EP0194127B1

EP0194127B1 - Articles and methods for treating fabrics

Info

Publication number: EP0194127B1
Application number: EP86301501A
Authority: EP
Inventors: Mark David Evans; Robert Lee Stewart; Peter Herman Wolf; Roger Earl Zimmerer; Gregory Bruce Huntington
Original assignee: Procter and Gamble Co
Current assignee: Procter and Gamble Co
Priority date: 1985-03-06
Filing date: 1986-03-04
Publication date: 1990-03-28
Anticipated expiration: 2006-03-04
Also published as: CA1273156A; DE3669886D1; EP0194127A3; ES552681A0; ES8704563A1; EP0194127A2

Description

Technical field

The present invention encompasses articles for providing soil release, softening, odor, and antistatic benefits to fabrics in an automatic laundry dryer.

Background of the invention

Treatment in an automatic clothes dryer has been shown to be an effective means for imparting desirable tactile properties to fabrics. For example, it is becoming common to soften fabrics in an automatic clothes dryer rather than during the rinse cycle of a laundering operation. (See U. S. Pat. No. 3,442,692, Gaiser, issued May 6, 1969).
Fabric « softness is an expression well-defined in the art and is usually understood to be that quality of the treated fabric whereby its handle or texture is smooth, pliable and fluffy to the touch. Various chemical compounds have long been known to possess the ability to soften fabrics when applied to them during a laundering operation.
Fabric softness also connotes the absence of static « cling » in the fabrics, and the commonly used cationic fabric softeners provide both softening and antistatic benefits when applied to fabrics. Indeed, with fabrics such as nylon and polyester, the user is more able to perceive and appreciate an antistatic benefit than a true softening benefit.
On the other hand, soil release treatment of fabrics in an automatic clothes dryer is not as common as softening treatment.
European Published Application No. 0 071 148 discloses a product for imparting fabric softening and antistatic properties to fabrics in a rotary dryer, comprising an absorbent sheet substrate bearing a fabric softening quaternary ammonium salt. together with a condensation product of a fatty acid triglyceride with a hydroxyalkyl polyamine and other optional components, one of which can be a soil release polymer.
U. S. Pat. No. 4,238,531, Rudy et al., issued Dec. 9, 1980, discloses in its Examples 8 and 9 a soil release agent adjuvant plus a « distributing aid », polyethylene glycol (PEG).
It is, therefore, an object of the present invention to provide fabric soil releasing plus softening articles for use in automatic dryers which are superior in soil release benefits and softening compared to the prior art.
This and other objects are obtained herein, as will be seen from the following disclosure.

Summary of the invention

According to the present invention, there is provided an article of manufacture adapted for providing fabric soil release and softening benefits within an automatic clothes dryer, said article comprising :

(a) a fabric conditioning composition having a melting point of at least 38 'C and being flowable at dryer operating temperatures, said fabric conditioning composition comprising :
- i. a polymeric soil release agent; and
- ii. a fabric softening agent selected from cationic and nonionic fabric softeners and mixtures thereof ;
(b) dispensing means comprising a flexible substrate to which said composition is releasably affixed in a weight ratio of from 0.5 : 1 to 10 : 1, and which provides for release of said conditioning composition within an automatic laundry dryer at dryer operating temperatures ; wherein the fabric softening agent comprises from 30 % to 99 % by weight of the composition and said polymeric soil release agent comprises from 1 % to 70 % by weight of the composition and has the formula :

