CA1268302A - Article for conditioning fabrics in a clothes drier - Google Patents
Article for conditioning fabrics in a clothes drierInfo
- Publication number
- CA1268302A CA1268302A CA000320190A CA320190A CA1268302A CA 1268302 A CA1268302 A CA 1268302A CA 000320190 A CA000320190 A CA 000320190A CA 320190 A CA320190 A CA 320190A CA 1268302 A CA1268302 A CA 1268302A
- Authority
- CA
- Canada
- Prior art keywords
- substrate
- article
- conditioning
- fabric
- agent
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired
Links
Classifications
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06F—LAUNDERING, DRYING, IRONING, PRESSING OR FOLDING TEXTILE ARTICLES
- D06F58/00—Domestic laundry dryers
- D06F58/20—General details of domestic laundry dryers
- D06F58/203—Laundry conditioning arrangements
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M23/00—Treatment of fibres, threads, yarns, fabrics or fibrous goods made from such materials, characterised by the process
Abstract
ABSTRACT OF THE DISCLOSURE
There is provided an article useful in the conditioning of recently washed fabric in a laundry dryer.
More particularly, it relates to an improved fabric conditioning article in the form of a flexible substrate carrying a conditioning agent removable to fabrics in a laundry dryer, said conditioning agent being applied to the substrate, preferably a non-woven, substantially porous substrate, in a discontinuous pattern.
There is provided an article useful in the conditioning of recently washed fabric in a laundry dryer.
More particularly, it relates to an improved fabric conditioning article in the form of a flexible substrate carrying a conditioning agent removable to fabrics in a laundry dryer, said conditioning agent being applied to the substrate, preferably a non-woven, substantially porous substrate, in a discontinuous pattern.
Description
~6~30~
BACKGROUND OF THE INVENTION
Description of the Prior Art The employment of fabric-conditioning articles to impart softening, antistatic, lubricating, 5 bacteriostatic mildew-proofing or other desirable fabric-conditioning effects has been described in the art. For example, U.S. Patent No. 3,442,692 to Gaiser ~May 6, 1969) describes the conditioning of fabrics in a laundry dryer by cotumbling the fabrics with a flexible substrate 10 carrying a conditioning agent. The conditioning agent is removed to the tumbling fabrics to provide a ~abric conditioning which otherwise might only inconveniently be effected by treatment -- for example, during the rinsing cycle of a laundering operation. Similarly, U.S. Patent No. 3,686,025, issued August 22l 1972 ~o Morton and U.S. Patent No. 3,956,S56 issued May 11, 1968 and U.S.
Patent No. 4,007,300 issued February 8, 1977 to McQueary, describe an article for conditioning fabrics in a laundry dryer. The articles comprise an absorptive substrate impregnated with a fabric-softening agent for the provision of fabric softening effects with minimal staining tendencies.
U.S. Patent No. 3,956,556, issued May 11, 1976, a~d the divisional thereof, U.S. Patent No. 4,00 7,300, issued Februaxy 8, 1977, both to McQueary, addressed themselves to a further problem in this partic;:ular art --namely, the tendency of an absorbed fabric conditioner substrate to adhere to the air outlet of the dryer which, if not rapidly unblocked, caused excessive heat build-up and possible burn-out o certain portions o the dryer.
Mc~2ueary addresses this problem by providing a plurality of perforations in the substrate so as to permit at least 70~ of the normal air 10w through the dryer when the coated subs~rate i~3 used therein. A similar approach to ~L26E~ Z
the same end is set forth in another McQueary patent, U.S. Patent No. 3,944,694, wherein the flexible substrate is provided with a plurality of slits in order to achieve the desired volume of air flow.
It should be noted that in the known prior art, which includes not only the above referenced patents but also those cited therein, the substrate which is preferably, but not solely, a non-woven material is coated by a process of dipping the substrate in a solution or dispersion of the conditioning agent. Indeed, McQueary, as in U.S. Patent No. 3,956,55~, column 6, lin~ 45 et seq, teaches that the manner of impregnating the substrate is not considered to be an important part of her invention~
The conditioning articles of the prior art, including in particular those made in accordance with the preferred or exemplified embodiments of the above identified patent, while operative, have two disadvantages which it would be desirable to avoid.
The coating technique employed covers the entire substrate and, therefore, utilizes a great deal of fabric conditioning agent, which agen-t constitutes a substantial portion of the material cost of the article. It would, therefore, be desirable to provide an operative articl2 utilizing a lesser amount of the conditionin~ agent.
The articles of the prior art have a tendency to crumple. Indeed, this quality is stated at McQueary, U.S. Patent No. 3~956/556~ column 7, lines 34 through 47, as being a desirable quality. While the reasons for the desirability of crumpling are understood, they carry with them the concomitant disad~antage that an article which has the tendency to crumple e~ually has a tendency to fold, as is admitted in McQueary, and, thus, in the ~olded condition does not offer the same amount of surface exposuxe to the clothlng which it is inten~ed to contact as would a softer and more flexible material which did not , ~2~i~3302 possess the crumpling properties.
It would, therefore, be desirable to pro~ide an article which has, in addition to the desirable qualities of the articles of prior art, the additional advantages of lower conditioning agent requirement together with a non-crumple quality while, at the same time, permitting the clearly desired volume of air to continue to pass through the dryer even under those conditions where the conditioning article is held up against the air exit vent of a dryer.
It should be noted that McQueary, U.S. Patent No. 3,956,556, at column 7~ lines 66 th.rough 68, mentions that the device disclosed and claimed in said patent possesses perforations which need not necessarily be cut into the substrate, but which could, it is alleged, be the result of the porousity or air permeability of the particular substrate material employed in its manufacture.
It should be noted, however, that the method o~
manufacture of the article disclosed therein is such as to effectively negate the air permeability of the substrate unless a perforation of substantial size, say 1/8" or more~ was inserted into the substrate prior to coating.
SUMM~RY_OF THE INVENTION
The present invention, in its article aspects, is directed to a fabric conditioning article comprising a substrate having a fabric conditioning agent applied to at least one surface thereof in a discontinuous or substantially discontinuous manner. The term "discontinuous" as used herein means that certain portions o~ the subskrate are coated with the conditioning agent and certain portions are not. Thus, if a line is drawn at random across the article in any manner other than along the axis of a straight line strip of conditioning material as applied to the substrate, said ~l~6~3~3~
line will cross both coated and uncoated portlons of the article.
There is thus provided an article comprising a substrate partially coated with conditioning agents. The substrate chosen i5 a material which, due to its normal structure, permits a substantial flow of air therethrough.
Non-woven fabrics well known in the art are especially suitable for this purpose. The conditioning agent is applied to the substrate suitably by printing in a pre-determined pattern, the sole criterion of the pattern being that it shall leave enough unoccupied area on the substrate to provide the necessary degree of air flow therethrough in operation in a conventional laundry dryer, In its method aspect, the invention provides, in the conditioning of fabrics, the addition of softening agents thereto in the step of co-mingling the fabrics to be conditioned with a substrate carrying the conditioning agent removable to the fabrics and having sufficient inherent interstices therein to provide for a satisfactory volume of air flowing therethrough.
The fabrlc~conditioning article comprises a flexible web, such as paper or cloth, carrying a conditioning agent, such as a fabric softening agent, and is normally made up into a tubular roll or individual sheets, A desired length of the treated web is torn off the roll or a sheet remov~d from its package and placed into the clothes dryer wherein the fabrics to be treated have been loaded. The dryer is then operated in customary fashion, and fabric conditioning occurs as the fabrics directly contact the treated web, whereby the conditioning agent is transferred from the web substrate to tha fabric, Particularly when small fabric loads are tumbled and the probability o~ a tumbling fabric-conditionin~ article of making repeated, or prolonged, contact with a laundry dryer exhaust outlet is enhanced, the perforations, or openings, in the treated web advantageously minimize the , ~z~o~
interruption of air flow through the dryer. This is ef~ected by passage of air through the natural interstices in the web on those portions of the web not coated with the conditioning agent.
BRIEF DESCRIPTION OF THE DRAWINGS
Figure 1 is a side elevational view of the article of the present invention (not to scale: verticle scale substantially expanded).
Figure 2 is a plan view of the article of Figure 1 viewed from 2-2.
Figure 3 is a plan view of a preferred embodiment of the invention~
Figure 4 is a plan view of an embodiment of the invention.
Figure 5 is a plan view of yet another embodiment of the invention showing fabric conditioner printed on both sides.
Figure 6 is a side elevational view of the embodiment of Figure 5 viewed from 6-6 (not to scale:
substantially expanded vertically).
Figure 7 is a side elevational view showing two sheets of Figure 1 sealed to each other at either end.
The drawings show samples of possible embodiments of the invention. Three and four digit numbers ending in a particular two digits signify the same type o~ member as the members carrying said two digits.
Figures 1 and 2 show a stripped embodiment where strips of conditioner 14 are printed on one side only of substrate 12. In the illustrated embodiments substrate 12 is an "open weave" non-woven fabric through which air may readily pass at those portions not carrying aonditioner 1~ .
Figure 3 shows a substrate 112 carrying a ...
~ILZ683(~2 plurality of dots 114.
Figure 4 shows a substrate 312 carrying a checker pattern 314.
Figure 5 shows a substrate 212 carrying wavy pattern 214 on one side and wavy pattern 2214 on the other.
Figure 7 shows two sheets 12 with strips 14 on one surface ~ed together with heat seals 16 at either end. An embodiment similar to this one, but using th~
dotted embodiment of Figure 3, is utilized in one of the comparative test procedures set forth in the Examples.
