fiber and yarn damaye which adversely affect the fabric, especially after multi-cycle treatmentsO
The particulate materials u ed herein have a .:
melting (softening) point above about 150C. Partic-. ulate materials having a melting point below that temperature do not provide the fabric benefits because . ..
of their tendency to melt, or soften, and spread throughout the fabric. This is undesirable in the context of this invention and the particulate materials must maintain their shape and integrity under ironing ..
conditions, i~e., at temperatures of ca. 150C.

~7~1L36(;1 The particulate material must be substantially water-insoluble, inasmuch as its function depends on its integrity, shape, firmness, etc~, as described in detail hereinaboveO It should be recogniz2d, however, that minor portions of the particulate ingredient, preferably not more than 20% by weight, can be water-soluble without markedly decrea~ing performance.
~ The water-insoluble particulate material is substantially free of exchangeable calcium and magnesium ions. The presence of exchangeable alkaline earth metal ions such as calcium and magnesium in the particulate materials appears to increase their hydrophilic properties. This results in enhanced swelling and constitutes an ohstacle to the uniform and ~table enmeshing of the particulate material within the fiber structure.
While not intending to be bound by theory, it appears that the particulate material herein interacts with fabrics at the fiber level to impart the described benefits to the textile fabric as a whole.
In this regard, it is known that yarns and fabrics consist of assemblies of fine flexible fibers arranged in more-or-less orderly arrays. Individuai fibers within such assemblies are usually in a bent or twisted configuration and are in various states of contact with neighboring fibers. When the assembly is deformed, , ' :
,; .

~ . ........... . .
. , . , : .

~07~36~

the fibers move relative to each other and ~his relative motion accounts for much of the characteristic flexi~ility of textile materials. To what extent a gi~en textile material will recover when a deforming force is removed determînes how much l'wrinkling"
occurs. Recovery is largely determined by the nature of the interaction of the individual fi~ers making up the textile material. Textile fibers are visco-~ elastic and exhibit delayed recovery from strain.
Moreover, the large number of interfiber contact points pro~ide significant frictional restraints which further hinder the recovery process. By overcoming such frictional restra~nts the recovery process is hastened.
This view of the microscopic nature of fi~ers }5 and textiles and the physical forces involved in deformation and recovery processes helps explain the efficacy of the particulate materials herein in impartLng anti-wrinkling, ease of ironing, etc.
benefits thereto. For purpose of conceptualization, 20 ~ the mode of action of the particulate materials herein is conveniently referred to as a "ball bearin~" effect.
This conceptualization is useful` in interpreting the interaction of the particulate material and the , textile matrix under deformation.
By means of microscopic analysis and staining techniques, it has been determined that textile fabrics "
treated with discrete parti~ulate materials have such .

~: - .. : ., ~7~36~

materials intimately and substantively dispersed in the interstices of the fiber matrix. It is believed that once interfiberly positloned, the particles act in the manner of ball bearings to reduce interfi~ar ~orces during deformation of the textile fabric as a whole. The overall effect is the enhancement of visco~lastic recovery (anti-wri~kling effect) and diminution of the forces operable at interfiber contact points (ease of ironing effect). The diameter limitation of the par~iculate materials used herein is appreciated since most commercially available textile fibers have diameters which fall within the range of about 10 ~m to about 30 ~m, and the particulate material of the invention must be comparable in diameter to the fibers.
Moreover, the appearance benefits imparted to textiles treated in the present manner are similarly related to the presence of the particulate material àt points within interstices of individua~ fiber yarns.
Microscopic examination of textile yarns in cross - section reveals that textiles treated with the instant particulate materials exhibit greater yarn diameters than untreated yarns. Apparently, the particulate materials positioned in the interfiber spaces effectively open up the yarn (apparent increase in bulX) resulting in a softer, fluffier fabric. The anti-static benefit imparted by the particles is related to a decrease in resistivity of the treated . .

- ., . . - . . ' -, : -- . . ~ , . - : , .:

~7~L36~

fabric matrix, perhaps occasioned by an increase in ~he equilibrium moisture content of the fabric.
Non-limiting examples of use~ul particulate materials herein include surface-modified, water-insolubl~ starch granules; beads o synthetic polymerssuch as poly~methylmethacrylate) m.p. 160C~200C:
poly(tetrafluoroethylene) m.p, 327C-330C: polystyrene m.p. 240C-250C, po}y(styrenedivinylbenzene) m.p~ ~150C;
~. poly(melamine urea formaldehyde) mOp. >150C; and poly(urea formaldehyde) m.p. >150C: glass, coated glass, and hollow glass beads and various ceramic beads.
Thus, both inorganic and organic particulates char-: acteri~ed by the above-described parameters are all useful herein.
Specific examples of particulate materials ~ ~ :
useful herein include the following. : .
(a~ Surface-treated starches (preferred herein~
:~ such as '!DRY-FLO'~ starch manufactured by ~hTION~h STARCH
PRODUCTS, New York. DRY-FLO starches are surface-; 20 modified starches bearing hydrophobic moieties which have been xeacted with the starch molecule through the foxmation of ester and ether linkages. As a result of this chemical modification, these derivatized starches are water-repellent and substantially water-insolu~le. D~Y-FLO starches have an average particle size diameter o about 9-11 micrometers.

*Trademark .
' - .

B

.

: L~7~3~0 [b) Glass microballoons, avg. size range 5-15 ~m, manufactured by EMERSO~ ~ CUMING, Canton, Mass.
(c~ Glass beads, avg. size ranse 5-44 ~m, manufactured by C~TAPHOTE CORP., Jackson, Miss., and marketed as PF 12-R, PF-ll, PF-12 and PF-12S.
Another substantially water-insoluble particulate material useful hexein is a s~arch granule having, in addition to the above-described characteristics, a swelling power of less than a~out 15 at a temperature of 65C. Modified starches, i.e., the more water~
soluble starches obtained by various common gelatinizing, derivatizing, or degrading techniques do not have a ~ :
firm shape and are not used in the present in~ention.
Such soluble or "gelatinizabl~" starch g anules having.a swelling power of more than about 15 at 65C .
tend to lose their shape ana run into the inter-fiber spaces, with the result that fabrics treated therewith become undesirably stiff.
The selection of starches based on their .
swelling power can ~e done using the standard method .
set forth in Cereal Chem., 36, pp. 534-544 tl959) Harry W~ Leach, et al.
Although the fir.al choice o starch which will ~::
meet the requirements of this invention depends on its origin and the processing to which it has been subjected, suitable starches are obtained from corn, wheat and rice. Most potato aAd tapioca starcles ` .

~3 13~

, -: , - : . -: .... . .. - ~ . . ... : . . :

~)7~3~

have a swelling power exceeding 15 at a temperature of 65C and are not suitable for use herein. More complete information concerning water--insoluble, low-; swelling starches, processes for their preparation and kheir isolation from a variety of raw materials appearsin THE STARCH~ USTRY, Knight, J~ W., Pergamon Press, London (1969), e~s ir ~ Mo.:n The particulate materials and softeners of the foregoing type can be employed by simply placing a measured amount in the dryer, e.g., as an aqueous : dispersion. However, in a preferred embodiment the particulate materials (preferably with the softener) are provi~ed as an article of manufacture in combination ; 15 with a dispensing means which effectively releases them in an automa.ic clothes dryer. SUCh dispensing means can be designed for single usage or for multiple uses.
One such article comprises a pouch releasably enclosing enough of the particulate material (with or without softener) to condition fabrics during several ' cycles of clothes. This ~ulti-use article can be made by rilling a hollow, open pore polyurethane sponge pouch with about 10 grams of the particulate material.
In use, the tu~bling action of the dryer causes the parti~les to pass through the pores o~ the sponge and onto the ~a~rics . Such a filled sponge can be used to treat several loads of fabrics in conventional dryers, and has the advantage that it can remain in the dryer after use and is not likely to be misplaced or lost.

.
- 14 - ~
, ., ~., lL~7136~

Another article comprises a cloth or paper bag releasably enclosing the particulate material and sealed with a wax which softens at dryer operating tempera~ures. The action o~ the dryer opens ~he bag and releases the particles to perform their conditioning function.
A highly preferred article herein comprises the particulate material releasably affixed to a sheet of -~ paper or woven or non-woven cloth substrate such that 10 " the action of the automatic dryer removes the material and deposits it on the fabrics. (As more ~ully described hereinafter, the particulate material can be releasably affLxed to the sheet substrates in various ways, but is preferably and conveniently affixed by means of lS a melt of a fabric softener component.) The sheet conformation has several advantages.
For example, effective amounts of the particulate material (and softener) for use in conventional dryers can be easily sorbed onto and into the sheet substrate by sim~le dipping or padding processes. Thus, the user need not measure the amount of material necessary to condition fabrics. Additionally, the flat configura-tion o the sheet provides a large surface area which results in efficient release of the materials onto fabrics by the tumbling action of the dryer.
The water-insoluble paper, or woven or non~woven substrates used in the articles her in can have a dense, or more pFeferably, open or porgus structure. Examples ~: .