wherein the A moieties are essentially
moieties ; the R' moieties are essentially 1,4-phenylene moieties ; and the R² moieties are essentially ethylene moieties, or substituted ethylene moieties having C₁-C₄ alkyl or alkoxy substituents; the R³ moieties are substituted C₂-C₁₈ hydrocarbylene moieties having at least one -S0₃M, -COOM, -0-[-R⁵O)_m(CH₂CH₂O)n-]-X or -A-[-(R²-A-R⁴-A)-]-_w-[-R⁵O)_m(CH₂CH₂O)_n-]-X substituent or at least one moiety -A-(-(R²-A-R⁴-A)-]-_wR²-A- crosslinked to another R³ moiety ; the R⁴ moieties are R¹ or R³ moieties, or a mixture thereof ; each R⁵ is C₃-C₄ alkylene, or the moiety -R²-A-R^6-, wherein R⁶ is a C₁-C₁₂ alkylene, alkenylene, arylene or alkarylene moiety ; each M is H or a water-soluble cation ; each X is H, C₁-C₄ alkyl or
wherein R⁷ is C₁-C₄ alkyl ; m and n are numbers such that the moiety -(CH₂CH₂0)- comprises at least 50 % by weight of the moiety -[-R⁵O)_m(CH₂CH₂O)_n-]-, provided that when R⁵ is the moiety -R²-A-R^6-, m is 1 ; each n is at least 10 ; u and v are numbers such that the sum of u + v is from 3 to 25 ; w is 0 or at least 1 ; and when w is at least 1, u, v and w are numbers such that the sum of u + v + w is from 3 to 25.

When the dispensing means is a flexible substrate in sheet configuration the fabric condition composition is releasably affixed on the substrate to provide a weight ratio of conditioning composition to dry substrate ranging from 10 : 1 to 0.5 : 1.
The term « fabric conditioning composition as used herein is defined as a mixture of polymeric soil release agent and a fabric softening agent as defined herein.

Polymeric Soil Release Agent

The polymeric soil release agents useful in the present invention are those disclosed in the commonly assigned European Published Application No. 0185427 which forms part of the state of the art under Article 54(3) EPC. The soil release agent is present at a level of from 1 % to 70 %, more preferably from 10 % to 70 %, and most preferably from 25 % to 50 %, by weight of the fabric conditioning composition.
The most preferred polymer is a solid at room temperature, has a softening phase transition temperature at or above 30 'C and becomes a flowable liquid below 100 'C, preferably below 90 'C. The softening phase transition temperature can be determined by the differential scanning calorimetry method. A polymer that is a hard solid at room temperature is desirable in order to keep the fabric conditioning sheets from having a tacky feel, while its softening and fluidity at higher temperatures facilitate the substrate coating process and the subsequent fabric conditioning active transfer from the fabric conditioning sheet to the fabrics in the clothes dryer at automatic dryer operating temperatures, i. e. 35 °C to 115 'C.
The polymeric soil release agent disclosed in the commonly assigned EP-A-0185427 has the formula :

wherein the A moieties are essentially
moieties ; the R¹ moieties are essentially 1,4-phenylene moieties ; and R² moieties are essentially ethylene moieties, or substituted ethylene moieties having C₁-C₄ alkyl or alkoxy substituents ; the R³ moieties are substituted C₂-C₁₈ hydrocarbylene moieties having at least one -S0₃M, -COOM, -0-[-R⁵O)_m(CH₂CH₂O)_n-]-X or -A-[-(R²-A-R⁴-A)-]-_w-[-R⁵O)_m(CH₂CH₂O)_n-]-X substituent or at least one moiety -A-[-(R²-A-R⁴-A)-]-_wR²-A- crosslinked to another R³ moiety ; the R⁴ moieties are R¹ or R³ moieties, or a mixture thereof ; each R⁵ is C₃-C₄ alkylene, or the moiety -R²-A-R^6-, wherein R⁶ is a C₁-C₁₂ alkylene, alkenylene, arylene or alkarylene moiety ; each M is H or a water-soluble cation ; each X is H, C₁-C₄ alkyl or
wherein R⁷ is C₁-C₄ alkyl ; m and n are numbers such that the moiety -(CH₂CH₂0)- comprises at least 50 % by weight of the moiety -[-R⁵O)_m(CH₂CH₂O)_n-]-, provided that when R⁵ is the moiety -R²-A-R⁶-, m is 1 ; each n is at least 10 ; u and v are numbers such that the sum of u + v is from 3 to 25 ; w is 0 or at least 1 ; and when w is at least 1, u, v and w are numbers such that the sum of u + v + w is from 3 to 25.
This latter polymer is particularly preferred when the formula is :