DESCRIPTION OF THE PREFERRED EMBODIMENT
The fabric conditioning articles of the invention comprise a flexible web substrate carrying a conditioning agent. Suitable suhstrate materials for carrying the conditioning agent include a variety of natural or synthetic substrate materials. Suitable substrates are those which have the ability to retain a fabric-conditioning agent in a form which is releaseable ;~
to fabrics tumbled therewith, and which h~ve a resistance to shredding or other tearing failures when tumbled with damp clothes in a dryer. Examples of suitable substrates include paper towelling, swatches of woven and non-woven cloth, papers/ sponges, plastics and felts. Fibrous materials can be natural or synthetic but are preferably cellulose. Foæm plastic web materials, such as the polyurethanes, can also be employed.
In one embodiment of the invention, a substrate which i9 relatively impermeable to the fabric-conditioning ~0 agent is employed so as to dispose the fabric-conditioning agent onto the substrate as a discrete surface coating.
Wet strength papers, regenerated cellulose, rayon, nylon, polyester, polyacrylonitrile, polyole~in and other synthetic woven or non-woven fibrous materials are .~ .
lZ~3t:~
suitable for this purpose. Wet strength paper is suitably employed and can be treated with a waterproo~ing or sizing material such as a thermosetting resin, starch or other impregnant, having the effect of reducing water absorption by fibrous cellulosic products, and allowing the formation of a coating of conditioning agent. Waxy papers which carry coatings or impregnations of paraffin or microcrystalline or synthetic wax can be used -- for example, "butcher paper" or dry waxed paper -- to the extent of reducing moisture absorption but permitting adherent coating of the paper with conditioning agent.
Wet strength papers, such as Kraft or bond papex, can be employed.
Preferred articles of the invention include those formed from a substrate having an absorption capacity in relation~ for example, to fabric softening agents as to provide an impregnated article capa~le of controllably releasing the softening agent to treated fabrics. Improved softness or feel of the treated fabrics is provided without overdosing or lo~alized concentration of softener in the form of spots or stains. Suitable absorbent substrate materials are described in considerable detail in U.S. Patent No. 3,686,025, issued August 22, 1972, to Morton.
While Morton teaches that an absorbant capacity of 5.5 through 12, as defined therein, is desirable for practicing the invention disclosed by him, it has been our finding that, in the present invention, substra~es having absorbencies substantially lower than 5.5 are entirely satisfactory and, indeed, constitute the pre~erred embodiment of the present invention.
While not limiting the invention thereto, the reason for this finding is that, while in the prior art it would appear that the conditioning agent is absorbed into the fiber of the substrate and held therein and ~Z~i~3~
between the interstices between the fibers. In the articles of the present invention the conditioning agent is, in ef~ect, placed u~on the substrate; in that the use of a finer denia fiber provides sufficient absorbency before the interstices only so that a very minimal amount of absorbency is adequate for the purposes of the present invention.
Preferred ahsorbent substrates are cellulosic materials such as multi-ply paper towel and non-woven cloth substrates. Preferred paper towel materials and their method of manufacture can be found in U.S. Patent No. 3,414,459, issued December 3, 1968, to Wells.
Preferred non-woven cloth substrates can be generally defined as adhesively-bonded fibrous or filamentous products having a web structura, in which the fibers or ~ilaments are distributed haphazardly, as in the "wet lay" processes, or with a degree of orientation, as in the "carding"
process. Such substrates exhibit desirable strength in all directions and are rasistant to shredding or tearing failures when tumbled with damp fabrics. The ~ibers or rilaments of such non-woven cloth substrates can be natural (for example, wool, silk, jute, hemp, cotton, linen, sisal or ramie) or syn-thetic (~o~ example, rayon, cellulose ester, polyvinyl derivatives, polyolefins, polyamides or polyesters) and bonded together with a polymetric binder resin such as polyvinyl acetate. While the invention is in no way limited thereto, it has been ~ound that the most satisfactory results are obtained using polyester ~ibers. ~hese ~ibers have the advantage, in the context o~ the present invention, of being so~ter, not as absorbent, and have the ability to be produced in a whiter - i.e., more hygenic appearing -- form than those materia1s which are dis~losed by t~e prior art and are presently to be found in t~e channels o commerce.
The factor of softness is advantagaous as it lZ683~2 tends to counter the crumpling and folding efects which were presen~, and indeed believed to be desirable, in the articles of the prior art. The softer touch, as well as the whiter appearance of the polyester fiber, are 5 considered to be specific advantages in a product closely related, in the mind of the consumer, with hygenic matters. The preferred, though not critical, range of absorbency of the materials used herein is between 100 and 500~. This lower absorbency has the advantage of permitting the easier removal of the conditioning agent to the fabric which it contacts in the dryer. This ratio of removability contributes to the efficiency of the present met~od since, inherently then, less material is required. Such substrates will normally have a void volume of from about 20% to about 80~ to provide desirable air flow properties.
The conditioning agents employed herein include any of a ~ariety of agents employed generally in textile treating operations. Accordingly, fabric softening anti-static, anti-mildew, germicidal, mothproofing and anti-wrinkling agents, perfumes and the like can be employed.
The most universal preference, however, is for agents which act to so~ten ~abrics or otherwise improve their feel or hand. Softening agents which also have anti-static properties and which reduce sta~ic charge or ~abxiccling are especially preferred.
Typically, the fabric softening agents that can be employed are compounds having a relati~ely-long hydrocarbon group serving to provide hydrophobicity or lubricity. Among such groups axe alkyl groups containing 8 or more carbon atoms and preferably from 12 to 22 carbon atoms. Suitable fabrlc softening agents include cationic, anionic, nonionic, or zwitterionic compounds. Cationic fabric-sotenlng agents include the cationic nitrogen-containin~ compounds such as quaternary ammonium compoundsand amine which ha~e one or two straight-chain or~anic .
~Z61~3~Z
groups of at least 8 carbon atoms. Preferably, they have one or two such groups of ~rom 12 to 22 carbon atoms.
Preferred cation-active softener compounds include the quaternary ammonium softener compounds corresponding to the formula G~X-,-'..
wherein R is hydrogen or an aliphatic group of from 12 to 22 carbon atoms; Rl is an aliphatic group having from 12 to 22 carbon atoms; R2 and R3 are each alkyl groups of from 1 to 3 carbon atoms; and X is an anion selected from halogen, acetate phosphate, nitrite and methyl sulfate radicals.
Because of their excellent softening e~icacy and ready availability, preferred cationic softener compounds of the invention are the dialkyl dimethyl ammonium chlorides, wherein the alkyl groups have rom 12 to 22 carbon atoms and are derived from long-chain fatty acids such as hydrogenated tallow. As employed herein, alkyl is intended as including unsakurated compounds such as are present in alkyl groups derived from naturally occurring fatty oils. The term "tallow" refers to fatty alkyl groups derived from tallow fatty acids. Such fatty acids give rise to quaternary softener compounds wherein R and R~ have predominantly from 16 to 18 carbon atoms.
The term "coconut" refers to fatty acid groups ~rom coconut oil fatty acids. The coconut-alkyl R and R
~2~i~33~;2 gxoups have from about 8 to about 18 carbon atoms and predominate in C12 to C14 alkyl groups. Representative examples of quaternary softeners of the invention include tallow trimethyl ammonium chloride; ditallow dimethyl ammonium chloride; ditallow dimethyl ammonium methyl sulfate; dihexadecyl dimethyl ammonium chloride;
di(hydrogenated tallow)dimethyl ammonium chloride;
dioctadecyl dimethyl ammonium chloride; dieicosyl dimethyl ammonium chloride; didocosyl dimethyl ammonium chloride;
di(hydrogenated tallow)dimethyl ammonium methyl sulfate;
dihexadecyl diethyl ammonium chloride; dihexadecyl diethyl ammonium chloride; dihexadecyl dimethyl ammonium acetate; ditallow dipropyl ammonium phosphate; ditallow dimethyl ammonium nitrite; di(coconut-alkyl)dimethyl ammonium chloride.
Suitable cation-active amine so~tener compounds are the primary, secondary and tertiary amine compounds having at least one straight-chain organic group of from 12 to 22 carbon atoms and 1,3-propylene diamine compounds having a straight-chain organic group of from 12 to 22 carbon atoms. Examples of such softener actives include primary tallow amine' primary hydrogenated-tallow amine;
tallow 1,3-prop~lene diamine; oleyl 1,3-propylene diamine; coconut 1,3-propylene diamine; soya 1,3-propylene diamine; and the like.
Other suitable cation-active softener compounds herein are the quaternary imidazolinium salts. Preferred salts are those conforming to the formula ~f~ ~
~LZ683~;Z
wherein R6 is an alkyl containing from 1 to 4, preferably from 1 to 2, carbon atoms; R7 is an alkyl containing from 1 to 4 carbon atoms or a hydrogen radical; R8 is an alkyl containing from 8 to 22, preferably at least 15, carbon atoms; R5 is hydrogen or an alkyl containing from 9 to 22, preferably at least 15, carbon atoms; and X is an anion, preferably methyl sulfate or chloride ions. Other suitable anions include those disclosed with reference to the cationic quaternary ammonium ~abric softeners described hereinbefore. Particularly preferred are those imidazolinium compounds in which both R5 and R8 are alkyls of from 12 to 22 carbon atoms -- for example,
BACKGROUND OF THE INVENTION
Description of the Prior Art The employment of fabric-conditioning articles to impart softening, antistatic, lubricating, 5 bacteriostatic mildew-proofing or other desirable fabric-conditioning effects has been described in the art. For example, U.S. Patent No. 3,442,692 to Gaiser ~May 6, 1969) describes the conditioning of fabrics in a laundry dryer by cotumbling the fabrics with a flexible substrate 10 carrying a conditioning agent. The conditioning agent is removed to the tumbling fabrics to provide a ~abric conditioning which otherwise might only inconveniently be effected by treatment -- for example, during the rinsing cycle of a laundering operation. Similarly, U.S. Patent No. 3,686,025, issued August 22l 1972 ~o Morton and U.S. Patent No. 3,956,S56 issued May 11, 1968 and U.S.