~ .
. ' .
r 15 -~37~L3~ .

of suitable materials which can be us d as substxatesherein include paper, woven cloth, and non-woven c~oth~
The term "cloth" herein means a woven or non-woven substrate for the articles o~ manufacture, as distin-5 guished from the term "fabric" which encompasses the ~lothing fabrics being dried in an automatic dryer.
Highly preferred paperr woven or non-woven "absorbent'l substrates useful herein are fully disclosed ~:
in UOSo Patent 3,686,025, Morton, TEXTI~E SOFTENING
10 AGENTS IMP~EGN~TED I~IT0 ABSORBENT MATERIALS, issued ~ugust ~2, 1972, These substrates are particularly useful with articles comprising both the particul~te material and a fabric softener. It is known that most substances are able to absorb a liquid substance to some degree; however, the term "absorbent", as used herein, is intended to mean a substance with an absorbent capacity (i.e., a :
parameter representing a substrate 's ability to take up and retain a li~uid) from 5.5 to 12, preferably 7 to 10, times its weight of water.
Determination of.a~sorbent capacity values is made by using the capacity testing procedures described ::
in U.S. Federal Specifications W -T-595b, modified as follows:
25. (1) tap water is used instead of distilled water~

(2) the specimen is immersed for 30 seconds instead of

3 minutes;
~3) the draining time is 15 seconds instead of 1 mi~ute;
and .,~ :
~ . - 16 -~6~7~60

(4) the specimen is immediately weighed on a torsion balance having a pan with turned-up edges.
Absorbent capacity values are then calculated in accordance with the formula given in said specification.
~ased on this test, one-ply~ dense bleached paper (eOg., kraft or bond having a basis weight of about 32 pounds per 3,000 square feet) has an absorbent capacity of 3.5 to 4; commexcially available household one-ply toweling paper has a value of 5 to 6; and commercially available two-ply household toweling paper has a value of 7 to about 9.5.
Using a substrate with an absorbent capacity of less than 5.5 tends to cause too rapid release of the softener ~rom the substrate resulting in several dis-advantages, one of which is uneven softening of the fabrics. Using a substrate wlth an absorbent capacity over 12 is undesirable, inasmuch as too little of the softening agent is released to soften the fabrics in optimal fashion during a normal drying cycle.
The preferred substrates used in this invention can also be defined in terms of "free space." Fxee space, also called ~void volume", as used herein is intended to mean that space within a structure that is unoccupied. For example, certain multi-ply paper structures comprise plies embossed with protuberances, the ends of which are mated and joined: this paper structure has a void volume or frea space between the fibers o~ the paper sheet, itself. A non-woven cloth , :
.. . :
- 17 - ~

3~iO

also has free space between each of its fibers. The free space of non~woven cloth or paper, having designated physical dimensions, can be varied by modifying ~he densi~y of the ~ibers o~ the paper or S non-woven cloth. substrates ~ith a hi~h amount of free space generally have low fiber density; high density substrates generally have a low amount of free space.
The preferred substrates of the invention herein ha~e from about 40% to about 90%, pre~erably about S5%, free space basea on the overall volume of the sub-strate's structure. This free space is directly related to the substrate's having an absorbency value of 5.5 to 12.
The use of dense, one-ply or ordinary kraft or bond paper for the softening agent substrate can result in in-creased staining of certain types of treated fabrics. Thisstaining is caused by too rapid or uneven release of the fatty (greasy) softener due to the low absorbent capacity of the paper substrate.
So~tening agents on dense papex can be rapidly and unevenly released in excessive quantities when subjected to customary dryer temperatures, with the result that treated fabrics can become stained at points of contact with the softener-coated paper.
Fabric staining can be eliminated altosether by em-ploying a substrate having an absorbent capacity inthe range o~ 5.5 to 12, surh that less of the so~tening agent is released at any given point of time when contacted with the fabric bein~ treatea.

-~

~7~36~

As noted above, suitable materials which can be used as a substrate ;n the invention herein include, among others, sponges, paper, and woven and non-woven ~loth, all having the absorbency parameters defined

5 above. The preferred substrates of the softening compositions herein are cellulosi~, parti~ularly multi-ply paper and non-woven cloth.
More specifically, a preferred paper substrate comprises a compressible, laminated, calendered, " multi-ply, absorbent paper structure. Preferably, the paper structure has 2 or 3 plies and a total bas is weight of from 14 to 90 pounds per 3,000 square feet and absorbent capacity values within the range of 7 to 10. Each ply of the preferred paper structure has a lS basis weight of about 7 to 30 pounds per 3,000 square feet, and the paper structure can consist of plies having the same or different basis weights. Each ply is preferably made from a creped, or otherwise extensible, paper with a creped pexcentage of about 15% to 40% and a machine direction (MD) tensile and cross-machine (CD) tensile of from about 100 to 1,500 ; grams per square inch of paper width. The two outer plies of a 3-ply paper structure or each ply of a 2-ply paper structure are embossed with identical repeating patterns consisting of about 16 to 200 discrete protuberances per square inc~, raised to a height of from about 0.010 inch to 0040 inch above the surface of the unembossed paper sheet. From about ' ' . :
' 1 ' .

,: , . -' - 19 -- ' 11)7~L3~1D

1~ to 60% of the paper sheet surface i~ raised.
The dis~al ends (i.e., the ends away from the unembossed paper sheet sur~ace) of the protuberances on each ply are ma~ed and adhesively joined toge~her, thereby providing a preferred paper structure exhibiting a ~ompressive modulus of from about 200 to 800 inch- .
grams per cubic inch and "Handle-O-Meter*" (HOM) MD and CD ~alues of from about 10 to 130.
~ Suitable adhesives for multi-ply paper are known : 10 in the ar~ and include water, starches, wet-strength resins, and polyvinyl acetates. A particularly suitable adhesive is prepa.ed by heating from about 2 to about 4 parts by weight of su~ tantially completely hydrolyzed polyvinyl alcohol resin in from about 96 to aboui 98 parts by weight of water. Preferably, about 0.03 pound : -: of adhesive solids are used-to join 3,000 square feet of the embossed plies, with the adhesive being applied to the distal surfa~es of the protubexances of one or all plies.
The compressive modulus values which define the compressive deformation.characteristics of a paper structure compressively loaded on its opposing sux-faces, the HOM values which ~efer to the stiffness or handle of a paper structure, the MD and CD HOM values :
which refer to ~OM values obtained from paper structure samples tested;in a m~chine and cross-machine direction, : : .
the methods of determining these values, the equipment used, and a more detailed disclosure of~the paper *Trademark -structure preferred herein, as well as methods of its preparation, can be found in U.S. Patent 3,414,459, Wells, COMPRESSIBLE LAMI~TED PAPER STRUCTURE, issued December 3, 1968, The preferred non-woven cloth substrates used in the invention herein can generally be defined as adhesively bonded fibrous or filamentous products ~ having a web or caxded fiber structure (where the ~iber strength is suitable to allow c~rding~, or comprising fibrous mats in which the fibers or filaments are distributed haphazar~ly or in random array ~i.e., an array of fibers in a carded web wherein partial orientation of the fibers is fre-quently present, as well as a completely haphazarddistributional orientation~, sr substantially aligned.
The fibers or filaments can be natural (e.g., wool, silk, jute, hemp, cotton, linen, sisal, or ramie) or synthetic (e.g., rayon, ceilulose ester, polyvinyl derivatives, poly-olefins, polyamides, or polyesters).
Methods of making non-woven cloths are not a part of this invention and, being well known in the art, are not described in detail herein. Generally, such cloths are made by air- or water-laying processes , in which the fibers or filaments are first cut to , . . . .
desired lengths from long strands, pass~d lnto a water or air stream~ and then deposited onto a screen through which the fiber-laden air or water is passed.

.

, - 21 -- - ~ . . . ~ :

10713GqD

~he deposited fibers or filaments are then adhesively bonded together, dried, cured, and otherwise treated as desire~ to form the non-woven cloth. Non-woven cloths made of polyesters, polyamides, vinyl resins, and other thermoplastic fibers can be spun-bonded, i.e., the fibers are spun out onto a flat surface and bonded (melted) together by heat or by chemical reactions~
~ The absorbent properties required in the --preferred particulate-plus-softener herein are quite easy to obtain with non-woven cloth~ and are pro-vided merely by building up the thickness of the cloth, i.e., by superimposing a plurality of carded webs or mats to a thickn2ss adequate .o ob'ain the r.ecessary absorbent properties, or by ~llowing a suf~icient thickness of the fibers to deposit on the screen.
Any diameter or denier of the fiber (generally up to about 10 denier) can be used, inasmuch as it is the ree space between each fiber that makes the thickness of the cloth directly related to the absorbent capacity of the cloth, and which, further, makes the non-woven cloth especially suitable for impregnation with a softening agent by means of intersectional or capil-lary action. ~hus, any thickness necessary to obtain ~ 25 the required absorbent capacity can be used.
-~ The choice of binder-resins used ln the manu-, facture of non-woven cloths can provide substrates ~' ' ..
..

~ - 22 ~

1~7~36~

possessing a variety of desirable traits. For example, the absorbent capacity of the clo~h can ~e increased, decreased, or regulated by respectively using a hyarophilic binder-resin, a hydrophobic binder-resin, or a mixture ~hexeof, in the fiber bonding stepO
Moreover, the hydrophohic binder-resin, when used singly or as the predominant compound of a hydro-phobic-~ydrophilic mixture, provides non-woven cloths ~ which are especially useful as substrates when the articles herein are used with damp fabrics in an automatic dryer.
When the substrate for the articles herein is a non-woven cloth made from fi~ers deposited hap-hazardly or in random array on the screen, the articles ~ -- 15 exhibit excellent strength in all directions and are , not prone to tear or separate when used in the automatic clothes dryer.
Preferably, the non-woven cloth is watar-laid or air-laid and is made from cellulosic fibers, particularly from regenerated cellulose or rayon, .. .
which are lubricated with any standard textile i lubricant. Preferably~ the iber~ are from 3/16"
to 2" in length and are from 1.5 to 5 denier.
Preferably, the fibers are at least partially oriented haphazardly, particularly substantially haphazardly, and are adhesively bonded together with a hydrophobic or substantially hydrophobic binder-resin, particular]y ' lL~7~316(1 with a nonionic self-crosslinking acrylic polymer or polymers. Preferably, the cloth comprises a~out 7~%
fiber and 30% binder-resin polymer by weight and has a basis weight of from about 20 to 24 grams per square yard.
~he fabric conditioning articles of the present inven~ion are structured to be compatible with conven-tional laundry dryer designs. While it is preferred to employ the articles of the present invention in an automatic laundry dryer, other equivalent machines can be employed, and in some instances, heat and drying air ma~ be omitted for part or all of the cycle.
Generally, however~ heated air will be employed and such air will be circulated frequently in the dryer.
Normally, there are from about 5 to 50 volume changes of drying air in the dryer drum per minute and the air moves at about 125 to 175 cubic feet per minute.
These changing volumes of air create a drawing or suction effect which can, especially with small fabric loads, cause an item such as a sock, handker~ -chief or the like, or a fabric conditioning article, to be disposed on the surface of the aix outlet of the dryer. A usual load of fabrics of from about 4 to 12 pounds dry weight will fill from ~bout 10% to 70% of the volume of ~ost dryerc and will normally pose little difficulty. A su~ficient number of tumbling items will normally be present tv prevent any item from being drawn to the exhaust outlet or to cause it to be - 24 - ;~
. .