wherein each R¹ is a 1,4-phenylene moiety ; the R² moieties consist essentially of ethylene moieties, 1,2-propylene moieties or a mixture thereof ; each X is ethyl or preferably methyl : each n is from about 12 to 43 and u is from 3 to 10.
A preferred polymeric soil release agent is POET (polyoxyethylene terephthalate), a compound with the general formula described hereinabove. It is synthesized from the following reactants :

1. Poly(ethylene glycol)methyl ester, M. W. 750, Aldrich Chemical Co., 1 000 g (1.33 moles)
2. Dimethyl terephthalate, M. W. 195, Aldrich Chemical Co., 359.9 g (1.85 moles)
3. Ethylene glycol, M. W. 62, Aldrich Chemical Co., 146.4 g (2.36 moles)
4. Calcium acetate, MCB, 7.9 g (catalyst)
5. Antimony trioxide, Fisher Scientific, 7.9 g (catalyst)
6. Butylated hydroxytoluene, Aldrich Chemical Co., 3.6 g (antioxidant).

The reaction was carried out by adding all of the above to a 2 liter round bottom flask equipped with mechanical agitation. A 335 mm unpacked column was also fitted to the flask for methanol distillation. The system was placed under a nitrogen atmosphere and the temperature was gradually raised to 200 'C once the reaction mixture melted. Reaction conditions of 200 'C, atmospheric pressure, and constant mechanical agitation were maintained for 20 hours. To further drive the ester interchange reaction to completion, the reaction mixture was cooled to 130 'C, the methanol receiving flask was emptied, and vacuum was applied while concurrently introducing nitrogen sparge below the level of the liquid reaction mixture. An absolute pressure of 3.3 kPa (25 mm Hg) was obtained. Over a period of 2 hours the temperature was gradually raised to 190 'C, distilling more methanol and ethylene glycol. To complete the reaction, the temperature was raised to 200 'C and the pressure was reduced to 20 mm Hg. The nitrogen flow into the reaction mixture was discontinued. After 3.5 hours, the reaction was essentially complete as indicated by reverse phase HPLC analysis. (Using a column packed with hexyl capped silica particles and an acetonitrile/water gradient elution). This analysis showed that a sizable part of the polymer contained 4 or more terephthalate units per molecule. The general formula for the resulting compound is :

wherein n = 1.75 on average.
The resulting polymer was submitted to a three-solvent (short chain alcohols) extraction (IPA, EtOH, MeOH) and the EtOH, MeOH soluble fractions were combined in the ratio of 67 33.
This extraction procedure resulted in a polymer sample containing predominantly 3 to 5 terephthalate units per molecule as shown by HPLC analysis.
In general, the soil release polymer is preferably a solid at room temperature, has a softening phase transition temperature at or above 30°C and becomes a flowable liquid below 100 'C, more preferably below 90 °C.