Patent No. 4,007,300 issued February 8, 1977 to McQueary, describe an article for conditioning fabrics in a laundry dryer. The articles comprise an absorptive substrate impregnated with a fabric-softening agent for the provision of fabric softening effects with minimal staining tendencies.
U.S. Patent No. 3,956,556, issued May 11, 1976, a~d the divisional thereof, U.S. Patent No. 4,00 7,300, issued Februaxy 8, 1977, both to McQueary, addressed themselves to a further problem in this partic;:ular art --namely, the tendency of an absorbed fabric conditioner substrate to adhere to the air outlet of the dryer which, if not rapidly unblocked, caused excessive heat build-up and possible burn-out o certain portions o the dryer.
Mc~2ueary addresses this problem by providing a plurality of perforations in the substrate so as to permit at least 70~ of the normal air 10w through the dryer when the coated subs~rate i~3 used therein. A similar approach to ~L26E~ Z
the same end is set forth in another McQueary patent, U.S. Patent No. 3,944,694, wherein the flexible substrate is provided with a plurality of slits in order to achieve the desired volume of air flow.
It should be noted that in the known prior art, which includes not only the above referenced patents but also those cited therein, the substrate which is preferably, but not solely, a non-woven material is coated by a process of dipping the substrate in a solution or dispersion of the conditioning agent. Indeed, McQueary, as in U.S. Patent No. 3,956,55~, column 6, lin~ 45 et seq, teaches that the manner of impregnating the substrate is not considered to be an important part of her invention~
The conditioning articles of the prior art, including in particular those made in accordance with the preferred or exemplified embodiments of the above identified patent, while operative, have two disadvantages which it would be desirable to avoid.
The coating technique employed covers the entire substrate and, therefore, utilizes a great deal of fabric conditioning agent, which agen-t constitutes a substantial portion of the material cost of the article. It would, therefore, be desirable to provide an operative articl2 utilizing a lesser amount of the conditionin~ agent.
The articles of the prior art have a tendency to crumple. Indeed, this quality is stated at McQueary, U.S. Patent No. 3~956/556~ column 7, lines 34 through 47, as being a desirable quality. While the reasons for the desirability of crumpling are understood, they carry with them the concomitant disad~antage that an article which has the tendency to crumple e~ually has a tendency to fold, as is admitted in McQueary, and, thus, in the ~olded condition does not offer the same amount of surface exposuxe to the clothlng which it is inten~ed to contact as would a softer and more flexible material which did not , ~2~i~3302 possess the crumpling properties.
It would, therefore, be desirable to pro~ide an article which has, in addition to the desirable qualities of the articles of prior art, the additional advantages of lower conditioning agent requirement together with a non-crumple quality while, at the same time, permitting the clearly desired volume of air to continue to pass through the dryer even under those conditions where the conditioning article is held up against the air exit vent of a dryer.
It should be noted that McQueary, U.S. Patent No. 3,956,556, at column 7~ lines 66 th.rough 68, mentions that the device disclosed and claimed in said patent possesses perforations which need not necessarily be cut into the substrate, but which could, it is alleged, be the result of the porousity or air permeability of the particular substrate material employed in its manufacture.
It should be noted, however, that the method o~
manufacture of the article disclosed therein is such as to effectively negate the air permeability of the substrate unless a perforation of substantial size, say 1/8" or more~ was inserted into the substrate prior to coating.
SUMM~RY_OF THE INVENTION
The present invention, in its article aspects, is directed to a fabric conditioning article comprising a substrate having a fabric conditioning agent applied to at least one surface thereof in a discontinuous or substantially discontinuous manner. The term "discontinuous" as used herein means that certain portions o~ the subskrate are coated with the conditioning agent and certain portions are not. Thus, if a line is drawn at random across the article in any manner other than along the axis of a straight line strip of conditioning material as applied to the substrate, said ~l~6~3~3~
line will cross both coated and uncoated portlons of the article.
There is thus provided an article comprising a substrate partially coated with conditioning agents. The substrate chosen i5 a material which, due to its normal structure, permits a substantial flow of air therethrough.
Non-woven fabrics well known in the art are especially suitable for this purpose. The conditioning agent is applied to the substrate suitably by printing in a pre-determined pattern, the sole criterion of the pattern being that it shall leave enough unoccupied area on the substrate to provide the necessary degree of air flow therethrough in operation in a conventional laundry dryer, In its method aspect, the invention provides, in the conditioning of fabrics, the addition of softening agents thereto in the step of co-mingling the fabrics to be conditioned with a substrate carrying the conditioning agent removable to the fabrics and having sufficient inherent interstices therein to provide for a satisfactory volume of air flowing therethrough.
The fabrlc~conditioning article comprises a flexible web, such as paper or cloth, carrying a conditioning agent, such as a fabric softening agent, and is normally made up into a tubular roll or individual sheets, A desired length of the treated web is torn off the roll or a sheet remov~d from its package and placed into the clothes dryer wherein the fabrics to be treated have been loaded. The dryer is then operated in customary fashion, and fabric conditioning occurs as the fabrics directly contact the treated web, whereby the conditioning agent is transferred from the web substrate to tha fabric, Particularly when small fabric loads are tumbled and the probability o~ a tumbling fabric-conditionin~ article of making repeated, or prolonged, contact with a laundry dryer exhaust outlet is enhanced, the perforations, or openings, in the treated web advantageously minimize the , ~z~o~
interruption of air flow through the dryer. This is ef~ected by passage of air through the natural interstices in the web on those portions of the web not coated with the conditioning agent.
BRIEF DESCRIPTION OF THE DRAWINGS
Figure 1 is a side elevational view of the article of the present invention (not to scale: verticle scale substantially expanded).
Figure 2 is a plan view of the article of Figure 1 viewed from 2-2.
Figure 3 is a plan view of a preferred embodiment of the invention~
Figure 4 is a plan view of an embodiment of the invention.
Figure 5 is a plan view of yet another embodiment of the invention showing fabric conditioner printed on both sides.
Figure 6 is a side elevational view of the embodiment of Figure 5 viewed from 6-6 (not to scale:
substantially expanded vertically).
Figure 7 is a side elevational view showing two sheets of Figure 1 sealed to each other at either end.
The drawings show samples of possible embodiments of the invention. Three and four digit numbers ending in a particular two digits signify the same type o~ member as the members carrying said two digits.
Figures 1 and 2 show a stripped embodiment where strips of conditioner 14 are printed on one side only of substrate 12. In the illustrated embodiments substrate 12 is an "open weave" non-woven fabric through which air may readily pass at those portions not carrying aonditioner 1~ .
Figure 3 shows a substrate 112 carrying a ...
~ILZ683(~2 plurality of dots 114.
Figure 4 shows a substrate 312 carrying a checker pattern 314.
Figure 5 shows a substrate 212 carrying wavy pattern 214 on one side and wavy pattern 2214 on the other.
Figure 7 shows two sheets 12 with strips 14 on one surface ~ed together with heat seals 16 at either end. An embodiment similar to this one, but using th~
dotted embodiment of Figure 3, is utilized in one of the comparative test procedures set forth in the Examples.
DESCRIPTION OF THE PREFERRED EMBODIMENT
The fabric conditioning articles of the invention comprise a flexible web substrate carrying a conditioning agent. Suitable suhstrate materials for carrying the conditioning agent include a variety of natural or synthetic substrate materials. Suitable substrates are those which have the ability to retain a fabric-conditioning agent in a form which is releaseable ;~
to fabrics tumbled therewith, and which h~ve a resistance to shredding or other tearing failures when tumbled with damp clothes in a dryer. Examples of suitable substrates include paper towelling, swatches of woven and non-woven cloth, papers/ sponges, plastics and felts. Fibrous materials can be natural or synthetic but are preferably cellulose. Foæm plastic web materials, such as the polyurethanes, can also be employed.
In one embodiment of the invention, a substrate which i9 relatively impermeable to the fabric-conditioning ~0 agent is employed so as to dispose the fabric-conditioning agent onto the substrate as a discrete surface coating.
Wet strength papers, regenerated cellulose, rayon, nylon, polyester, polyacrylonitrile, polyole~in and other synthetic woven or non-woven fibrous materials are .~ .
lZ~3t:~
suitable for this purpose. Wet strength paper is suitably employed and can be treated with a waterproo~ing or sizing material such as a thermosetting resin, starch or other impregnant, having the effect of reducing water absorption by fibrous cellulosic products, and allowing the formation of a coating of conditioning agent. Waxy papers which carry coatings or impregnations of paraffin or microcrystalline or synthetic wax can be used -- for example, "butcher paper" or dry waxed paper -- to the extent of reducing moisture absorption but permitting adherent coating of the paper with conditioning agent.
Wet strength papers, such as Kraft or bond papex, can be employed.
Preferred articles of the invention include those formed from a substrate having an absorption capacity in relation~ for example, to fabric softening agents as to provide an impregnated article capa~le of controllably releasing the softening agent to treated fabrics. Improved softness or feel of the treated fabrics is provided without overdosing or lo~alized concentration of softener in the form of spots or stains. Suitable absorbent substrate materials are described in considerable detail in U.S. Patent No. 3,686,025, issued August 22, 1972, to Morton.