-107~3~

removed from the outlet. In the e~ent, however, a ~abric conditioning article is caused to be disposed in relation to the air exhaus~ outlet in such a manner as to cause bloc~age of passing air, undesirable temperature increases can result. ~n ~he case o~
fabric conditioning articles employing the normally solid or waxy softener~ (e.g.t sorbit~n esters) which soften or melt under conditions o heat, the ar~icla may tend to aahere to an exhaust ou~let. ~ :
The problem of blockage can be solvëd by pro- ;
~ viding openings in the article in the manner described ; in Canadian Patents 1,033,916 and 1,033,917 of A.R. Mcnueary, . granted July 4, 197B.
` '' "-More specifically, slits or ; holes are cut through the substrate to allow free :-, pa~sage of air.
~ he slit openings are provided in the fabric conditioning articies of the invention for two principal 20 , purposes. Importantly, the slits permit passage of air in t~e event the article is placed in a blockin~
relationship to the air exhaust outlet. Moreover, the slit openings provide a degree of flexibility or resiliency which causes the article to crumple or pucker. The effect o~ such crumpling is that only a :
portion of the air exhaust outlet will be covered by ~071360 the conditioning article in the event it is carried by the moving air s~ream to the exhaust outletO
~oreovex~ the crumpled article is more readily removed ~y tumbling fabrics than would be the case if the article were placed in a flat ralationship to the exhaust outlet.
The type and number of slit openings can vary considerably and will depend upon the nature o the ` substrate material, its inherent flexibility or rigidity, the nature of the conditioning agent carried therein or thereon, and the extent to which increased passage of air therethrough is desired. The articles of this invention can comprise a large number of small slits o. various types or configurat-ons, or fewer larger slits. For example, a single rectilinear , .
or wavy slit, or a plurality thereof, con~ined to within the area of a sheet and extending close to opposite edges of the article, can be employed. By maintaining a border around all edges of the condi-tioning article, a desired degree of flexibility and surfa~e area availability to tumbling fabrics can ~e maintained. Whilej for example, rectilinear slits can be cut into a conditioning article completely to the edges of the article, confinement of the slits 2~ to within the area of the article will be preferred .. . .
where the convenience of packaging the conditioning ; article in rolI form is desired.

.

.
, .

107~36~

According to one preferred em~odiment of th~
invention, a sheet of fabric-conditioning article is provi~ed with a plurality of rectilinear slits extending in one direction, e.g., the machine direc-tion of the web substrate, and in a ~ubstantiallyparallel relationshi!?. The slits can be aligned or in a staggered relationship. A ~referred embodiment will contain from 5 to 9 of such slits which will ~ extend to within about 2 inches and preferably 1 inch ;~ 10 from the edge of the web material which is, for example, a 9" x 11" sheet. In general, the great~r the number and the longer the slits, the greater the effect in preventing restriction o~ air flow.
Such an article permits the individual panel areas or sections within the rectilinear slits to f}ex or move in independent relationship to each other and out of the plane of the sheet. ~his flexing minimizes the probability that such an article will align itself in a flat and blocking relationship to an exhaust outlet. The inherent puckering or crumpling tendency of the article allows the article to contact the air outlet in such a manner as to leave at least a portion of the air exhaust outlet uncovered. In addition, the tumbling fabric5 in the dryer will colllde with the crumpled article causing it to be removed from the exhaust outlet. Removal is readily accomplished by reason of the protrusion o~

. , .
~,. __ .

1~ 7~L3~0 the ~rumpled ~rticle which makes it more available for contact with the tumbling load of fabrics in the dryer.
The sli~ openings in the conditioning articles S of the invention can be in a variety of configurations and sizes, as can be readily appreciated~ In some instances, it may be desirable to provide slit openings as C-, U-, or v-shaped siits. Such slits arranged in a continuous or regular or irregular pattern are desirable from the standpoint of permitting gate-like or flap structures whic~ permit the passage of air therethrough.
In accordance with a preferred embodiment of the invention, a plurality of curvilinear slit openings, such as U-shaped, or C-shaped slits, are provided in a continuously pStterned arrangement.
These slit arxangement~ provide flap-like or gate-like structures which should approximate the size of the per~orations normally employed in laundry dryer exhaust outlets. A width dimension of from about 0.02 ' to about 0.40 inch is preferred. U- or C-shaped slits, e.g., about l/8" in diameter, are desirably provided in close proximity to each other, e.g., about l/8"
apart, as to simula~e, for example, a fish-scale pattern. Such design, in addition to permitting passage of air, provides a d~gree of flexibility to the~substrate and allows flexing or puckering of the article in use. Similarly, the slit openings can be : ~ : f .
arranged as spaced rows of slits or as a plurality of geometrical patterns. For example, a sheeted article of this invention can comprise a plurality of squares, circles, ~riangles or the like, each of which is comprised of a plurality of individual slits. Other embodiments including small or large S-shaped slits, X-slits or crosses, slits conforming to alphabeti~al or numerical patterns, logograms, ~ marks, floral and other designs can also be employed.
As an alternative to slits, the article can be provided with one or more circular holes having a diameter of from about 0.02 inches to about 4 inches, from about 5% to a~out 40~ of the surface area of the article comprising said holes. The holes can be dis-posed in any convenient relationship to one another but it is simplest,~ from a manufacturing standpoint, to punch the holes through the substrate in evenly spaced rows.
. , ~ .
Fabric Softener 20 , The present articles are preferably fashioned in combination with a fabric softener. Such fabric softeners are selected from ihose which melt ~or flow) at dryer operating temperatures and which are trans-ferred from the dispensing means onto clothes coming in contact therewith in the dryer. The fabric ~
. .
softeners used herein are characterized by a melting ` point above a~out 38~C. Lower melting softeners flow ,.

' :' 1~7136a~ -at room temperature and result in ~n undesirable tackiness, both in the article and on the fabrics t~eated therewith. ~ighly preferred so~teners herein melt (or ~low) at temperatures of about 45c to about 70Cf i~e., temperatures within the range found in most home dryers. However, softeners which melt at temperatures up ~o 100C, and higher~ are useful in some commercial dryers. Moreovert many softeners can be admixed with diluents of the type disclosed herein~
after to adjust their melting points to within a desired range.
It is to be understood that mixtures of fabric softeners can be employed herein concurrently to achieve multiple conditioning benefi.s. For example, various alcohol-type softeners and quaternary ammonium softeners can ~e used as admixtures which ~oth soften and provide static control benefits.
The abric softener employed in the present invention can be any o~ the cationic (including imidazolinium) compounds listed in U.S. Patent 3,686,025, Morton, TEXTILE SOFTENING AGENTS IMPREG~TED INTO : ~ .
ABSORBE~ MATERIALS, is ued August 22, 1~72, :~
Such materials are well known in the art and include, for example, the ~uaternary ammonium salts having at least one, preferably two~ Clo-C20 fatty alkyl substituent groups, alkyl imida~olinium salts wherein at least one alkyl. .:
.
'" '~.:

- 3~ - ~
- .

:~Ci 7~3gi~

group contains a C8-C25 carbon "chain"; the C12-C20 alkyl pyridinium salts, and the like.
Preerrea cationic softeners herein include the quaternary ammonium salts of the general ~ormula S RlR2R3R4N~X , wherein groups Rl, R2, R3 and R4 ar~, -for example, alkyl and X is an anion, e.g., halide, methylsulfate, and the liXe, Especially preferred softeners herein are those wherein Rl and R2 are each ~ C12~C20 fatty alkyl and R3 and R4 are each Cl-C3 alkyl.
The fatty alkyl groups can be mixed, i.e., the mixed C14-C18 coconutalkyl and mixed C16-Cl~ tallowalkyl quaternary compounds. Alkyl groups R and R are preferably methyl.
Particularly useful quaterna_y a~monium softeners herein include ditallowalkyldimethylammonium methyl-sul~ate and dicoconutalkyldimethylammonium methylsulfate.
A preferred type o~ fabric softener employed in the present articles comprises the esterified cyclic dehydra-tion products of sorbitol. sorbitol, itsel~ prepared by the catalytic hydrogenation of glucose, can be dehydrated in well-known fashion to form mixtures of cyclic 1,4-and 1,5-sorbitol anhydrides and "sorbitan". (See U.S.
Patent 2,322,821, Brown, P~RTIAL ESTERS OF ETHERS OF
POLYHYDROXYLIC COMPOUNDS, issued June 29, 1943.) l'he resulting complex mixtures of cyclic anhydrides of . . ~ .
~orbitol ~re collectively referred to herein as "sorbitan", ; .

. ~ .