Fabric Softening Agent

The term « fabric softening agent as used herein includes cationic and nonionic fabric softeners used alone and also in combination with each other. The preferred fabric softening agent of the present invention is a mixture of cationic and nonionic fabric softeners.
Examples of fabric softening agents are the compositions described in U. S. Pat. Nos. 4,103,047, Zaki et al., issued July 25, 1978 ; 4,237,155, Kardouche, issued Dec. 2, 1980 ; 3,686,025, Morton, issued Aug. 22, 1972; 3,849,435, Diery et al., issued Nov. 19, 1974; and U. S. Pat. No. 4,037,996, Bedenk, issued Feb. 14, 1978.
Particularly preferred cationic fabric softeners of this type include quaternary ammonium salts such as dialkyl dimethylammonium chlorides, methylsulfates and ethylsulfates wherein the alkyl groups can be the same or different and contain from 14 to 22 carbon atoms. Examples of such preferred materials include ditallowalkyldimethylammonium methylsulfate, distearyldimethylammonium methylsulfate, dipal- mityldimethylammonium methylsulfate and dibehenyldimethylammonium methylsulfate. Also particularly preferred is the carboxylic acid salt of a tertiary alkylamine disclosed in said Kardouche patent. Examples include stearyldimethylammonium stearate, distearylmethylammonium myristate, stearyldimethylammonium palmitate, distearylmethylammonium palmitate, and distearylmethylammonium laurate. These carboxylic salts can be made in situ by mixing the corresponding amine and carboxylic acid in the molten fabric conditioning composition.
Examples of nonionic fabric softeners are the sorbitan esters, described herein and C₁₂-C₂₆ fatty alcohols and fatty amines as described herein.
A preferred article of the present invention includes a fabric conditioning composition which comprises 10 % to 70 % of polymeric soil release agent, and 30 % to 90 % of a fabric softening agent, wherein said fabric softening agent is selected from cationic and nonionic fabric softeners, and mixtures thereof. Preferably, said fabric softening agent comprises a mixture of 5 % to 80 % of a cationic fabric softener and 10 % to 85 % of a nonionic fabric softener by weight of said fabric conditioning composition. The selection of the components is such that the resulting fabric conditioning composition has a melting point above 38 'C and is flowable at dryer operating temperatures.
A preferred fabric softening agent comprises a mixture of C₁₀-C₂₆ alkyl sorbitan esters and mixtures thereof, a quaternary ammonium salt and an tertiary alkylamine. The quaternary ammonium salt is preferably present at a level of from 5 % to 25 %, more preferably from 7 % to 20 % of the fabric conditioning composition. The sorbitan ester is preferably present at a level of from 10 % to 50 %, more preferably from 20 % to 40 %, by weight of the fabric conditioning composition. The tertiary alkylamine is present at a level of from 5 % to 25 %, more preferably from 7 % to 20 % by weight of the fabric conditioning composition. The preferred sorbitan ester comprises a member selected from C,_o-C₂₆ alkyl sorbitan monoesters and C_lO-C₂₆ alkyl sorbitan di-esters, and ethoxylates of said esters wherein one or more of the unesterified hydroxyl groups in said esters contain from 1 to 6 oxyethylene units, and mixtures thereof. The quaternary ammonium salt is preferably in the methylsulfate form. The preferred tertiary alkylamine is selected from alkyldimethylamine and dialkylmethylamine and mixtures thereof, wherein the alkyl groups can be the same on different and contain from 14 to 22 carbon atoms.
Another preferred fabric softening agent comprises a carboxylic acid salt of a tertiary alkylamine, in combination with a fatty alcohol and a quaternary ammonium salt. The carboxylic acid salt of a tertiary amine is used in the fabric conditioning composition preferably at a level of from 5 % to 50 %, and more preferably from 15 % to 35 %, by weight of the fabric conditioning composition. The quaternary ammonium salt is used preferably at a level of from 5 % to 25 %, and more preferably from 7 % to 20 %, by weight of the total fabric conditioning composition. The fatty alcohol can be used preferably at a level of from 10% to 25%, and more preferably from 10% to 20%, by weight of the fabric conditioning composition. The preferred quaternary ammonium salt is selected from dialkyl dimethylammonium salts wherein the alkyl groups can be the same or different and contain from 14 to 22 carbon atoms and wherein the counteranion is selected from chloride, methylsulfate and ethylsulfate, preferably methylsulfate. The preferred carboxylic acid salft of a tertiary alkylamine is selected from fatty acid salts of alkyldimethylamines wherein the alkyl group contains from 14 to 22 carbon atoms. The preferred fatty alcohol contains from 14 to 22 carbon atoms.

Optional Ingredients

Well known optional components included in the fabric conditioning composition which are useful in the present invention are narrated in U. S. Pat. No. 4,103,047, Zaki et al., issued July 25, 1978, for « Fabric Treatment Compositions ».