While Morton teaches that an absorbant capacity of 5.5 through 12, as defined therein, is desirable for practicing the invention disclosed by him, it has been our finding that, in the present invention, substra~es having absorbencies substantially lower than 5.5 are entirely satisfactory and, indeed, constitute the pre~erred embodiment of the present invention.
While not limiting the invention thereto, the reason for this finding is that, while in the prior art it would appear that the conditioning agent is absorbed into the fiber of the substrate and held therein and ~Z~i~3~
between the interstices between the fibers. In the articles of the present invention the conditioning agent is, in ef~ect, placed u~on the substrate; in that the use of a finer denia fiber provides sufficient absorbency before the interstices only so that a very minimal amount of absorbency is adequate for the purposes of the present invention.
Preferred ahsorbent substrates are cellulosic materials such as multi-ply paper towel and non-woven cloth substrates. Preferred paper towel materials and their method of manufacture can be found in U.S. Patent No. 3,414,459, issued December 3, 1968, to Wells.
Preferred non-woven cloth substrates can be generally defined as adhesively-bonded fibrous or filamentous products having a web structura, in which the fibers or ~ilaments are distributed haphazardly, as in the "wet lay" processes, or with a degree of orientation, as in the "carding"
process. Such substrates exhibit desirable strength in all directions and are rasistant to shredding or tearing failures when tumbled with damp fabrics. The ~ibers or rilaments of such non-woven cloth substrates can be natural (for example, wool, silk, jute, hemp, cotton, linen, sisal or ramie) or syn-thetic (~o~ example, rayon, cellulose ester, polyvinyl derivatives, polyolefins, polyamides or polyesters) and bonded together with a polymetric binder resin such as polyvinyl acetate. While the invention is in no way limited thereto, it has been ~ound that the most satisfactory results are obtained using polyester ~ibers. ~hese ~ibers have the advantage, in the context o~ the present invention, of being so~ter, not as absorbent, and have the ability to be produced in a whiter - i.e., more hygenic appearing -- form than those materia1s which are dis~losed by t~e prior art and are presently to be found in t~e channels o commerce.
The factor of softness is advantagaous as it lZ683~2 tends to counter the crumpling and folding efects which were presen~, and indeed believed to be desirable, in the articles of the prior art. The softer touch, as well as the whiter appearance of the polyester fiber, are 5 considered to be specific advantages in a product closely related, in the mind of the consumer, with hygenic matters. The preferred, though not critical, range of absorbency of the materials used herein is between 100 and 500~. This lower absorbency has the advantage of permitting the easier removal of the conditioning agent to the fabric which it contacts in the dryer. This ratio of removability contributes to the efficiency of the present met~od since, inherently then, less material is required. Such substrates will normally have a void volume of from about 20% to about 80~ to provide desirable air flow properties.
The conditioning agents employed herein include any of a ~ariety of agents employed generally in textile treating operations. Accordingly, fabric softening anti-static, anti-mildew, germicidal, mothproofing and anti-wrinkling agents, perfumes and the like can be employed.
The most universal preference, however, is for agents which act to so~ten ~abrics or otherwise improve their feel or hand. Softening agents which also have anti-static properties and which reduce sta~ic charge or ~abxiccling are especially preferred.
Typically, the fabric softening agents that can be employed are compounds having a relati~ely-long hydrocarbon group serving to provide hydrophobicity or lubricity. Among such groups axe alkyl groups containing 8 or more carbon atoms and preferably from 12 to 22 carbon atoms. Suitable fabrlc softening agents include cationic, anionic, nonionic, or zwitterionic compounds. Cationic fabric-sotenlng agents include the cationic nitrogen-containin~ compounds such as quaternary ammonium compoundsand amine which ha~e one or two straight-chain or~anic .
~Z61~3~Z
groups of at least 8 carbon atoms. Preferably, they have one or two such groups of ~rom 12 to 22 carbon atoms.
Preferred cation-active softener compounds include the quaternary ammonium softener compounds corresponding to the formula G~X-,-'..
wherein R is hydrogen or an aliphatic group of from 12 to 22 carbon atoms; Rl is an aliphatic group having from 12 to 22 carbon atoms; R2 and R3 are each alkyl groups of from 1 to 3 carbon atoms; and X is an anion selected from halogen, acetate phosphate, nitrite and methyl sulfate radicals.
Because of their excellent softening e~icacy and ready availability, preferred cationic softener compounds of the invention are the dialkyl dimethyl ammonium chlorides, wherein the alkyl groups have rom 12 to 22 carbon atoms and are derived from long-chain fatty acids such as hydrogenated tallow. As employed herein, alkyl is intended as including unsakurated compounds such as are present in alkyl groups derived from naturally occurring fatty oils. The term "tallow" refers to fatty alkyl groups derived from tallow fatty acids. Such fatty acids give rise to quaternary softener compounds wherein R and R~ have predominantly from 16 to 18 carbon atoms.
The term "coconut" refers to fatty acid groups ~rom coconut oil fatty acids. The coconut-alkyl R and R
~2~i~33~;2 gxoups have from about 8 to about 18 carbon atoms and predominate in C12 to C14 alkyl groups. Representative examples of quaternary softeners of the invention include tallow trimethyl ammonium chloride; ditallow dimethyl ammonium chloride; ditallow dimethyl ammonium methyl sulfate; dihexadecyl dimethyl ammonium chloride;
di(hydrogenated tallow)dimethyl ammonium chloride;
dioctadecyl dimethyl ammonium chloride; dieicosyl dimethyl ammonium chloride; didocosyl dimethyl ammonium chloride;
di(hydrogenated tallow)dimethyl ammonium methyl sulfate;
dihexadecyl diethyl ammonium chloride; dihexadecyl diethyl ammonium chloride; dihexadecyl dimethyl ammonium acetate; ditallow dipropyl ammonium phosphate; ditallow dimethyl ammonium nitrite; di(coconut-alkyl)dimethyl ammonium chloride.
Suitable cation-active amine so~tener compounds are the primary, secondary and tertiary amine compounds having at least one straight-chain organic group of from 12 to 22 carbon atoms and 1,3-propylene diamine compounds having a straight-chain organic group of from 12 to 22 carbon atoms. Examples of such softener actives include primary tallow amine' primary hydrogenated-tallow amine;
tallow 1,3-prop~lene diamine; oleyl 1,3-propylene diamine; coconut 1,3-propylene diamine; soya 1,3-propylene diamine; and the like.
Other suitable cation-active softener compounds herein are the quaternary imidazolinium salts. Preferred salts are those conforming to the formula ~f~ ~
~LZ683~;Z
wherein R6 is an alkyl containing from 1 to 4, preferably from 1 to 2, carbon atoms; R7 is an alkyl containing from 1 to 4 carbon atoms or a hydrogen radical; R8 is an alkyl containing from 8 to 22, preferably at least 15, carbon atoms; R5 is hydrogen or an alkyl containing from 9 to 22, preferably at least 15, carbon atoms; and X is an anion, preferably methyl sulfate or chloride ions. Other suitable anions include those disclosed with reference to the cationic quaternary ammonium ~abric softeners described hereinbefore. Particularly preferred are those imidazolinium compounds in which both R5 and R8 are alkyls of from 12 to 22 carbon atoms -- for example,
2-heptadecyl-1,1-methyl[(2-stearoylamide)ethyl]~
imidazolinium methyl sulfate.
Other cationic quaternary ammonium fabric softeners which are useful herein includ~, for example, alkyl(C12 to C22)-pyridinium chlorides, alkyl(C12 to C22)-[Cl to C3)-morpholinium chlorides, and quaternary derivatives of amino acids and amino esters.
The anionic conditioning agents can include any of the various surface-active anionic fabric-softening and anti-static agents such as alkali metal or ammonium salts of higher ~atty alcohol sulates, higher a~ty alcohol ether sulfates, higher fatty alcohol sul~onates, the linear higher alkyl benzene sulfonates, the higher fatty acyl taurides and isothionates. Generallyr the cation of such compounds will be an alkali metal or other water-solubilizing radical. The hydrophobic moiety of such compounds will normally contain from 10 to 22 carbon atoms. Alkali metal and ammonium soaps of fatty acids of fxom 10 to 22 carbon atoms can also be employed and include the sodium or potassium coconut or tallow soaps.
Suitable nonionic abric softeners and anti-static agents that can be employed are the polyoxyalkylene glycols, the higher fatty alcohol esters of polyoxyalkylene glycols, the higher ~atty alcohol esters , .
:~Z6~30;Z
of polyoxyalkylene glycols. Also suitable are the ethoxylates of long-chain alcohols of from B to 22 carbon atoms such as the ethoxylates of tallow alcohol with, for example, 10 to 40 moles of ethylene oxide. Other nonionics include the amides such as the alkanolamides --for example, the higher fatty amides and higher fatty acid mono- and di-lower alkanolamides, wherein the long-chain hydrophobic groups have from about 10 to 22 carbon atoms.
Other suitable softening agents include the zwitterionic compounds of the formula R'~ CH,--R"--CH,SO,-wherein Rg and RlO are each methyl, ethyl, n-propyl, isopropyl, 2-hydroxyethyl or 2-hydroxypropyl; R8 is a 12 to 22 carbon atom alkyl or alkenyl and wherein said alkyl or alkenyl contains from 0 to 2 hydroxyl substituents, from 0 to 5 ether linkages, and from 0 to l amide linkage;
and Rll is an alkylene group containing ~rom 1 to 4 carbon atoms with from 0 to l hydroxyl substituents; particularly preferred are compounds wherein R3 is a carbon chain containing from 14 to 18 caxbon atoms selected rom the group consisting of alkyls and alkenyl and wherein said alkyls and alkenyls contain 0 to 2 hydroxyl substituents.