3~) Fabric softeners of the type employed hPrein are prepared by esterifying the "sorbitan" mixture with a fatty acyl group in standard fashion, e.g , by reaction with a fatty acid halide. The 6sterification S reaction can occur at any o~ the available hydroxyl groups, and various mono-, di-, etc., esters can be prepared~ In fact, mixtures of mono-, di-, tri-, etc., esters almost always r0sult from such reactions, ~ and the stoichiometric ratios of the reactants can simply be adjusted to favor the desired reaction product. The sorbitan mono-esters and di-esters are preferred for use in the present invention. While not intending to be limited by theory, it appears that to be optimally useful as a softener, the sorbitan esters`should contain unesterified hydroxyl groups to provide hydrogen bonding with, and attachment to, fabric surfaces. The mono- and di-esters of sorbitan fulfill this requirement.
The mixtures of hydroxy-substituted sorbitan esters useful herein contain, inter _lia, compounds of the following formulae, as well as the corresponding hydroxy-substituted di-esters:
.
. .

~: :
: '.; .

,~:

~71~6~

H~ ~H
H ~ O~ CH20-C ( O) R
~/--C-CH20-C (O) R and 1 J~
OH OH y OH
OH
.~ ' .' and ~1 o-C t) R
:, ~ ' ' ~.,:

' ;
.
. . . ' ~':

.

' : ' ' , ' .

!

, ~ 3 3 ~ ; .

1~7~36(~

wherein group Rc(O)- is a fatty alkyl residue. The foregoing complex mixtures of esterified cyclic dehydration products of sorbitol are collectively referred to herein as "sor~itan esters''O sorbitan S mono- and ~i-e~ters of lauric, myristic, palmitic, and stearic acids are particularly useful herein for im-parting a soft, lubricious feel and anti-static benefit to fabrics. Mixed sorbitan esters, e.g.~
mixtures of the foregoing esters, and mixtures prepared ` by esterifying sor~itan with fatty acid mixtures such as the mixed tallow and hy~rogenated palm oil fatty acids, are useful herein and are economically attractive.
; Unsaturated ClO-Cl8 sorbitan esters, e.g., sorbitan mono-oleate, usually are present in such mixtures.
It is to be recognized that all sorbitan esters con~
taining free -OH groups which soften and flow at dryer operating temperatures, i.e., above about 38C-~0C, but which are solid below this temperature range, and which have fatty hydrocarbyl "tails", are useful softeners in the context of the present invention~
Preparation of the sorbitan esters herein can be achieved by cyclizing sorbitol to form a mixture of cyclic anhydrides of the type set forth above, and separating and esteri~ying the various cyclic anhydrides usins a l:l stoichiometry for the esterification reaction. However, s~paration o~ the cyclization products is difficult and expensive. Accordingly, it is easier and more economical not to separate the various cyclic anhydrides, hut simply to esterify the i~7:~36~

total mixture. Of course, this results in esterified mLxtures of the type disclosed above. SUCh mixtures of esterified reaction products are commercially available under various trademarks, eOg~, Span ~ .
The preferred alkyl sorbitan esters herein comprise sorbitan monolaurate, sorbitan monomyristate, ~orbitan monopalmitate, corbitan monostearate~
sorbitan dilaurate, sorbitan dimyristate, sorbitan ~ dipalmitate, sorbitan distearate, and mixtures thereof, and mixed coconutalXyl sorbitan mono- and di-esters and mixed tallowalkyl sorbitan mono- and di-esters.
Such mLxtures are readily prepared by reacting the foregoing cyclic, hydroxy substituted sorbitans, particularly the 1,4- and 1,5-sor~itans, with the corresponding acid or acid chloride in a simple esterification reaction. It is to be recognized, of course, that commercial materials prepared in this manner will comprise mixtures containing minor proportions o~ various tri-esters, uncyclized sorbitol, fatty acids, polymers, isosorbide structures, and the like. The presence or absence of such materials as minor components of the sorbitan mixtures is of no consequence to this invention. For most purposes, ; the commercially available sorbitan esters which comprise a~ove about 40~O by weight, preerably above about 60%
~ by weight, of ClO~C~2 mono- and di-esters and which have - melting polnts of at least about 38C-40C can be advantageously employed to soften clothes in the manner OL this in~ention. Highly ~re~erred materials include ~-Lr~ _ ~lCI 71366~

sorbitan monostearate, sorbitan monopalmitate, and 1:10 to 10:1 (wt.) mixtures thereof. Both the 1,4-and 1,5-cyclic sorbitan stearates and palmitates are useful herein, inasmuch as their melking points are 5 above abou 38C-40C~ and they contain at least one hydroxyl group which provides a mode of attachment to fabric surfaces.
Other types of fabric softeners which can be employed herein comprise higher melting fatty alcohols, 10 fatty acids, glycerides, and ~he like. When employed in an automatic clothes dryer~ such materials impark the tactile impression of "crispne$s 1l or "newness"
to the finally dried fabricsO The term "crispness"
as used herein means a distinctive tactile impression best described as "dry" and, in some cases, "crunchy"O
The fabric crispness properties achieved by these agents provide an added dimension to fabric softnessJ
as it is generally understood. ~risp, soft fabrics can be obtained without the undesira~le excess lubricity and greasin~ss associated with some other fabric softeners.
Useful soteners (or, more broadly, conditioners) of this type encompass the substantially water~insoluble compounds selected from the group consisting of alcohols, carboxylic acids, carboxylic acid salks~ and mixtures ~5 of these compounds. By "substantially water-insoluble"
herein is meant a water solubility of 1% by weight, or less, at 30C. The alcohols are preferred for use herein by virtue of their excellent fabric crlsping ~ ~-....

- 3~ -~7136~

properties. Moreover, alcohol from the treated ~abrics can be slowly transferred to skin on contact with the fabric to pro~ide prolonged emolliency benefits.
Mono-ols, di-ols and poly-ols having the requisite melting points and water-insolubility properties set forth above are use~ul hereinO Such alcohol-type materials include the mono- and di-fatty glycerides :~
which contain a~ least one l'free" OH group The ~ ~ono-ols are preferred in that they are non-hygroscopic and non-tacky when applied to fabrics.
All manner o~ water-insoluble, high melting alcohols tincluding mono- and di-glycerides), carboxylic acids and carboxylate salts are useful herein, inasmuch as all such materials coat fibers and dry to a non-ta~ky fabric finish. Of course, it is desirable to ~- use those materials which a~e colorless 9 50 as not to alter the color of the fabrics being treated~ Toxi-cologicaLly acceptable materials which are safe for use in contact with skin should be chosen.
Primary, secondary and tertiary alcohols are all useful as the softening/conditioning c~mponent of the present articles. The hydrocarbyl moiety of the alcohol can be alkyl, olefinic, acetylenic or multiple unsaturated . alkyl, cycloalkyl, heterocyclic, aralkyl, e.g., phenyl-; : 25- alkyl, and the like. hryl alcohols, i.el, the p~enolics, provide the fabric crispness benefits hexein :
but are not preferred when treated fabrics are to be . . '. '' 107~1L3~0 in contact with skin for prolonged periods. In short, any alcohol having the requisite water-insolubility and high melting point range is useful herein.
For example, iso-propyl alcohol, a common secondary aliphatic alcohol, is not useful as the fabric crisping component herein due to its low melting point and high water solubility. In contrast 2-heptadecanol, another common secondary alcohol, is useful herein by ~irtue of its low water solubility and high melting point.
~any highly substituted alcohols are known to be water-insoluble and to have high melting points, and these are also uceful herein. For example, although methanol is not useful herein because of its low melting point and high water solubility, 4-methyl benzyl alcohol is useful. -~-Alcohols and mixtures thereof with melting points below about 38C are not useful herein. Only those alcohols which are solid or substantially solid at climatic temperatures commonly encountered are employed in the present compositions. Liquid (low melting) alcohols can be applied to fabrics to increase lubricity, but the solid ~high melting) alcohols provide the desired benefits without tackiness.
Alcohols employed as the fabric crisping component herein are most preferahly those which have melting points of from about 38C to about lOO~C, i.e., at temperatures within the range commonly encountered .

.', '

6~

in a typical automatic clothes dryer. A melting point within this dryer operating range ensures that, in use, the alcohols are fluidizea and are more efficiently transferred and deposited uniformly on the fabric surface. After the drying operation, the alcohol cools and solidi*ies to condition and soften the ~abric~ Alcohols melting above dryer temperatures are useful herein, but are not as ef~iciently trans-ferred to fabricsO Such extremely high melting alcohols can be diluted with various adjunct materials, as described hereinafter, to lower their melting points to that encountered in a dryer.
In addition, the alcohols having melting point~
within the preferred range recited above are more easily trans~erred from the treated fabric to human skin through mechanical fri¢tion and body heat to provide desirable emolliency benefits. Such considera~
tions are important when an alcohol such as cetyl ~lcohol, which is known to be a s~in emollient, is employed in the articles of this inven~ion.
A preferred class of alcohols use~ul herein includes the higher melting members of the so~called fatty alcohol class. Although once limited to alcohols obtained from natuxal fats and oils, the term "fatty alcohols" has come to mean those alcohols which correspond to the alcohols obtainable from fats and oils, and all such alcohols can be made by synthetic processes.

~7~36V

Fatty alcohols prepared by the mild oxidation of petroleum products are useful herein~
All fatty alcohols are substantially water-insolu~le and the C14 to Cl~ fatty alcoho;s have the preferred melting points for us~ herein. Moreover, the fatty alcohols are preferred from the overall standpoint of availability, low cost, low color, and toxicological acceptability. A further consideration ~ is that many fatty alcohols are known to impart 10 emollient benefits to the skinO The saturated C14 to C18 fatty alcohols are most highly pre~erred for use herein, inasmuch as the corresponding unsaturated alcohols ~an oxidize at dryer temperatures and un-desirably yellow fabrics.
Table I sets forth typical alcohols which are useful in the present articl-es, but is not intended to be limiting ther i.