Dispensing Means

The fabric conditioning compositions are provided as an article of manufacture in combination with a dispensing means such as a flexible substrate which effectively releases the composition in an automatic clothes dryer. Such dispensing means can be designed for single usage or for multiple uses.
One such article comprises a sponge material releasably enclosing enough fabric conditioning composition to effectively impart fabric soil release and softness benefits during several cycles of clothes. This multi-use article can be made by filling a hollow sponge with 20 grams of the fabric conditioning composition.
Other devices and articles suitable for dispensing the fabric conditioning composition into automatic dryers include those described in U. S. Pat. Nos. 4,103,047, Zaki et al., issued July 25, 1978 ; 3,736,668, Dillarstone, issued June 5, 1973 ; 3,701,202, Compa et al., issued Oct. 31, 1972 ; 3,634,947, Furgal, issued Jan. 18, 1972 ; 3,633,538, Hoeflin, issued Jan. 11, 1972; and 3,435,537, Rumsey, issued Apr. 1, 1969.
A highly preferred article herein comprises the fabric conditioning composition releasably affixed to a flexible substrate in a sheet configuration. Highly preferred paper, woven or nonwoven absorbent substrates usefut herein are fully disclosed in Morton, U. S. Pat. No. 3,686,026, issued Aug. 22, 1987.
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 liquid) from 4 to 12, preferably 5 to 7, times its weight of water.
Determination of absorbent capacity values is made by using the capacity testing procedures described in U. S. Federal Specifications UU-T-595b, modified as follows :

1. tap water is used instead of distilled water;
2. the specimen is immersed for 30 seconds instead of 3 minutes ;
3. draining time is 15 seconds instead of 1 minute ; and
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. Based on this test, one-ply, dense bleached paper (e. g., kraft or bond having a basis weight of 52 g/m²) has an absorbent capacity of 3.5 to 4, commercially 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 4 tends to cause too rapid release of the fabric conditioning composition from the substrate resulting in several disadvantages, one of which is uneven conditioning of the fabrics. Using a substrate with an absorbent capacity over 12 is undesirable, inasmuch as too little of the fabric conditioning composition is released to condition the fabrics in optimal fashion during a normal drying cycle.
Such a substrate comprises a nonwoven cloth having an absorbent capacity of preferably from 5 to 7 and wherein the weight ratio of fabric conditioning composition to substrate on a dry weight basis ranges from 5 : 1 to 1 : 1.
Nonwoven cloth substrate preferably comprises cellulosic fibers having a length of from 4.8 mm to 51 mm and a linear density of from 0.166 to 0.55 Tex and the substrate is adhesively bonded together with a binder resin.
The flexible substrate preferably has openings sufficient in size and number to reduce restriction by said article of the flow of air through an automatic laundry dryer. The'preferred openings comprise a plurality of rectilinear slits extended along one dimension of the substrate.