Speci~ic examples of the particularly preferred compounds of this class include the following: 3-(N-hexadecyl-N,N-dimethylammonio)-2-hydroxypropane-1-sulfonate; and 3-(N-25~ octadecyl-N,N-dimethylammonio)-propane-l sulfonate.
Other examples of conditioning agents suitable or the articles herein are described in detail in U.S.
Patent No. 3,688,025 at column 5, line 51, to column 14, ~26~3302 line 6.
The amount of conditioning agent carried by the substrate is an amount sufficient to provide the desired conditioning effect without substantial excess. The amount will vary in any given case and will depend, for example, upon the nature of the particular conditioning agent or substrate material and the type of conditioning effect desired. When the conditioning agent is a fabric softening agent, such agent will preferably be employed in a weight ratio of agent to untreated substra~e from 0.5:1 to 4:1 or more. Generally, the amount of softener will range from about 40 mg to about 1.2 grams per centimeter length of a substrate no more than 28 cm wide, with small amounts of softener being used on lightweight su~strates, such as non-woven cloths, and large amounts on heavy substrates, such as multi-ply paper.
The manner of applying the fabric conditioning agent to the substrate in such a manner as to provide a discontinuous pattern in at least one direction, is not critical. It has been found most convenient, however, to apply the conditioning agent by a printing proces~ which will permit a ready repetition of the pre-determined discontinuous pattern, as well as a means for applying the conditioning agent on one, or both, principal surfaces of the substrate in a pre-determined amount.
The sole criterion of the pattern o fabric conditioner applied is that it shall leave an adequate amount of ree space upon the substrate, pre~erably upon a non-woven substrate, to allow a sufficient amount of air to pass through the substrate that the air outlet of a typical domestic dryer should not be blocked thereby.
While the preferred embodiments of the present application contemplate the use of non-woven fabrics which, because of the nature of their construction, possess a substantial , ... . . .
33~1Z
number of interstices between the fibers thereof through which air may pass, the scope of the invention does not exclude the use of woven fabrics, or other flexible substrates in which perforations have been placed in the manner of McQueary, U.S. Patent No. 3,956,556. Provided that the important criterion of air permeability is maintained, the pattern carrying the fabric conditioner is purely a matter of economic and aesthetic convenience. As specifically exemplified herein, a pattern of dots has 1~ been employed. There may also be employed patterns including strips running with the length of the substrate, strips running diagonally across the width of the substrate, and strips running straight across the width of the substrate. The strips may be straight, they may be curved, they may be sinusoidal, or they may be totally random. There may be included checkerboard patterns, aesthetic, repeating designs, printed text having meaning and not having meaning, and so forth. It is also contemplated within the scope of the invention to utilize a fabric conditioner having a different color from the substrate. Because of the need to be able to employ the articles of the present invention with colored and non-colored fabrics, it would be preferred -to utilize a non-colored or white conditioner upon a substra~e of a dif~erent shade or color.
This latter type o~ patterning goes solely to the appearance of the goods rather than their basic function which is to transfer fabric conditioner to fabrics without the disadvantages possessed by certain prior art fabric conditioning articles.
In order to comply with the principal criterion of the pattern set forth above, however, the pattern, selected should be one which does not involve large areas of fabric conditioner located in one portion of the 126~33~)2 article since such large areas of conditioner tend to block air flow and tend to permit adhesion of the article to the air flow outlet. The more open the applied pattern of fabric conditioner, the better.
The fabric conditioning articles of the present invention are structured to be compatible with conventional 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 may 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 five to fifty volume changes of drying gas 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 aan, especially in small loads, cause a fabric, such as a sock, handkerchief or the like, or a fabric-conditioning article, to be disposed on the surface of the air outlet of the dryer. A usual load of fabrics of from about four to twelve pounds dry weight will fill from about 10% to 70%
of the volume of most dryers and will normally pose little difficulty. A sufficient number of tumbling items will normally be present to prevent any item from being drawn to the exhaust outlet or to cause it to be removed from the outlet.
Preferably, a fabric conditioning article of the invention will contain a sufficient number of perforations as to permit ~he passage of at least about 75% of the normal volume of air flow of the laundry dryer. This permits fabrics to be dried efficiently without undesirable temperature build-up or alternate on/off cycling of the heater and resulting rise and fall of dryer temperature. Normal operating temperatures are adhered to , .
~z~3302 and extended drying times are thereby avoided, Preferabl~, an article will have a sufficient number of perforations as to allow at least 85~ of the volume of air to pass through the dryer.
The fabric conditioning articles of the invention are simple to employ and normally will be employed in a laundry dryer which is operated at a temperature, for example, of from 75 F to 210 F and for a drying period of from about five to sixty minutes. A
load of fabrics to be dried is placed into the dryer and a sheet, such as may be detached by tearing from a perforated roll, is simply added to the dryer which is operated in usual fashion. The treated fabrics are then removed and handled in customary fashion.
The following Examples illustrate certain preferred embodiments of the invention and are not intended as limiting the invention. The quaternary ammonium fabric softening agent of Examples I - III was di tallow dimethyl ammonium chloride. Other of the various fabric conditioning agents described hereinbefore in detail can be employed to advantage.
, ~LZ6i330Z
EXAMPI,E I
There is utilized as a substrate a non-woven fabric cut to a desired size (7.6 x 22.8 centimeters).
The substrate consists of 100% airlaid polyester fiber bonded with a hydrophobic binder, has a thickness of 280 microns, weighs 24 grams per square meter, and has an absorbency of 4 (400%).
The fabric conditioning formulation consists of 100% Arquad 2HT-75 (a di tallow dimethyl ammonium chloride manufactured by Armak Co., Chicago, Illinois.) (Arquad is a registered trademark of the manufacturer.) A nickel sheet, 127 microns in thickness, perforated with dot shaped perforations at a rate of 26 perforations per square centimeter, each perforation having a diameter of 0.7 millimeters diameter, is placed on top of the substrate sheet. The soEtening formulation is warmed to a temperature of approximately 40 C, and squeegeed through the perforated sheet onto the substrate.
The foregoing procedure provides substrate application at the rate of 30 grams per square meter.
EXAMPLE II
.
The procedure of Example I was repeated utilizing, however, in place of the substrate of Example I, a 100% rayon fiber non-woven substrate bonded with an acrylic binder (Sterns & Foster, Style F-3387, a material similar to that utilized in commercially available ~abric softeners produced under the trademark Bounce, a product of Proctor & Gamble.) The substrate has a thickness of 254 microns, weighs 24 grams per square meter, and has an absorbency of 6.5 (650%)~
--lg--~L26l~3~Z
EXAMPLE III
Comparison of Exam~le I and II Products Four samples produced in accordance with each of the foregoing Examples were, at separate times, placed in a commercially available home-size clothes dryer (Frigidaire Model LCT-120, manufactured by General Motors) together with six spin dried but damp terrycloth towels, and dried in the dryer for 120 minutes. Examination of the samples after use showed that the substrates of Example I (absorbency 4.0) released over 60~ of the fabric conditioning agent and those of Example II
(absorbency 6.5) released less than 40% of the fabric conditioning agent.
EXAMPLE IV
Pairs of sheets, produced in accordance with Example I, are heat sealed together at two opposite ends yielding a two-layer sample containing 38 grams of fabric conditioning agent per square meter.
EXAMPLE V
Samples were prepared in accordance with the procedure of Example ~ but, in place of utilizing a sheet having 26 dots per s~uare centimeter of 0.7 millimeter diameter, there is utilized a masking sheet having 15 dots per square centimeter of 1.4 millimeters in diameter.
2S The resulting sheets carry 38 grams of fabric conditioning agent per square meter. The resultant sheets are then joined together in accordance wi~h the procedure of Example IV.
imidazolinium methyl sulfate.
Other cationic quaternary ammonium fabric softeners which are useful herein includ~, for example, alkyl(C12 to C22)-pyridinium chlorides, alkyl(C12 to C22)-[Cl to C3)-morpholinium chlorides, and quaternary derivatives of amino acids and amino esters.
The anionic conditioning agents can include any of the various surface-active anionic fabric-softening and anti-static agents such as alkali metal or ammonium salts of higher ~atty alcohol sulates, higher a~ty alcohol ether sulfates, higher fatty alcohol sul~onates, the linear higher alkyl benzene sulfonates, the higher fatty acyl taurides and isothionates. Generallyr the cation of such compounds will be an alkali metal or other water-solubilizing radical. The hydrophobic moiety of such compounds will normally contain from 10 to 22 carbon atoms. Alkali metal and ammonium soaps of fatty acids of fxom 10 to 22 carbon atoms can also be employed and include the sodium or potassium coconut or tallow soaps.
Suitable nonionic abric softeners and anti-static agents that can be employed are the polyoxyalkylene glycols, the higher fatty alcohol esters of polyoxyalkylene glycols, the higher ~atty alcohol esters , .
:~Z6~30;Z
of polyoxyalkylene glycols. Also suitable are the ethoxylates of long-chain alcohols of from B to 22 carbon atoms such as the ethoxylates of tallow alcohol with, for example, 10 to 40 moles of ethylene oxide. Other nonionics include the amides such as the alkanolamides --for example, the higher fatty amides and higher fatty acid mono- and di-lower alkanolamides, wherein the long-chain hydrophobic groups have from about 10 to 22 carbon atoms.