;:~

~,~
.'~ . . -';

~' ., . '.
.' ., , :
,, . . '.

: - 40 ~

. ..

TABLE I
Melting Point Alcohol C
~ _ . .
l-Tricosanol 74 l-Tetradecanol (myristyl alcohol) 37.7 l-Pentadecanol 44 l-Hexadecanol (cetyl alcohol) 49.3 l-Heptadecanol 54 l-Octadecanol (stearyl alcohol) S~5.~ .
LO l~onadecanol . 62 l-Eicosanol 65 l5~Methyl hexadecanol 40.7 - 41~2 16-Methyl heptadecanol . 40.1 - 40.3 ` l-Heneicosanol 6905 .LS l-Docosanol 73.S
2-Octadecanol 52 2-Nonadecanol 52 2-Eicosanol . 60 2-Hexadecanol 44 2Q 2-Heptadecanol 44.5 TallowalXyl alcohol (mixture) 46 - 47 l,l-Diphenyl hexadecanol 47 - 48 2-Methyl-2-nonadecanol 44 - 45 ` l,l-Diphenyl octadecanol 58 4-Methylbenzyl alcohol 59 - 60 Phenyl 4-tolyl carbanol (4~methylbenzhydrol~ . `58 (42, 53 Isofenchyl alcohol . 62 . ~ Propyl benzyl alcohol 49 3,3,5-Trimethylcyclohexanol 55.8 ; Diols 1,12-Octadecanediol 66 - 67 l,10-Decanediol (decanmethylene glycol~ 72 ~ 75.5 3-~octadecyloxy)-1-2-propanediol ~5 ~batyl alcohol) 70 - 71 a-Hexadecylglyceryl ether (chimyl : alcohol) 64 ' '' ~

: ' .

~7~360 While any of the foregoing alcohols are useful in the compositions, processes and articles of manu-facture of this invention, cetyl alcohol is especially preferred from the standpoint of excellent crispness and desirable skin emolliency benefits. stearyl alcohol is also pre~erred from the standpoint of commercial availabillty. The fatty alcohol mixture derived from tallow carboxylic acids, and commonly referred to as tallowalkyl alcohol, is preferred from ` the standpoint of cost and availability. Mix~ures of these alcohols are a~so useful herein.
Another type of material which can be classified as an alcohol and w~ich can be employed in the instant articles encompasses various e~ters of polyhydric alco~ols. Such "ester-alcohol" materials which have a melting point within the range recited herein and ., , ;
which are substantially water-insoluble can be employed herein when they contain at least one free hydrox~l group, i.e., when they can be classified chemically as alcohols. Such materials meet the requirements of the alcohols employed herein, and it is intended that the term "alcohol" encompasses such -OH containing ester-alcohol materials. This class of materials includes, for example, the mono- and di-esters of glycerol, such as those obtained from various oils ! .
and fats. The glycerol di-esters are particularly useful ~erein, inasmuch as they contain the requisite free hydroxyl group for bondin~ with fabric sur~acesJ

: - . .

, 1~7~36~

are water-insoluble, and can be selected to have melting points within the required and preferred ranges herein. Finally, such di-es~ers of glycerol are available from commercial fats and waxes and are known to be toxicologically acceptable.
The alcoholic di-esters of glycerol preferred for use herein include both th~ ~,3-di glycerides and the 1,2-di-glycerides. It is to be recognized that, inasmuch as glycerides containing one, or more, free hyaroxyl groups are properly classifiable as alcohol~, such materials can be employed as the whole of the fabric softener and conditioner herein. Alternatively, the glycerides can be mixed with waxes, triglycerides, and the like, to provide a spectrum of tactile stimuli on the fabrics. In particular, di-glycerides containing ~wo C8 C20t preferably C10-Ç18, alkyl groups in the molecule provide a soft handle to fabrics which is reminiscent of the effect achieved with the di-long chain alkylammonium fabric softeners in common use.
~ The di-long chain alkyl groups in such di-ester alcohols provide a soft, lubricious feel when these materials are employed in the articles herein.
Mono- and di-ether alcohols, especially the C10-C18 di-ether alcohols having at least one free -OH
group, also fall within the definition of alcohols useful herein.
The ester-alcohols employed herein can be synthetically produced in well-known fashion by ester-ifying a poly-ol with an amount of a carboxylic acid - ~3 -1~7~L36~1 or anhydride such that one, or more, of the -OH groups remain unesterified. For example, reacking one mole of glycerol ~3-OH groups) with 2 moles of lauric acid provides mixtures of 1,2- and 1,3-dilauryl esters of glycerol~ SUCh mixtures can be separated if desired, but the mixtures~ themselves~ are suitable for use herein. In like manner there can be produced 1,2- and 1,3-di-myristic, di-palmitic and di-stearic acid esters of glycerol. Mixed tallow fatty acids can also be employed to prepare mixed e~ters and are economically attractive.
The ether-alcohols useful herein can be pre-pared by the classic Williamson ether synthesis. As with the ester-alcohols, the reaction conditions are chosen such that at least one free, unetherified -OH
group remains in the molecule.
: The esterralcohols are preferred for use herein over the ether-alcohols due to ~heir availability and known toxicological acceptability.
~on-limiting examples of ester~alcohols useful herein include: glycerol-1,2-dilaurate, glycerol-1,3-dilaurate, glycerol-1,2-myristate, glycerol-1l3-dimyristate, glycerol-l,~-dipalmitate, glycerol-1,3-dipalmitate, glycerol-1,2-distearate and glycerol-1,3~distearate.
Mixed glycerides available from mixed tallowalkyl fatty acids, i.e., 1,2-ditallowalkyl glycerol and ; 1,3-ditallowalkyl glycerol, are economically attractive ~or use herein. The foregoing e~ter alcohols are - .' . . . ' ' '. ' ' ,. . : .

preferred for use herein due to their ready availability from natural fats and oilsD
Other ester-alcohols useful herein include glycerol-l-ustearate-2-palmitate, butane tetra-ol-1,2,3-5 tristearate, sorbitol tristearate and the like.
Ether-alcohols useful herein include glycerol-1,2-dilauryl ether, glycerol-1,3-distearyl ether, and butane tetra-ol-l t 2,3-trioctanyl etheru ~ The substantially water-insoluble car~oxylic acids and the substantially water-insoluble salts thereof having melting points as set forth above are also useful conditioners in the articles of this invention.
When selecting a carboxylic acid or carboxylate ; salt for use herein, the same considerations apply as to operable and preferred melting point ranges, water solubility, lack of color, non-hygroccopicity, etc., as in the case of the fatty alcohols. ~s with the alcohols, all manner of water-insoluble aliphatic, aromatic, olefinic, aralkyl, heterocyclic, etc., .
carboxylic acids and salts are useful herein.
Fatty acids, synthetic or natural, especially the saturated fatty acids, are preferred herein because of their availability and price. Fatty acids are also recognized as skin emollients. saturated fatty acids are preferred herein since they do not decompose at dryer operating temperaturesu ~ ~ _ , ..... . . ............... .

7~36~1 Water-insoluble carboxylate salts~ especially the salts of the C8-C20 fatty acids, are also useful herein. SUCh salts can be prepared by neutralizing the free ac-ds with a metallo base, e.g., Mg~OH)2, S Ca(OH)2, and the like, in well-known fashion. The cation of the base then becomes the cation of the carboxylate salts. Of course~ it is preferred to use salts of non-toxic cations. Colorless carboxylate ~ salts are pxeerred, and lack of color will dictate the selection of cation for use in the case of the most preferred carboxylates. The Ca~ and Mg~
carboxylate salts are pr~ferred herein by virtue of low cost, ready availability, and the foregoing con~
siderations.
Table II sets forth a selection of non-limiting examples of carboxylic acids which can be employed herein. It i~ to be understood that the Ca~+ and Mg~+
salts of each of these listed acids are also useful for this purpose.
.
,, , ':~ ; , .
., . .
. .

.:

- 46 - ~ ~

~L~7~L36~

TABLE II
.
n~
Dodecanoic acid 44.2 Tridecanoic acid 41.5 Tetradecanoic acid 53.9 ~entadecanoic acid - 52.3 Hexadecanoic acid 63.1 ~eptadecanoic acid 61.
Octadecanoic aci~ 69.6 ~onadecanoic acid 68~6 Eicosanic acid 75.~
Heneicosanoic acid 74.3 ~-Propyloctadecanoic acid 46 5 Methyloctadecanoic acid 48 . 6-Methyloctadecanoic acid 45 12-Methyltridecanoic acid 53 15-Methyloctadecanoic acid 43O5 .l 2-Butyloctadecanoic acid 50 ~ 2-Hexyloctadecanoic acid 5~.5 2-Nonyloctadecanoic acid ~7 2-Hexadecenoic acid 57.5 Trans-6-Octadecenoic acid 54 I

` Trans-9-Octadecenoic acid 46.5 .
Phenylacetic acid . 76.5 Y-Phenyl butyric acid 52 .

, ' , . ~ . . ~.

. . .

''', ~.

~L07:~L36~

Optional Components Various optional additives can also be used in the articles herein~ Although not essential to the invention, certain fabric treating additives are s particularly desirable and useful, e.g.~ bright~ning agents, shrinkage controllers, spotting agents, and the like.
While not essential, liquids which serve as a diluent for the softening agent can be employed~ Such ~ liquids can be used to more evenly impregnate absorbent carrier substrates with the softening agent. When a liquid diluent is so used, it should preferably be inert or stable with the fabric softener and with the particulate material herein. Moreover, the liquid carrier should be substantially evaporated at roGm temperatures, and the residue (i.e., the softening agent) should then be sufficiently hardened so as not to run or drip off the substrate, or cause ~he substrate to stick ~ogether when folded. Isopropyl alcohol or isopropyl alcohol/water mixtures are the preferred liquid carriers fOr these purposes; methanol, ethanol, ' acetone, ethylene glycol or propylene glycol can also be used.
- Other additives can include various finishing .j , . . .:
aids, fumigants, lubricants, fungicides, and sizins . . . . .
agents. Specific examples of useful additives can be found in any current Year Book of the American i~
;
Association of Te~tile Chemists and Colorists.

i ~', ~:' v ' , - 4~ - !