Usage

The method for imparting the above-described fabric conditioning composition to provide soil release, softening and antistatic effects to fabrics in an automatic laundry dryer comprises : co-mingling pieces of damp fabrics by tumbling said fabrics under heat in an automatic clothes dryer with an effective amount of the fabric conditioning composition, said composition having a melting point greater than 38 °C and being flowable at dryer operating temperature, said composition comprising from 1 % to 70 % of a polymeric soil release agent, and 30 % to 99 % of a fabric softening agent selected from the above- defined cationic and nonionic fabric softeners and mixtures thereof.
The method herein is carried out in the following manner. Damp fabrics, usually containing from 1 to 1.5 times their weight of water, are placed in the drum of an automatic clothes dryer. In practice, such damp fabrics are commonly obtained by laundering, rinsing and spin-drying the fabrics in a standard washing machine. The dryer is then operated in standard fashion to dry the fabrics, usually at a temperature from 50 °C to 80 'C for a period from 10 minutes to 60 minutes, depending on the fabric load and type. On removal from the dryer, the dried fabrics have been treated for soil release benefits and are softened. Moreover, the fabrics instantaneously sorb a minute quantity of water which increases the electrical conductivity of the fabric surfaces, thereby quickly and effectively dissipating static charge.
The process is carried out by fashioning an article comprising the substrate-like dispensing means of the type hereinabove described in releasable combination with a fabric conditioning composition. This article is simply added to a clothes dryer together with the damp fabrics to be treated. The heat and tumbling action of the revolving dryer drum evenly distributes the composition over all fabric surfaces, and dries the fabrics.
The following are nonlimiting examples of the instant articles and methods.
The components in Examples 1 and 2 were admixed and liquified at 70 'C. Each nonwoven substrate, comprised of 70 % 0.33 Tex, 39.7 mm long rayon fibers with 30 % polyvinyl acetate binder, is cut into a 229 x 279 mm sheet. Slightly more than target coating weight is distributed on a heating plate and the nonwoven cloth is placed over it. A small paint roller is used to impregnate the mixture into the interstices of the substrate. The article is removed from the hot plate and allowed to cool to room temperature whereby the mixture solidifies. Following solidification of the fabric conditioning composition, the cloth is slit with a knife. (Conveniently, the cloth is provided with 3 to 9 rectilinear slits extending along one dimension of the substrate, said slits being in substantially parallel relationship and extending to within 25 mm from at least one edge of said dimension of the substrate). The width of an individual slit is 5 mm.

Fabric Softening and Soil Release Evaluations

The fabric softening and soil release performance of the articles is determined by means of a fabric softening evaluation and a soil release evaluation. In such evaluations, 2.38 kg loads of fabric representing a range of fabric types (cotton, polyester/cotton, polyester, acrylics, and nylon) are washed using a leading detergent, a 14 minute wash cycle with warm (37.8 °C) medium hardness (137-172 ppm CaC0₃) water, a 2 minute rinse in cold (15 °C) water, and are dried for 45 minutes in a standard household clothes dryer with the appropriate test treatment (product). Included in each 2.38 kg. Fabric load are four 100 % cotton terry cloths to be used for softness grading and four each, selected 305 x 305 mm swatches of 100 % polyester, or 65 %/35 % polyester/cotton to be used for soil release evaluation. [All terries and soil release swatches are prewashed in the following manner to remove any « factory finishes » : terries and swatches are laundered using IVORY SNOW^R detergent, a 14 minute wash cycle with hot (65.5 'C) medium hardness (137-172 ppm CaC0₃) water, and a 2 minute rinse in hot (65.5 °C) water. The entire wash and rinse cycles are then repeated in ERA^R detergent. This is followed by two 6 minute wash and 2 minute rinse cycles in hot (65.5 °C) water. The prewashed terries and swatches are then dried and added to the test wash load.] Following washing and drying, the cotton terry cloths are removed from each fabric load for subsequent softening evaluation. The 2.38 kg bundles containing the swatches for soil release evaluation are then rewashed and dried using the same procedures cited above for a total of 3 washes and 3 dries.

Softness Evaluation

For fabric softening evaluation, the cotton terry cloths are graded « blind by three qualified judges to determine softness performance of the different treatments (products). The comparison between treatments is expressed in terms of grading scale units (GSU) where :

0 GSU ₌ no difference
1 GSU = a slight difference
2 GSU = a moderate difference
3 GSU = a large difference
4 GSU = a very large difference

All treatment comparisons (judges grades) are summarized and subjected to a statistical one way analysis of variance. The treatment relationships are reported in terms of grading scale units (GSU) along with a statistical estimate of test precision. (Least significant difference, i. e., LSD).
For softness evaluation, the articles of Example 1 and Comparative Example 3 are compared to a « no softener control.
Results of the softness grading are summarized in Table II.

Average LSD = 0.31

The Table II data demonstrate that an article in accordance with the present invention provides fabric softening performance comparable to that of a prior art fabric softening article (Comparative Example 3).