Other suitable softening agents include the zwitterionic compounds of the formula R'~ CH,--R"--CH,SO,-wherein Rg and RlO are each methyl, ethyl, n-propyl, isopropyl, 2-hydroxyethyl or 2-hydroxypropyl; R8 is a 12 to 22 carbon atom alkyl or alkenyl and wherein said alkyl or alkenyl contains from 0 to 2 hydroxyl substituents, from 0 to 5 ether linkages, and from 0 to l amide linkage;
and Rll is an alkylene group containing ~rom 1 to 4 carbon atoms with from 0 to l hydroxyl substituents; particularly preferred are compounds wherein R3 is a carbon chain containing from 14 to 18 caxbon atoms selected rom the group consisting of alkyls and alkenyl and wherein said alkyls and alkenyls contain 0 to 2 hydroxyl substituents.
Speci~ic examples of the particularly preferred compounds of this class include the following: 3-(N-hexadecyl-N,N-dimethylammonio)-2-hydroxypropane-1-sulfonate; and 3-(N-25~ octadecyl-N,N-dimethylammonio)-propane-l sulfonate.
Other examples of conditioning agents suitable or the articles herein are described in detail in U.S.
Patent No. 3,688,025 at column 5, line 51, to column 14, ~26~3302 line 6.
The amount of conditioning agent carried by the substrate is an amount sufficient to provide the desired conditioning effect without substantial excess. The amount will vary in any given case and will depend, for example, upon the nature of the particular conditioning agent or substrate material and the type of conditioning effect desired. When the conditioning agent is a fabric softening agent, such agent will preferably be employed in a weight ratio of agent to untreated substra~e from 0.5:1 to 4:1 or more. Generally, the amount of softener will range from about 40 mg to about 1.2 grams per centimeter length of a substrate no more than 28 cm wide, with small amounts of softener being used on lightweight su~strates, such as non-woven cloths, and large amounts on heavy substrates, such as multi-ply paper.
The manner of applying the fabric conditioning agent to the substrate in such a manner as to provide a discontinuous pattern in at least one direction, is not critical. It has been found most convenient, however, to apply the conditioning agent by a printing proces~ which will permit a ready repetition of the pre-determined discontinuous pattern, as well as a means for applying the conditioning agent on one, or both, principal surfaces of the substrate in a pre-determined amount.
The sole criterion of the pattern o fabric conditioner applied is that it shall leave an adequate amount of ree space upon the substrate, pre~erably upon a non-woven substrate, to allow a sufficient amount of air to pass through the substrate that the air outlet of a typical domestic dryer should not be blocked thereby.
While the preferred embodiments of the present application contemplate the use of non-woven fabrics which, because of the nature of their construction, possess a substantial , ... . . .
33~1Z
number of interstices between the fibers thereof through which air may pass, the scope of the invention does not exclude the use of woven fabrics, or other flexible substrates in which perforations have been placed in the manner of McQueary, U.S. Patent No. 3,956,556. Provided that the important criterion of air permeability is maintained, the pattern carrying the fabric conditioner is purely a matter of economic and aesthetic convenience. As specifically exemplified herein, a pattern of dots has 1~ been employed. There may also be employed patterns including strips running with the length of the substrate, strips running diagonally across the width of the substrate, and strips running straight across the width of the substrate. The strips may be straight, they may be curved, they may be sinusoidal, or they may be totally random. There may be included checkerboard patterns, aesthetic, repeating designs, printed text having meaning and not having meaning, and so forth. It is also contemplated within the scope of the invention to utilize a fabric conditioner having a different color from the substrate. Because of the need to be able to employ the articles of the present invention with colored and non-colored fabrics, it would be preferred -to utilize a non-colored or white conditioner upon a substra~e of a dif~erent shade or color.
This latter type o~ patterning goes solely to the appearance of the goods rather than their basic function which is to transfer fabric conditioner to fabrics without the disadvantages possessed by certain prior art fabric conditioning articles.
In order to comply with the principal criterion of the pattern set forth above, however, the pattern, selected should be one which does not involve large areas of fabric conditioner located in one portion of the 126~33~)2 article since such large areas of conditioner tend to block air flow and tend to permit adhesion of the article to the air flow outlet. The more open the applied pattern of fabric conditioner, the better.
The fabric conditioning articles of the present invention are structured to be compatible with conventional 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 may 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 five to fifty volume changes of drying gas 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 aan, especially in small loads, cause a fabric, such as a sock, handkerchief or the like, or a fabric-conditioning article, to be disposed on the surface of the air outlet of the dryer. A usual load of fabrics of from about four to twelve pounds dry weight will fill from about 10% to 70%
of the volume of most dryers and will normally pose little difficulty. A sufficient number of tumbling items will normally be present to prevent any item from being drawn to the exhaust outlet or to cause it to be removed from the outlet.
Preferably, a fabric conditioning article of the invention will contain a sufficient number of perforations as to permit ~he passage of at least about 75% of the normal volume of air flow of the laundry dryer. This permits fabrics to be dried efficiently without undesirable temperature build-up or alternate on/off cycling of the heater and resulting rise and fall of dryer temperature. Normal operating temperatures are adhered to , .
~z~3302 and extended drying times are thereby avoided, Preferabl~, an article will have a sufficient number of perforations as to allow at least 85~ of the volume of air to pass through the dryer.
The fabric conditioning articles of the invention are simple to employ and normally will be employed in a laundry dryer which is operated at a temperature, for example, of from 75 F to 210 F and for a drying period of from about five to sixty minutes. A
load of fabrics to be dried is placed into the dryer and a sheet, such as may be detached by tearing from a perforated roll, is simply added to the dryer which is operated in usual fashion. The treated fabrics are then removed and handled in customary fashion.
The following Examples illustrate certain preferred embodiments of the invention and are not intended as limiting the invention. The quaternary ammonium fabric softening agent of Examples I - III was di tallow dimethyl ammonium chloride. Other of the various fabric conditioning agents described hereinbefore in detail can be employed to advantage.
, ~LZ6i330Z
EXAMPI,E I
There is utilized as a substrate a non-woven fabric cut to a desired size (7.6 x 22.8 centimeters).
The substrate consists of 100% airlaid polyester fiber bonded with a hydrophobic binder, has a thickness of 280 microns, weighs 24 grams per square meter, and has an absorbency of 4 (400%).
The fabric conditioning formulation consists of 100% Arquad 2HT-75 (a di tallow dimethyl ammonium chloride manufactured by Armak Co., Chicago, Illinois.) (Arquad is a registered trademark of the manufacturer.) A nickel sheet, 127 microns in thickness, perforated with dot shaped perforations at a rate of 26 perforations per square centimeter, each perforation having a diameter of 0.7 millimeters diameter, is placed on top of the substrate sheet. The soEtening formulation is warmed to a temperature of approximately 40 C, and squeegeed through the perforated sheet onto the substrate.
The foregoing procedure provides substrate application at the rate of 30 grams per square meter.
EXAMPLE II
.
The procedure of Example I was repeated utilizing, however, in place of the substrate of Example I, a 100% rayon fiber non-woven substrate bonded with an acrylic binder (Sterns & Foster, Style F-3387, a material similar to that utilized in commercially available ~abric softeners produced under the trademark Bounce, a product of Proctor & Gamble.) The substrate has a thickness of 254 microns, weighs 24 grams per square meter, and has an absorbency of 6.5 (650%)~
--lg--~L26l~3~Z
EXAMPLE III
Comparison of Exam~le I and II Products Four samples produced in accordance with each of the foregoing Examples were, at separate times, placed in a commercially available home-size clothes dryer (Frigidaire Model LCT-120, manufactured by General Motors) together with six spin dried but damp terrycloth towels, and dried in the dryer for 120 minutes. Examination of the samples after use showed that the substrates of Example I (absorbency 4.0) released over 60~ of the fabric conditioning agent and those of Example II
(absorbency 6.5) released less than 40% of the fabric conditioning agent.
EXAMPLE IV
Pairs of sheets, produced in accordance with Example I, are heat sealed together at two opposite ends yielding a two-layer sample containing 38 grams of fabric conditioning agent per square meter.
EXAMPLE V
Samples were prepared in accordance with the procedure of Example ~ but, in place of utilizing a sheet having 26 dots per s~uare centimeter of 0.7 millimeter diameter, there is utilized a masking sheet having 15 dots per square centimeter of 1.4 millimeters in diameter.
2S The resulting sheets carry 38 grams of fabric conditioning agent per square meter. The resultant sheets are then joined together in accordance wi~h the procedure of Example IV.
3~
EXAMPLE VI
Comparl n of Example IV and V Products The samples compared in accordance with Examples IV and V were tested in accordance with the test procedures utilized for the products of Examples I
and II and showed that the product of Example IV
released 20% more fabric conditioning agent than the product of Example V.
EXAMPLE VII
Samples were prepared in accordance with Example IV, except that the fabric conditioning formulation utilized consisted of Arquad 2HT-75 and Ethomeen T/12 (4:1). Ethomeen T/12 is a Bis-2-hydroxy-etnyl tallow amine manufactured by Armak Co., Chicago,Illinois. (Ethomeen is the registered trademark of the manufacturer.) The sheets utilized were 7.6 x 24.76 centimeters, and the weight of fabric softening agent is 57 grams per square meter.
EXAMPLE VIII
Comparison of Example VII Product with a Commercial Sheet A sample of Example VII is evaluated in the home dryers previously described. The dryer load consisted of two cotton terrycloth dishclo~hes, four cotton terrycloth dish towels, four blue polyester pillow cases, and four velour terrycloth bath towels, all spin dried but damp. The quantitative and qualitative results are set forth below.