7~360 The amounts of such additiJes (e.g., fumigants and brighteners) used in ~he articles herein are generally small, being in the range of from 0.001% to about 10% by weight of the article.
In preparing the preferred articles herein con-taining bo~h the particulate material and the softener it is often advantageous to include a surfactant to heip pro~ide easyt yet controlled and uniform release of the softener from the carrier. Uniform release ` o~ the softener helps prevent staining of synthetic fabrics.
Various surfactants are useful herein. For example, the nonionics, especially the well-known ethoxylated fatty alcohols having a hydrophilic-lipophllic balance of from about 2 to about 15 areuseful herein. Anionic surfactants, especially tallow alkyl sulfate, can also be employed.
The selection of optimal surfactants will vary somewhat, depending on the type of softener chosen for use in the articles. For example, anionic sur-factants are preferably not used in combination with cationic softeners, inasmuch as cation-anion reactions occur~ Nonionic surfactants are employed with cationic softeners. When nonionic softeners ~i.e., the alcohol, glyceride and sorbitan softeners) are used in the articles, they can be combined with either anionic or nonionic surfactant~

.~
'.

_ 49 _ ~a~7~L3~

It is to be understood that, while the selection of surfacta~ts is not critical to the operation of the articles herein, surfactant-softener mixtures can ~e employed to modify their performance properties. The S articles herein can contain from about 0.001% to about 10% by weight of article of a surfactant.

., . .
- Article Manufacture ` Th~ articles herein comprise the particulate material, preferably in combination with a softener, and carrier cubstrate. When the carrier is to be a porous pouch, the particulate material, and optional ingredients and softener, are simply admixed thoroughly and placed in the pouch, which is then sewn, or otherwise permanently sealed. The pouch ; is fashioned from a material whose average pore diameter is 10% to 1S% larger than the particulate material con-tained therein. The tumbling action of the dryer causes the material to sift through the pores evenly onto all fabric surfaces.
Preferred articles herein are provided in sh~et form, for the reasons disclosed a~ove. A carrier sheet is releasably coated with sufficient particulate material to treat one average load (5-8 lbs.~ of fabrics. The coating process involves, for example, coating the sheet with an inert, unobjectionable, somewhat tacky material such as any of the marine ' .
:
; ~ :

13~0 agars and thereafter impressing the desired amount of particulate material into the coating. Heat and the tumbling action of the dryer releases the particulate material onto fabric surfacec.
Highly preferred sheeted articles herein are those comprising both the particulate material and a softener, most preferably wherein the softener is impregnated into the absorbent sheet substrate.
~ In such articles, the softener provides both a fabric softening action and a means whereby the particulate ; material can be releasably affixed to the sheet~
Impregnation with the softener can be done in any convenient manner, and many methods are known in the art. For example, the softener, in liquid form, can be sprayed onto a su~strate or can be added to a wood-pulp slurry from which;the substrate is manu-factured. Sufficient softener remains on the surface to conveniently affix the particles to the substrate~
Impregnating, rather than merely coating, the substrate with a softener provides optimal so$tening r without fabric staining. The term "coating" connotes the adjoining of one sub~tance to.the external surface of another: "impregnating" is intended to mean the permeation of the entire substrate structure, internally as well as externally. One factor affecting a g.iven substrate's absorbent capacity is its free space. Accordingly, when a softening agent is applied to an absorbent substrate, it penetrates .: ' ' ' -~ 51 -' ,'' .'. '~ ~; ...
. ~

~L~7~3~

into the free space; hence, the substrate is deemed impregnated. The free space in a substrate of low absorbency, such as a one-ply kraft or bond paper, is very limited such a substrate is, therefore, termed "dense". Thus, while a small portion of the softening agent penetrates into the limited free space available in a dense substrate, a rather substantial balance of the softener does not penetrate and remains on the surface of the substrate so that it is deemed a coating. The difference between coating and impreg-nating is believed to explain why the s~ftener-impregnated sheet substrates of the invention herein eliminate or .. . .
- substantially reduce the staining of fabrics observed when a softener-coated dense substrate is utilized~
In a preferred method of making the softener plus p~rticulate sheeted articles herein, the softener (alone or with the optional additives) is applied to a~sorbent paper or non-woven cloth by a method generally known as padding. The ~oftening agent is preerably applied in liquid form to the substrate. For example, sorbitan ester softeners which are normally solid at room temperature should first be melted and/or solvent treated with one of the liquid carriers mentioned hereinbefore. Methods of melting the softener and/or for treating the softener with a solvent are knowm and can easily be done to provide a satisactory softener-tr-ated substrate.

., .
.

.

~a7~360 In another preferred method, the softener is placed in a pan or trough which can be heated to maintain the so~tener in liquid form. To the liquid softener are then added any desired additives~ A
roll of absorbent paper (~x cloth) is then set up on an apparatus so that it can unroll freely. As the paper unrolls, it trav~ls aownwardly and, submersed, pa~ses through the pan or trough containing the liquid softener at a slow enough speed to allow sufficient impregnàtion~ The absorbent paper then travels upwardly and through a pair of rollers which remove exces~ bath liqyid and provide the absorbent paper with about 1 to about 12 grams of the softening agent per 100 in.2 to 150 inO2 of substrate sheet. The impregnated paper is then coated with the particulate material (generally 0.1 g. to 5 g.~per 100 in. ;to 150 in. ) and cooled to room temperature, after which it can be folded, cut or perforated at uniform lengths, and subsequently packaged and/or used.
In another method, the so~tening agent, in yid form, is sprayed onto absorbent paper as it unrolls and the excess so~tener is then squeezed Off by the use of squeeze rollers or by a doctor-~nife.
-~ther variations include the use of metal l'nip" rollers on the leading or entering surfaces of the sheets onto which the softening agent is sprayed: this variation allows the absoxbent paper to be treated, usually on one side only, just prior to passing between the rollers '...

:............... ~- .- . - - . . . . .
,, ~ . ~ , . . : .
- ., ..... ~ . . , ~ " ., . : . ..

11~7~36~) whereby excess softener i5 squeezed off. This variation can optionally involve the use of metal rollers which can be heated to maintain t~e softener in the liquid phase. Optionally, the particulate material can be S impressed onto the sheet hy means of such rollers.
A further method involves separately treating a desired number of the individual plies of a mul~i-ply paper and su~sequently adhesi~ely joining the plies with a known adhesive-joinder compound; this provides an ~ article which can be untreated on one of its outer ~ides, yet contains several other plies, each treated on both sides.
Xn applying the softening a~ent to the absorbent ; substrate, the amount of softener impregnated into the absorbent substrate is conveniently in the ratio range of lO:i to 1:1 by weight softener:dry, untreated ~ub-strate. Preferably, the amount of the softening agent impregnated is from about 4:1 to about 1.2:1, particularly 1.25:1, by weight~of the dry, untreated substrate.
Following application of the liquified softener and the particulate material, the articles are held at room temperature until the softener solidifies.
The resulting dry articles, prepared at the softener:
substrate ratios set forth above, remain flexible;
the sheet articles are suitable for packaging in rolls. The sheet articles can optionally be slitted or punched to provide a non-blocking aspect at any convenient tim during the manufacturing process.
.

.

~7~36~

The most highly preferred articles herein are those whexe the particulate material and softener are releasably affixed to a sheet substrate of the type disclosed hereinabove having an absorbent capacity of from about 5.5 to about 12. A highly preferred substrate for such an article has from about 4~O to about 90% free space based on the overall ~olume of the substrate~ The most highly preferred .substrate for the articles comprises a water-laid or air~laid non-woven cloth consisting essentially of lubricated cellulosic fibers, said fibers having a length of about 3~16 inches to about 2 inches and a denier from about 1.5 to about 5g said fibers being at least ~ partially oriented haphazardly, and adhesively bonded 15 together with a binder-resin. Such water-laid or air-laid non woven cloths can easily be prepared having the preferred absorbent capacities and fxee space set .:
forth above.
, The most highly preferred articles herein are those wherein the flexible sheet substrate is provided . with openings sufficient in size and numbe.r to reduce restriction by said article of the flow of air through the automatic dryerO Articles wherein the openinys comprise a pluralit~ of rectilinear slits extending ~5 along one dimension of the substrate, especially those wherein the slits extend to within 1 inch from at least one edge of said dimension of the substrate, -:.

- 55 ~

~C~7~3~

articles whPrein the slits comprise a plurality of curvilinear slits in a continuous pattern of U-shaped - or C-shaped slits, and article wherein the openings comprise circular holes, are highly preferred herein.
It is most convenient to provide an article in the form of a non-blocking ~heet ~ubstrate having the physical parameters noted hereinabove, said ~ubstrate having an area of from about 50 in.~ to about 200 in~2, comprising from about 0.1 ~rams to about 10 grams of the particulate material releasably affixed thereto and from about 1.5 grams to about 7.5 gra~s of the so~tener releasably impregnated in said substrate.
Such articles can be provided with, as an additional component, any of the fabric treating additives of the type disclosed hereinabove. The articles are provided with openings such as the hole~ or slits described hereina~ove, said openings comp~ising from about 0~5%
to about 75%, preferably 5/~ to about 40%, of the area of the article, said openings being so disposed as to provide a non-blocking effect.