Soil Release Evaluation

For soil release evaluation, the polyester and polyester/cotton swatches are removed from the fabric loads after the third wash and dry cycle. Stains such as dirty motor oil, spaghetti, grass, and clay are applied to each swatch in a 51 mm circle using a standard paint brush. Swatches are stored overnight (12-16 hours) at 4.5 'C. to set the stains. The next day swatches are allowed to equilibrate to room temperature and are then washed in identical 2.38 kg fabric loads and under the same conditions as described above. They are dried for 45 minutes in standard household clothes dryers using no fabric conditioning material.
The swatches are graded « blind by three qualified judges to determine soil release performance of the different treatments (products). The comparison between treatments is expressed in terms of grading scale units (GSU) where :

0 GSU = no difference
1 GSU = a slight difference
2 GSU = a moderate difference
3 GSU ₌ a large difference
4 GSU = a very large difference

All treatment comparisons (judges grades) are summarized and subjected to typical one way analysis of variance. The treatment relationships are reported in terms of grading scale units (GSU) along with a statistical estimate of test precision. (Least significant difference, i. e., LSD).
For soil release evaluation, the article of Example 1 of the present invention, together with Comparative Examples 3 and 4 are used. In addition, data from direct application of a soil release polymer are included. (Comparative Example 5).
In Comparative Example 5 Zelcon 4780 (dispersion) is applied directly (by pipette) to swatches in the amount of approximately 1.0 g of Zelcon polymer/lb. swatch (2.2 g/_Kg). These swatches are air dried, then stained, stored, and washed as described above. The results of the soil release gradings are summarized in Tables III A & B.
The above-described fabric treatment and soil release evaluation procedures are illustrative of the invention herein and are not to be construed as limiting thereof.
It should be noted that where 2 sheets of the article per cycle are used the benefits are thereby increased. These data are relative to the detergent only control. These data demonstrate that the articles of the present invention, Examples 1 & 2 provide soil release performance on both greasy/oily and clay stains, whereas Comparative Examples 3, 4 and 5 provided soil release performance on only greasy/oily stains or clay stains. In fact, Comparative Example 5, showing soil release performance of the soil release action directly applied, exhibited poorer clay removal than detergent alone.

Claims

1. An article of manufacture adapted for providing fabric soil release and softening benefits within an automatic clothes dryer, said article comprising :

(a) a fabric conditioning composition having a melting point of at least 38 'C and being flowable at dryer operating temperatures, said fabric conditioning composition comprising :

i. a polymeric soil release agent ; and

ii. a fabric softening agent selected from cationic and nonionic fabric softeners and mixtures thereof ;

(b) dispensing means comprising a flexible substrate to which said composition is releasably affixed in a weight ratio of from 0.5 : 1 to 10: 1, and which provides for release of said conditioning composition within an automatic laundry dryer at dryer operating temperatures ; characterised in that the fabric softening agent comprises from 30 % to 99 % by weight of the composition and said polymeric soil release agent comprises from 1 % to 70 % by weight of the composition and has the formula :

wherein the A moieties are essentially

moieties ; the R¹ moieties are essentially 1,4-phenylene moieties ; and R² moieties are essentially ethylene moieties, or substituted ethylene moieties having C₁-C₄ alkyl or alkoxy substituents ; the R³ moieties are substituted C₂-C₁₈ hydrocarbylene moieties having at least one -SO₃M, -COOM, -0-[-R⁵O)_m(CH₂CH₂O)_n-]-X or -A-[-(R²-A-R⁴-A)-]-_w-[-R₅O)_m(CH₂CH₂O)_n-]-X substituent or at least one moiety -A-[-(R²-A-R⁴-A)-]-_wR²-A- crosslinked to another R³ moiety ; the R⁴ moieties are R¹ or R³ moieties, or a mixture thereof ; each R⁵ is C₃-C₄ alkylene, or the moiety -R²-A-R^6-, wherein R⁶ is a C₁-C₁₂ alkylene, alkenylene, arylene or alkarylene moiety ; each M is H or a water-soluble cation ; each X is H, C₁-C₄alkyl or