.~ .
~L~6~30~
Example #VII Commercial Sheet Density 57 gm/sq. m. 32.45 gm/sq~ m.
applied weight 1.073 gram 2.072 gram amount transferred 0.651 1.184 ~ transferred 60.7% 57.2~
A panel of ten women judged the fabrics treated with Example VII product to be superior in perceived softness to similar goods treated using the commercial material even though the actual amount of fabric conditioning agent transferred to the fabric by the commercial softener is almost twice the amount transferred by the Example VII product.
EXAMPLE IX
Samples were prepared in accordance with Example I with the following ~ariants. The samples were 28 x 22.8 centimeters in size (full commercial size).
The fabric conditioning agent utilized was Arquad 2HT-75 and Carbowax (9:1) (Carbowax is a polyethylene glycol, molecular weight range 190 - 210, manufactured by Union Carbide Corporation, New York, New York. Carbowax is a registered trademark of the manufa~turer. The conditioner is applied in various weight per unit area ranges -- i.e., 29, 24, and 12 grams per square meter.
(Commercial sheet density is 39.5 grams per square meter.) E~AMPLE X
Comparison of Example IX Product with Commercial Sheet The procedures relating to the evaluation o~
Example VII material (comparison No. 3) were repeated utilizing samples prepared according to Example VIII with commercial sheets. (Quantitative and Qualitative Tests) ~2~33C~2 Quantitative Tests Commercial Sheet A B_ C
applied wt. 1.859 1.541 0.761 2.526 density 29 24 12 39.5 amount agent transferred 1.044 0.970 O.S16 0.933 % transferred 56.2% 63% 67.8% 37%
Qualitative Tests A panel of ten women judged the clothes being treated for perceived softness. The women were asked to evalute the treated clothing by rating each lot from 1 to 5 with 1 being the highest degree of softness and 5 being the least degree of softness. The results are tabulated with the lowest score being rated as the highest degree of softness. For purposes of the panel test a control, Column E, was included. This control was dryed under normal conditions and not treated with softening agents. The panel test appears below.
Commercial Sheet A B C D E
Woman #1 1 5 2 3 Woman #2 2 I 3 4 5 Woman #3 3 1 2 4 5 Woman #4 1 2 4 3 5 Woman #5 2 1 4 3 5 Woman #6 1 2 4 3 s Woman #7 3 2 1 5 4 Woman #8 1 2 4 3 5 Woman #9 2 1 3 4 5 Woman ~10 2 1 3 4 5 The foregoing te~ts show that, utilizing ~6~30;2 commercial size sheets, approximately twice as much softening agent is released by products produced in accordance with the present invention than from products presently commercaill~ available. It is further shown that the least satisfactory product produced in accordance with the present invention compares favorably with the commercial product, but requires a conditioning agent load of approximately 1/3 of the amount utilized in the commercial product.
EXAMPLE XI
400 grams of a softening formulation consisting of 90 parts Arquad 2HT-75 , 10 parts polyethylene glycol 200, and 300 parts water was prepared by placi~g said materials in a container and immersing the container in a water bath heated at 44 C. A non-woven substrate of the type described in Example I was prepared. The softening agent was applied by immersing the substrate in the softenincJ agent, completely saturating the substrate, and removing the excess with a spatula. The polyester material is dried in an oven for five minutes at 104 C to remove excess moisture. A dried coating weight of approximately 0.8 grams per 175 centimeters squared sheet (i.e., 4.6 mg/cm2) is achieved.
EXAMPLE XII
Example XI is repeated but a non-woven substrate of the type described in Example II is substituted. A
coating weight of 0.75 grams per 175 square centimeters t4.3mg/cm ) is achieved, ~L2~3302 EXAMPLE XIII
Evaluation of Samples from Examples XI and XII
_ _ _ The treated samples were evaluated by testing them under actual drying conditions. Four samples from 5 Example XI were placed in a home dryer, Sears Model Kenmore 77656100, along with six damp terry towels and dried for thirty minutes.
It was found that Example XI using a fabric of 100% polyester fiber with an absorbency of 400%, there 10 was released over 60% of the softening agents.
It was noted that the finished coated polyester material was stiff, waxy and had an objectionable feel and hand.
Using a 100% rayon fiber fahric of Example XII
15 substrate with 650% absorbency, there was released under 7061 45% of the softening agent.
EXAMPLE VI
Comparl n of Example IV and V Products The samples compared in accordance with Examples IV and V were tested in accordance with the test procedures utilized for the products of Examples I
and II and showed that the product of Example IV
released 20% more fabric conditioning agent than the product of Example V.
EXAMPLE VII
Samples were prepared in accordance with Example IV, except that the fabric conditioning formulation utilized consisted of Arquad 2HT-75 and Ethomeen T/12 (4:1). Ethomeen T/12 is a Bis-2-hydroxy-etnyl tallow amine manufactured by Armak Co., Chicago,Illinois. (Ethomeen is the registered trademark of the manufacturer.) The sheets utilized were 7.6 x 24.76 centimeters, and the weight of fabric softening agent is 57 grams per square meter.
EXAMPLE VIII
Comparison of Example VII Product with a Commercial Sheet A sample of Example VII is evaluated in the home dryers previously described. The dryer load consisted of two cotton terrycloth dishclo~hes, four cotton terrycloth dish towels, four blue polyester pillow cases, and four velour terrycloth bath towels, all spin dried but damp. The quantitative and qualitative results are set forth below.
.~ .
~L~6~30~
Example #VII Commercial Sheet Density 57 gm/sq. m. 32.45 gm/sq~ m.
applied weight 1.073 gram 2.072 gram amount transferred 0.651 1.184 ~ transferred 60.7% 57.2~
A panel of ten women judged the fabrics treated with Example VII product to be superior in perceived softness to similar goods treated using the commercial material even though the actual amount of fabric conditioning agent transferred to the fabric by the commercial softener is almost twice the amount transferred by the Example VII product.
EXAMPLE IX
Samples were prepared in accordance with Example I with the following ~ariants. The samples were 28 x 22.8 centimeters in size (full commercial size).
The fabric conditioning agent utilized was Arquad 2HT-75 and Carbowax (9:1) (Carbowax is a polyethylene glycol, molecular weight range 190 - 210, manufactured by Union Carbide Corporation, New York, New York. Carbowax is a registered trademark of the manufa~turer. The conditioner is applied in various weight per unit area ranges -- i.e., 29, 24, and 12 grams per square meter.
(Commercial sheet density is 39.5 grams per square meter.) E~AMPLE X
Comparison of Example IX Product with Commercial Sheet The procedures relating to the evaluation o~
Example VII material (comparison No. 3) were repeated utilizing samples prepared according to Example VIII with commercial sheets. (Quantitative and Qualitative Tests) ~2~33C~2 Quantitative Tests Commercial Sheet A B_ C
applied wt. 1.859 1.541 0.761 2.526 density 29 24 12 39.5 amount agent transferred 1.044 0.970 O.S16 0.933 % transferred 56.2% 63% 67.8% 37%
Qualitative Tests A panel of ten women judged the clothes being treated for perceived softness. The women were asked to evalute the treated clothing by rating each lot from 1 to 5 with 1 being the highest degree of softness and 5 being the least degree of softness. The results are tabulated with the lowest score being rated as the highest degree of softness. For purposes of the panel test a control, Column E, was included. This control was dryed under normal conditions and not treated with softening agents. The panel test appears below.
Commercial Sheet A B C D E
Woman #1 1 5 2 3 Woman #2 2 I 3 4 5 Woman #3 3 1 2 4 5 Woman #4 1 2 4 3 5 Woman #5 2 1 4 3 5 Woman #6 1 2 4 3 s Woman #7 3 2 1 5 4 Woman #8 1 2 4 3 5 Woman #9 2 1 3 4 5 Woman ~10 2 1 3 4 5 The foregoing te~ts show that, utilizing ~6~30;2 commercial size sheets, approximately twice as much softening agent is released by products produced in accordance with the present invention than from products presently commercaill~ available. It is further shown that the least satisfactory product produced in accordance with the present invention compares favorably with the commercial product, but requires a conditioning agent load of approximately 1/3 of the amount utilized in the commercial product.
EXAMPLE XI
400 grams of a softening formulation consisting of 90 parts Arquad 2HT-75 , 10 parts polyethylene glycol 200, and 300 parts water was prepared by placi~g said materials in a container and immersing the container in a water bath heated at 44 C. A non-woven substrate of the type described in Example I was prepared. The softening agent was applied by immersing the substrate in the softenincJ agent, completely saturating the substrate, and removing the excess with a spatula. The polyester material is dried in an oven for five minutes at 104 C to remove excess moisture. A dried coating weight of approximately 0.8 grams per 175 centimeters squared sheet (i.e., 4.6 mg/cm2) is achieved.
EXAMPLE XII
Example XI is repeated but a non-woven substrate of the type described in Example II is substituted. A
coating weight of 0.75 grams per 175 square centimeters t4.3mg/cm ) is achieved, ~L2~3302 EXAMPLE XIII
Evaluation of Samples from Examples XI and XII
_ _ _ The treated samples were evaluated by testing them under actual drying conditions. Four samples from 5 Example XI were placed in a home dryer, Sears Model Kenmore 77656100, along with six damp terry towels and dried for thirty minutes.
It was found that Example XI using a fabric of 100% polyester fiber with an absorbency of 400%, there 10 was released over 60% of the softening agents.
It was noted that the finished coated polyester material was stiff, waxy and had an objectionable feel and hand.
Using a 100% rayon fiber fahric of Example XII
15 substrate with 650% absorbency, there was released under 7061 45% of the softening agent.