Usaqe In the process aspect of this invention the articles are used to condition and soften fabrics in an automatic dryer~ The effective, i.e~, conditioning and softening, amount of the active ingredients used in the articles of this invention will depend somewhat on the type of fabric being treated. For illOst purposes, ' - . :
' - ` . . , :: : . :' . :
.

~al7~3~i~

the particulate materials are applied to ~abrics at a level of about 0.01 gram to 12 grams, preferably 1 gram to 7 grams, and the sof~ener is applied at a level of 0~01 gram to a~out 12.0 grams, preferably 2 g. to a~out 7 gO, all based on a fabric load of 5 lbs~ (ca. 180 sq. ft~) of fabric (dry fabric weight basis)~ Hi~her usage rates can be employed, if desired, but with little noticeable advantage.
The process herein is carried out in the following ` manner. Damp fabrics, usually containing from about 1 to about 1.5 times their weight of wa~er, are placed in the drum of an automatic clothes dryer. In practice, such damp fabrics ~re commonly obtained by laundering, rinsing and spin-drying the fabrics in a standard washing machine. An article prepared in the manner of this invention is simply added thereto. The dryer is then operated in -tandard fashion to dry the ~abrics, usually at a temperature from about 50C to about 80~C
for a period from about 10 minutes to about 60 minutes, depending on the fabric load and type. The heat and tumbling action of the revolving dryer drum evenly ; distributes the active ingredients from the article over all fabric surfaces, and dries the fabrics. On removal from the dryer, the dried fabrics are condi~
25 - tioned and softened.
Th~ following examples illustrate the articles of this invention but are not intended to be limiting thereof. - i i' ~ '' ; - 57 l;

3L~7~3S~ -:
EX~MPLE I~
A dryer-added fabric softening article is prepared ~y sprinkling 5 . O grams of a sorbitan ester mixture comprising about 50% (wt.3 of 1,4-sorbitan S monostearate uniformly over the surface of an air-laid non woven cloth comprising 70% regenerated cellulose ~American Viscose Corporation) and 3a~O hydrophobic binder-resin ("Rhoplex HA-8*" on one si~e of the cloth, and "Rhoplex HA-16**" on the o~her side; Rohm & Haas, Inc.).
The cloth has a thickness o 4 to 5 mils, a bas is weight of abou~ 24 gram~ per s~uare yard and an absorbent capacity of 6. A one-foot length of the cloth, 8-1/3 inches wide, weighs about 1.78 grams.
The fibers in the cloth are ca. 1/4 inch in length, lS 1.5 denier, and are oriented substantially haphazardly.
The fibers in the cloth are lubricated with sodium oleate. The substrate cloth is 10 inch x 11 inch.
The sorbitan ester-covered cloth is transferred to a heated plate, whereupon the ester melts and impregnates the inter-fiber free space in the cloth substrate. DRY-FLO starch, 1.5 grams, avg. particle diameter 10 ~m, is sprinkle~ uniformly over the surface of the ester-covered cloth and pressed in place with a wide-blade spatula. The article is removed from the hot plate and allowed to cool to room temperature, whereby the ester solidifies. The cloth retains its flexibility. he starch particles are releasably - ::
affixed thereto.
*Trademark **Trademark .

, ;, ~. ... '.: :,., , . -- : ' - . - :

~7~36(~

Following solidification of the sorbitan ester, the cloth is slitted with a knife. (Conveniently, the cloth is provided with S to 9 rectilinear slits extending along one dimension of the substrate, said slits beinq in a substantially parallel relationship and extending to within about one inch from at least one edge of said dimension of the substrate.) The width of an individual ~lit is ~a. 0.2 inches.
~ An article prepared in the foregoing manner is placed in an automatic clothes dryer together with 5 lbsO of freshly washed, damp tca. 5.5 lbs.
water) mixed cotton, polyester, and polyestericotton blend clothes. The automatic dryer is operated at an aYerage temperature of 60~C for a period o 45 minutes.
During the course of the drying operation the clothes and softener article are constantly tu~hled together by the rotation of ~he dryer drum.. After the drying cycle, the clothes are removed from the dryer into a room having a relative humidity o~ S0. The d othes are found to exhibit excellent softness and anti-static :
properties with no substantial staining. The clothes are provided with an anti-wrinkli.ng finish and require ~ less force to ironO Moreover, the clothes are provided with an anti-static ~inish. (The extent of static control is measured in a Faraday cage: the ,.:
.~ anti-wrinkling effect is measured photoelectrically;
ease-of-ironing is measured by means of a commercial hand iron equipped with force measuring sensors, all :-~ ................................................. : :.

: ; :
- 59 - :
... .. . . . . . .. . . . . . .

. ~ . . .. . . . . .. -~Lq)7~36~ -as de s c ri he d 1 n Can adi an P ate n t 1, 0 2 9, 15 4 o f Edw a rds and Diehl, entitled FABRIC SOFTENING COMPOSITIONS WITH IMPROVED
CONDI TI ON I N G P ROP ERTI ES, s ai d p aten t h avin g an i s s ue da te of Aprll 11, 1978.
S Equivalen~ results axe secured when, in the foregoing article, the l,4-sorbitan monostearate is replaced by an equivalent amount of 1,5-sorbitan monostearate, a 1:1 (wt.) m1xture of 1,4-sorbitan monostearate and 1,4-sorbitan distearate; a 1:1 ~w~.) mixture of 1,5-sorbi~an monostearate and 1,5-sorbitan distearate, a 1:1 (wt.) mixture of 1,4-sorbitan mono-stearate and 1,5-sorbitan monostearate, a 1:1 (w~
mixture of 1,4-sorbitan monostearate and 1,5-sorbitan distearate; a l:l (wt.) mixture of 1,4-~orbitan distearate and 1,5-sorbitan ~onosteara~e: and a 1~1 (wt.) mixture of 1,4-sorbitan distearate and 1~5-sorbitan distearate, respectively~

EX~MPTE II
A dryer-added fabric softening article is :~
; 20 , prepared in the following manner. A 70~30 (wt.) ~:
mixture of ditallowalkyldimethylammonium methylsulfate and SPAN 60*(ICI's commercial mixture o~ sorbitan :
"stearate" comprising a total of about 90% by weight total sorbitan and isosorbi.de fatty esters, and ~ .
approximately equal amounts of free fatty acid~ free eorbitol, free sorbitan, minor proportions of iso-~ sorbide, about 31% by weight of the mixtuxe comprising : *Trademark ' :' .

~1~7136(~

sorbitan monoesters) is placed in a trough and heated until melted.
A 10-inch wide roll o paper substrate, said substrate ~eing a compressible, laminated and calendered 5 absorbent paper structure comprising two extensible paper sheets, each sheet (or ply3 ha~ing a basis weight of about 16 lbs. per 3iOOO square feet and a MD value of about 660, a CD value of about 380 and 20% dry-crepe is used as the ~arrier. ~ach sheet of the paper substrate is ambossea wi~h identical raised patterns consisting of about 70 inwardly dire~ted discrete protuberances per square inch, raised about 0.02 inches above the surface of the paper sheets.
The protuberances constitute about 45% of the surface of each sheet and are mated and adhesively joined with polyvinyl alcohol resin. The paper structure exhibits a compressive modulus of about 340 together with HOM
~- MD/CD values of about 36/31 and has an absorbent .
capacity of about 7. ~This paper is a par~icularly preferred paper substrate herein and weighs about 3.7 grams per 11 inch x 12 inch sheet.~
The paper sheet substrate is mounted on a roll and is unrolled in the trough. The paper travels at - .
a rate of 5-6 eet per minute and is then directed ~5 upwardly and through the pair of hard, rubber rollers mounted so that their surfaces just touch. The turning rollers squeeze off excess softener liquid ~-and impregnate the paper~with the softener at a ~oftener:paper impregnation ratio of ca. 207~1 by ,,:

:
, .- . ., ': ~' .. - .' , :

~7~36~

weight of the dry, untreated paper~
DRY-FLo starch (avg. particle diameter 10 ~m) is blown onto the warm softener-impregnated substrate at an angle perpendicular to the plane of the substrate using air pressure of ca. 30 psia. The starch is applied at a starch:substrate weight ratio of ca. 2:1.
~ he impinging stream o* air/starch affixes the starch xeleasably ~o the surface of the softener-~ impregnated paper and concurrently cools and solidifies the softener. The resulting paper article is substantially~olid, yet flexible, is stable to decomposition, not "runny" or dripping, and which, although waxy to the touch, does not s~ick together when folded.
An 11 in. x 12 in. paper-impxegnated article prepared in the foregoing manner is punched with 9 ev~nly-spaced O r S in. diameter holes. The article is placed in an automatic clothes dryer together with S lbs~ of mixed clothes which are dampened with an equal amount of water. The dryer is operated at an average temperature of 56C for a period of 40 minutes, with tumbling. At the end of the drying cycleO the dry clothing has an improved appearance and handle, is easy to iron. No substantial staining of the .
i' ' .

: ~
i `:
~ - 62 - Z

, .

~7136~

~abrics is observed. The dryer operates without any vent blockage.
In the foregoing article the SPAN 60 is replaced by an equivalent amount of SPAN ~0* (the corresponding 5 complex mixture of sorbitan palmitates marketed by - ICI) and equivalent results are secured. An article according to Example II is prepared us ing an e~uivalent amou~t of m~xed sorbitan stearates and ~ palmitates prepared by mixing the SPAN 60 and SPAN 40 a~ weight ra~ios of SPAN 60:SPP,N 40 of lO:l, 5~
2 1: 1~2, l:S, and 9 :10, reepectively, and equivalent results are secured.
An article according to Example II is prepared using an equivalent amount of dicoconutalky'dim.~th~
ammonium methylsulfate, ditallowalkyldimethylammonium chloride and ditallowalkyldimethylammonium bromide, respectively, to replace the ditallowalkyldimethylammonium methylsulfate, and equivalent fabric conditioning benefits are secured.
,.