wherein R⁷ is C₁-C₄ alkyl ; m and n are numbers such that the moiety -(CH₂CH₂0)-comprises at least 50 % by weight of the moiety -[-R₅O)_m(CH₂CH₂O)_n-]-, provided that when R⁵ is the moiety -R²-A-R^6-, m is 1 ; each n is at least 10 ; u and v are numbers such that the sum of u ₊ v is from 3 to 25 ; w is 0 or at least 1 ; and when w is at least 1, u, v and w are numbers such that the sum of u + v + w is from 3 to 25.

2. An article according to Claim 1 wherein said polymeric soil release agent has the following formula :

wherein each R¹ is a 1,4-phenylene moiety ; the R² consist essentially of ethylene moieties, 1,2-propylene moieties or a mixture thereof ; each X is ethyl or preferably methyl ; each n is from about 12 to 43 ; and u is from 3 to 10.

3. An article according to Claim 2 wherein said polymeric soil release agent is present at a level of from 10 % to 70 % by weight of the fabric conditioning composition.

4. An article according to any one of claims 1-3 wherein said polymeric soil release agent has a softening phase transition temperature of at least 30 'C and becomes a flowable liquid below 100 'C.

5. An article according to Claim 4 wherein said polymeric soil release agent becomes a flowable liquid below 90°'C and is present at a level of from 25 % to 50 % by weight of the fabric conditioning composition.

6. An article according to any one of claims 1-5 wherein said fabric softening agent comprises a mixture of from 5 % to 80 % of a cationic fabric softener and from 10 % to 85 % of a nonionic. fabric softener by weight of said fabric conditioning composition.

7. An article according to claim 6 wherein said cationic fabric softener is selected from :

(a) a quaternary ammonium salt ; and

(b) a carboxylic acid salt of a tertiary alkylamine ; and mixtures of (a) and (b) ; and wherein said nonionic fabric softener is selected from :

(c) a fatty alkyl sorbitan ester ;

(d) a fatty alcohol ; and

(e) a fatty amine ; and binary and ternary mixtures of (c), (d) and (e).

8. An article according to claim 7 wherein said fabric softening agent comprises a mixture of from 5 % to 25 % of a quaternary ammonium salt, from 10 % to 50 % of a fatty sorbitan polyester, and from 5 % to 25 % of a fatty amine, all percentages being by weight of the fabric conditioning composition.

9. An article according to claim 8 wherein said fabric softening agent comprises a mixture of from 7% to 20 % of di-C₁₄-C₂₂ alkyl dimethyl ammonium methylsulfate, from 20 % to 40 % of C₁₀-C₁₆ alkyl sorbitan polyester, and from 7 % to 20 % of C_14-C₂₂ alkyldimethylamine and/or- C₁₄-C₂₂ dialkylmethylamine, all percentages being by weight of the fabric conditioning composition.

10. An article according to claim 7 wherein said fabric softening agent comprises a mixture of from 5 % to 25 % of a quaternary ammonium salt, from 10 % to 50 % of a carboxylic acid salt of a tertiary alkylamine, and from 10 % to 25 % of a fatty alcohol, all percentages being by weight of the fabric conditioning composition.

11. An article according to claim 10 wherein said fabric softening agent comprises a mixture of from 7% to 20 % of di-C₁₄-C₂₂ alkyldimethyl quaternary ammonium methylsulfate, from 15 % to 35% of C₁₄-C₂₂ carboxylic acid salt of a tertiary C₁₄-C₂₂ alkylamine, and from 10% to 20 % of a C₁₄-C₂₂ fatty alcohol.

12. An article according to any one of the preceding claims wherein said substrate is a bonded nonwoven cloth comprising cellulosic fibers, of length from 4.8 to 51 mm and of 0.166 to 0.56 Tex, said cloth being provided with a plurality of rectilinear slits extending along one dimension of the cloth.