Claims (19)
1. A fabric conditioning article comprising a flexible substrate having an upper and a lower princi-pal surface, said substrate carrying a non-soap fabric conditioning agent removable to fabrics by contact therewith in a laundry dryer, said agent being absorbed onto at least one of the two principal surfaces of said substrate in a discontinuous pattern with respect to the horizontal plane on the principal surface of the substrate upon which it is absorbed, said substrate being of a degree of porousity sufficient to prevent its adhesion to the air outlet of a domestic laundry dryer in normal usage.
2. An article in accordance with Claim 1 wherein the article is of sufficient porousity to permit at least about 75% of the normal air flow through said dryer when said article is used therein.
3. An article in accordance with Claim 1 wherein the agent is absorbed on one of the principal sur-faces.
4. An article in accordance with Claim 1 wherein the agent is applied in a pattern which is con-tinuous in one direction, said pattern comprising a plurality of strips of pre-determined design spaced apart by a pre-determined amount.
5. An article in accordance with Claim 1 wherein the conditioning agent is applied in a pre-determined arrangement in a discreet non-overlapping pattern.
26 Cl??? 6. A fabric conditioning article comprising a substantially air permeable flexible substrate, said substrate carrying a non-soap fabric conditioning agent removable to fabrics by contact therewith, in a laundry dryer, said agent being absorbed onto said substrate in a discontinuous pattern with respect to the horizontal plane of the substrate upon which it is absorbed the protions of said article free of conditioning agent in the horizontal plane also being free of substrate in the vertical plane above and below said portion.
Claim 7. An article of claim 6 wherein the spacing between the absorbed pattern is sufficient to permit at least 75 of the normal volume of air flow through said dryer when said article is used therein.
Claim 8. An article of claim 6 wherein the substrate has an absorbency of less than 5.5.
Claim 9 . The method of conditioning fabrics in a laundry dryer which comprises co-mingling said fabrics in said dryer with a fabric-conditioning article of claim 1.
Claim 10. The method of conditioning fabrics in a laundry dryer which comprises co-mingling said fabrics in said dryer with a fabric-conditioning article of claim 6.
Claim 11. A method of claim 10 wherein the spacing between said discontinuous pattern of fabric-conditioning agent is such as to permit at least 75% of the normal air flow through said dryer when said article is used therein.
Claim 12. A method of conditioning fabrics in a laundry dryer which comprises co-mingling said fabrics in said dryer with a fabric-conditioning article of claim 8.
13. A method of producing a fabric-conditioning article comprising a flexible substantially air permeable substrate said substrate carrying a non-soap fabric condi-tioning agent removable to fabrics by contact therewith in a laundry dryer, comprising printing said agent onto said substrate in a pattern such that portions of said substrate are not coated by said conditioning agent.
14. A method according to Claim 13 wherein the printing process is a screen printing process.
15. A method in accordance with Claim 10 wherein discontinuous pattern is so oriented upon the substrate as to permit at least 75% of the normal volume of air flow through said dryer when said article is used therein.
16. A method in accordance with Claim 14 wherein the substrate has an absorbency of less than 5.5.
17. A multiple-use fabric conditioning product comprising a substrate of sheet form with a layer of a fabric conditioning formulation exposed on at least one major surface, characterized in that the layer has at least one area of reduced depth extending down to the substrate surface.
18. A method of producing a fabric condition-ing article comprising a flexible substantially air per-meable substrate, said substrate carrying a non-soap fabric conditioning agent removable to fabrics by contact therewith in a laundry dryer, comprising the single step of printing a layer of said agent onto said substrate in a series of individual and spaced units such that portions of said substrate are not coated by said conditioning agent.
19. A fabric conditioning article comprising a flexible substrate having an upper and a lower princi-pal surface, said substrate carrying a series of indivi-dual and spaced units of a single layer of a non-soap fabric conditioning agent removable to fabrics by con-tact therewith in a laundry dryer, said agent being absorbed onto a portion of at least one of the two prin-cipal surfaces of said substrate in a discontinuous pat-tern with respect to the horizontal plane on the princi-pal surface of the substrate upon which it is absorbed, said substrate being of a degree of porousity sufficient to prevent its adhesion to the air outlet of a domestic laundry dryer in normal usage.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CA000320190A CA1268302A (en) | 1978-01-27 | 1979-01-24 | Article for conditioning fabrics in a clothes drier |
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US87278178A | 1978-01-27 | 1978-01-27 | |
| US872,781 | 1978-01-27 | ||
| CA000320190A CA1268302A (en) | 1978-01-27 | 1979-01-24 | Article for conditioning fabrics in a clothes drier |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1268302A true CA1268302A (en) | 1990-05-01 |
Family
ID=25360278
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA000320190A Expired CA1268302A (en) | 1978-01-27 | 1979-01-24 | Article for conditioning fabrics in a clothes drier |
Country Status (11)
| Country | Link |
|---|---|
| JP (1) | JPS54112297A (en) |
| BR (1) | BR7900458A (en) |
| CA (1) | CA1268302A (en) |
| CH (1) | CH643779A5 (en) |
| DE (1) | DE2902580A1 (en) |
| DK (1) | DK33779A (en) |
| FR (1) | FR2416972A1 (en) |
| GB (2) | GB2097830A (en) |
| IT (1) | IT1127823B (en) |
| NL (1) | NL7900619A (en) |
| SE (1) | SE443587B (en) |
Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB1603940A (en) * | 1978-04-11 | 1981-12-02 | Procter & Gamble | Fabric conditioning articles for use in laundry dryers |
| US4423105A (en) * | 1982-08-02 | 1983-12-27 | Colgate-Palmolive Company | Article for clothes conditioning and method of making same |
| GB8306308D0 (en) * | 1983-03-08 | 1983-04-13 | Unilever Plc | Conditioning fabrics in tumbledryer |
| JPH03259052A (en) * | 1990-03-09 | 1991-11-19 | Sanyo Electric Co Ltd | Automatic apparatus for cooking food |
| US20050192205A1 (en) * | 2004-02-27 | 2005-09-01 | Toan Trinh | Multiple use fabric conditioning article with replacement indicium |
| JP5539508B2 (en) * | 2009-07-01 | 2014-07-02 | ザ プロクター アンド ギャンブル カンパニー | Dryer bar with void volume |
Family Cites Families (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3895128A (en) * | 1965-08-13 | 1975-07-15 | Procter & Gamble | Method of conditioning fabrics and product therefor |
| CA941692A (en) * | 1970-02-03 | 1974-02-12 | Shunya Ida | Specific processed cloths and a method of producing the same |
| US3633538A (en) * | 1970-10-20 | 1972-01-11 | Colgate Palmolive Co | Spherical device for conditioning fabrics in dryer |
| BE793213A (en) * | 1972-04-07 | 1973-06-22 | Ciba Geigy | DRY COATING PROCESS OF A MATERIAL |
| US4012540A (en) * | 1973-04-03 | 1977-03-15 | The Procter & Gamble Company | Method of conditioning fabrics in a clothes dryer |
| US3956556A (en) * | 1973-04-03 | 1976-05-11 | The Procter & Gamble Company | Article for conditioning fabrics in a clothes dryer |
| US4070520A (en) * | 1976-09-03 | 1978-01-24 | Scott Paper Company | Fabric softener composition |
| US4095946A (en) * | 1977-03-25 | 1978-06-20 | The Procter & Gamble Company | Article for cleaning and conditioning fabrics |
| CA1262806A (en) * | 1977-09-06 | 1989-11-14 | Ernst Stahli | Fabric conditioning products |
-
1979
- 1979-01-19 CH CH53479A patent/CH643779A5/en not_active IP Right Cessation
- 1979-01-24 DE DE19792902580 patent/DE2902580A1/en not_active Withdrawn
- 1979-01-24 CA CA000320190A patent/CA1268302A/en not_active Expired
- 1979-01-25 BR BR7900458A patent/BR7900458A/en unknown
- 1979-01-25 GB GB8213145A patent/GB2097830A/en not_active Withdrawn
- 1979-01-25 GB GB7902653A patent/GB2013260B/en not_active Expired
- 1979-01-26 NL NL7900619A patent/NL7900619A/en not_active Application Discontinuation
- 1979-01-26 DK DK33779A patent/DK33779A/en not_active Application Discontinuation
- 1979-01-26 JP JP729679A patent/JPS54112297A/en active Granted
- 1979-01-26 SE SE7900725A patent/SE443587B/en not_active IP Right Cessation
- 1979-01-26 IT IT83319/79A patent/IT1127823B/en active
- 1979-01-26 FR FR7902114A patent/FR2416972A1/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| IT7983319A0 (en) | 1979-01-26 |
| BR7900458A (en) | 1979-08-21 |
| FR2416972A1 (en) | 1979-09-07 |
| JPS54112297A (en) | 1979-09-03 |
| IT1127823B (en) | 1986-05-28 |
| GB2013260B (en) | 1983-03-30 |
| NL7900619A (en) | 1979-07-31 |
| DE2902580A1 (en) | 1979-08-02 |
| DK33779A (en) | 1979-07-28 |
| SE443587B (en) | 1986-03-03 |
| CH643779A5 (en) | 1984-06-29 |
| FR2416972B1 (en) | 1984-10-26 |
| GB2097830A (en) | 1982-11-10 |
| SE7900725L (en) | 1979-07-28 |
| GB2013260A (en) | 1979-08-08 |
| JPS616188B2 (en) | 1986-02-24 |
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| Date | Code | Title | Description |
|---|---|---|---|
| MKLA | Lapsed |