EX~MPLE~
A non-staining dryer-added softener article is as follows. DURTAN 60** (Durkee Foods; comprising greater than 30% by weight stearic and palmitic acid este~s of sorbitan, free stearic acid, free palmitic acid, 2~ free sorbitol, free sorbitan and minor amounts of ' .-isocor~ide and esters t~,ereof, 10 grams) i5 added to , " .
25 mls. of isopropyl alcohol. Ditallowalkyldimethyl-ammonium methylsulfate (0.5 gram), 0.1 g. of mixed *Trademark **Trademark ~13~

coconut alcohol ethoxylates ~aving an average degree of ethoxylation of 6, and 0.01 g. of perfume are added to the mixture. DRY-FLO starch (avg. diameter 10 ~m; 1.5 grams) is added and the mixture is stirred and warmed to a~out 35C to provide a free flowing slurry of the fabric treating components.
The substrate used is an 11 in. x 12 in.
water-laid, no~-woven cloth commercially avai~able from the C. H. Dexter Co., Inc.. comprising fibers of regenerated cellulose/ about 3/8 in. in length~ about 1.5 denier, and lubricated with a standard ~extile lubricant. The ~ibers comprice about 70% of the non-woven cloth by weight and are oriented sub~
s~antially haphazardly; a binder-resin("~oPl~ HA-8) ~ses l about 30O~ by weight of the cloth. The cloth is about 4 mils thick, has a basis weight of about 24 grams per square yard and an absorbent capacity of 5.7.
One foot length of the cloth, 8-1/3 inches wide, - weighs about 1.66 grams.
The substrate cloth is placed in a shallow trough and is sprayed uniformly with the above-described isopropyl alcohol mixture. Four separate sprayin~s are used, i.e., each spraying uses ca i~4 of the above-described mixture. The isopropvl alcohol is allowed to evaporate from the substrate after each spraying~ A~ter the final spraying, the article is allowed to dry at room temperature, overnight. The ~inal article is substantially free from isopropyl .
~ 64 -: .-', ' , ' :' ~ .

11D7~36CI
.
alcohol, is flexible, and contains ~he fabric treating components uniformly and releasably impregnated through-out the substrate free space and on its surface.
The article prepared in the foregoing manner is placed in an automatic dryer together with 5.5 lbs. of damp (3 lbs. water) clothes and the dryer is operated with tumbling at an average temperature of 65C for a period of 35 minutes. On removal from the dryer, the clothes are found to be provided with ~ a uniform soft and anti~static finish, are easy to iron, and are substantially stain-free.
- The article of Example III is modified by xeplacing the DRY-FLO starch with an equivalent amount of PF-ll glass beads ~as described above), glass micro~alloons ~avg. diameter 30 ~m), polystyrene spheroid beads (avg. diameter 14-16 ~m), and poly(styrenedivinylbenzene) spheres (avg. diameter -~ 6 ~m), respectively, and equivalent fabxic conditioning 'I results are secured.
,1 .
; 20 EXAMPLE_IV
Cornstarch ~ungelatinized, average particle diameter 20 ~m: anisotropy ca. 1.1) 200 grams, is suspended in anhydrous diethyl ether. Stearoyl chloride, 20 g., is added to the suspension ~f corn-starch, with agitation. The mixture is refluxed for 1 hour, after which the starch particles are recovered .
by filtration. The starch particles, which are ' O . .
:, ~L~7~36~

rendered hydrophobic by virtue of their esterification with the stearoyl chloride, are placed in vacuo to remove remaining traces of ether.
A dryer-added fabric conditioning article is S prepared in the following manner. A sheet of non-woven rayon cloth, 10 inches square, is uniformly impregnated and oated with a syrupy aqueous solution of ood-grade gelatin at a weight ratio of cloth:gelatin of 1:1.
Following this treatment, and while the gelatin is still acky, l.S grams of the stearylated cornstarch prepared in the foregoing manner is uniformly blown over both sides of the cloth. Following this, the cloth is blown dry using a stream of 30C dry air.
The resulting article is flexible and retains the starch granules releasably on its surface.
An article prepared in the foregoing manner is placed together with 5 lbs. of damp (spun dry) fabrics in an automatic clothes dryer. The dryer is operated i at an average temperature of 57C over a period of 40 ; 20 minutes. After this time, the fabrics are removed from the dryer and are found to be provided with an anti~wrinkling finish which is substantially easier to iron than corresponding untreated ~abrics.
In the article of Example IV, the stearylated cornstarch is replaced by an equivalent amount of stearylated rice starch, and equivalent results are secured.

.

~- :

- .. .. . . ~ ,. . ~ . . -. - . .:

~7~

In the article of Example IV, the surface-modified (stearylated) starches are replaced by an equivalent amoun. of cornstarch, wheat staxch and rice starch, said starches being ungelatinized and char-acterized by a swelling power of less than about lSat a temperature of 65C, substant~'al water-insolubilit~, and a particle size witnin t~e range of about lS ~m to about 25 YmJ and equivalent fabric conditioning results are secured.

, . .

~ : I

.
~:

~ . .. ... . : . - . . . ~ . ., . ~ . .. .. . . .

.: . ; . :. . : , . ~ :. . ~, .

Claims (17)

The embodiments of the invention in which an exclusive property or privilege is claimed are defined as follows:

1. A fabric treating article especially adapted for use in an automatic dryer, comprising:
(a) a fabric conditioning amount of a water-insoluble particulate material characterized by:
(i) an average particle size of from about 1.0 µm to about 50 µm;
(ii) a shape having an anisotropy of from about 5:1 to about 1:1;
(iii) a hardness of less than about 5.5 on the Mohs scale;
(iv) a melting temperature above about 150°C; and (v) substantial freedom from exchangeable calcium and magnesium ions, said particulate material being in releasable combination with:
(b) a water-insoluble dispensing means.

2. An article according to Claim 1 which comprises from about 1 gram to about 7 grams of the particulate material.

3. An article according to Claim 1 wherein the particulate material is selected from the group consisting of surface-treated starches, glass micro-balloons, glass beads, and water-insoluble starches having a swelling power of less than about 15 at a temperature of 65°C.

4. An article according to Claim 1 wherein the dispensing means is in a sheet conformation.

5. An article according to Claim 4 wherein the dispensing means is selected from water-insoluble paper, woven cloth or non-woven cloth substrates.

6. An article adapted for concurrently softening and conditioning fabrics in an automatic clothes dryer, comprising:
(a) a softening amount of a fabric softener characterized by a molting point above about 38°C
(b) a fabric conditioning amount of a substantially water-insoluble particulate material character-ized by:
(i) an average particle size of from about 1.0 µm to about 50 µm;
(ii) a shape having an anisotropy of from about 5:1 to about 1:1:
(iii) a hardness of less than about 5.5 on the Mohs scale;
(iv) a melting temperature above about 150°C: and (v) substantial freedom from exchange-able calcium and magnesium ions;
said softener and said particulate material being in releasable combination with;
(c) a water-insoluble dispensing means.

7. An article according to Claim 6 wherein the fabric softener is a quarternary ammonium salt having two C10-C20 fatty alkyl substituents.

8. An article according to Claim 7 wherein the quaternary ammonium salt is selected from ditallow-alkyldimethylammonium methylsulfate, dicoconutalkyl-dimethylammonium methylsulfate, and mixtures thereof

9. An article according to Claim 6 wherein the fabric softener is selected from C10-C22 alkyl mono- and di-sorbitan esters, and mixtures thereof.

10. An article according to Claim 9 wherein the sorbitan esters are selected from the group con-sisting of sorbitan monolaurate, sorbitan monomyristate, sorbitan monopalmitate, sorbitan monostearate, sorbitan dilaurate, sorbitan dimyristate, sorbitan dipalmitate, sorbitan distearate, and mixtures thereof, and mixed coconutalkyl sorbitan mono- and di esters and mixed tallowalkyl sorbitan mono- and di-esters.

11. An article according to Claim 6 wherein the fabric softener is a member selected from the group consisting of quaternary ammonium salts containing two C10-C20 alkyl substituents, C10-C22 alkyl sorbitan mono- and di-esters, and mixtures thereof, and wherein the particulate material is selected from substantially water-insoluble surface-treated starches or starches having a swelling power of less than about 15 at a temperature of 65°C.

12. An article according to Claim 6 wherein the dispensing means is in a sheet conformation.

13. An article according to Claim 12 wherein the dispensing means is selected from water-insoluble paper, woven cloth or non-woven cloth sheets.

.

14. An article according to Claim 13 wherein the sheets are provided with slits or holes.

15. An article according to Claim 14 wherein the water-insoluble particulate material is a surface-treated starch or a starch having a swelling power of less than about 15 at a temperature of 65°C, and wherein the fabric softener is selected from C10-C22 mono- and ' di-alkyl sorbitan esters, and mixtures thereof.

16. An article according to Claim 14 wherein the water-insoluble particulate material is a surface-treated starch or a starch having a swelling power of less than about 15 at a temperature of 65°C, and wherein the fabric softener is a quaternary ammonium salt selected from ditallowalkyldimethylammonium methyl-sulfate, dicoconutalkyldimethylammonium methylsulfate, and mixtures thereof.

17. An article according to Claim 14 wherein.
the water-insoluble particulate material is a surface-treated starch or a starch having a swelling power of less than about 15 at a temperature of 65°C, and wherein the fabric softener comprises a mixture of quaternary ammonium salts and sorbitan esters, said quaternary ammonium salts being characterized by two C10-C20 alkyl substituents, or mixtures thereof, said ammonium salts being in the methylsulfate form, and wherein the sorbitan esters are selected from the C10-C22 alkyl sorbitan mono- and di-esters, and mixtures thereof.