(19)
(11) EP 0 612 841 A2

(12) EUROPEAN PATENT APPLICATION

(43) Date of publication:
31.08.1994 Bulletin 1994/35

(21) Application number: 94300963.9

(22) Date of filing: 10.02.1994
(51) International Patent Classification (IPC)5C11D 3/12, D06M 11/79
(84) Designated Contracting States:
CH DE ES FR GB IT LI NL SE

(30) Priority: 25.02.1993 GB 9303815

(71) Applicants:
  • UNILEVER PLC
    London EC4P 4BQ (GB)

    GB 
  • UNILEVER N.V.
    NL-3013 AL Rotterdam (NL)

    CH DE ES FR IT LI NL SE 

(72) Inventors:
  • Ashdown, Janice Dawn, Unilever Research Port
    Wirral, Merseyside,L63 3JW (GB)
  • Chapple, Andrew Paul, Unilever Research Port
    Wirral, Merseyside,L63 3JW (GB)
  • Prescott, Andrew John, Unilever Research Port
    Wirral, Merseyside,L63 3JW (GB)

(74) Representative: Fransella, Mary Evelyn et al
Unilever PLC Patent Division Colworth House Sharnbrook
Bedford MK44 1LQ
Bedford MK44 1LQ (GB)


(56) References cited: : 
   
       


    (54) Use of fabric treatment compostions


    (57) The use of fabric softening clay on keratin containing fibres for controlling and for preventing pilling.


    Description


    [0001] The invention relates to the use of a fabric softening clay for control and prevention of pilling caused by washing and use of fabrics.

    [0002] The phenomenon of pilling of fabrics is well known. It is caused by rubbing the fabrics and fibres, both in use, referred to as the wear cycle, and during the washing process, referred to as the wash cycle. The rubbing causes fibres to migrate within the fabric structure and tends to increase the number of fibres, "fuzz fibres" protruding from the fabric surface. This results in the formation of surface fuzz. Continued rubbing causes damage to, and entanglement of, those "fuzz fibres" to form "pills" or "fuzz balls". The occurrence of pills on fabrics is very common and the unsightly appearance gained thereby is associated with old age and hard wear although the problem may, in fact, develop quickly on a neww garment. Pilling often leads to an article or garment being discarded. Pilling is particularly a problem on knitted fabrics; especially those comprising long staple fibres such as wool, mohair etc.

    [0003] Attempts have been made to solve the problem of pilling by bonding fibres of a textile together as part of an industrially applied textile treatment usually by a process of impregnating the fibres with a polymer followed by crosslinking the polymer in-situ to form a bonded whole. Such or similar processes are described in EP 311 642, EP 190 672, US 4 225 646 and US 4 098 701. An alternative solution is to ion-irradiate animal yarns before or after spinning as described in JP 61047836.

    [0004] The disadvantages of these industrial processes are that they often require high temperatures or direct application of the composition to the textile, for example by padding, which makes them inappropriate for the treatment of articles or garments as part of a domestic process. Furthermore, they are often ineffective as is shown by the ready occurrence of pills on so-called treated textiles. This is probably due to the composition, which has been deposited on the fibres during the treatment, being washed off or worn off as the article is used and cleaned.

    [0005] WO 89/04862 relates to a detergent composition for cleaning and softening fabrics in which cellulase granulates containing calcium carbonate are used in certain combinations with a fabric softening clay to wash cotton swatches. A composition comprising cellulase and clay is said to improve the appearance of the cotton fabric by improved colour and anti-pilling performance. These improvements are probably due to the action of cellulase on cotton which is a cellulosic fibre.

    [0006] GB 1 400 898 relates to the use of certain clays in detergent compositions for imparting a softening benefit to fabrics washed therewith. No pilling prevention or control is mentioned.

    [0007] We have now found that pilling can be controlled or prevented by the use of a fabric softening clay.

    [0008] Accordingly the invention provides the use of a fabric softening clay for controlling pilling and for prevention of pilling of keratin containing fibres.

    [0009] The invention has the advantage that pilling of fabrics containing keratin containing fibres can be prevented and controlled by use of a fabric softening clay in a process compatible with the domestic washing process. Use of the invention can also give colour care and shrinkage benefits.

    [0010] Examples of keratin containing fibres include lambswool, shetland wool, botany wool, merino wool, mohair, cashmere, or fibres from animals such as: llama, vicuna, camel, angora and alpaca and yak. Pilling on fabrics made of keratin containing fibres or blends of keratin containing fibres with synthetic fibres is particularly noticeable. The invention is beneficial when used with both shrink resist treated and untreated wool; either alone or blended with other fibres.

    [0011] The invention further provides the use of a fabric softening clay in a composition comprising a detergent active for controlling pilling and for preventing pilling of fabrics made of keratin containing fibres.

    [0012] This aspect of the invention has the advantage that the use of the fabric softening clay can be carried out as part of a washing process giving a desirable overall effect of cleaning and pilling control or prevention.

    [0013] The invention further provides the use of a fabric softening clay in a composition in the form of an aqueous dispersion comprising a fabric substantive compound for controlling pilling and for preventative pilling control of fabrics made of keratin containing fibres.

    [0014] This aspect of the invention has the advantage that the use of the fabric softening clay can be carried out as part of a rinsing process giving a desirable overall effect of softening and pilling control or prevention.

    [0015] Examples of suitable fabric softening clays for use in the present invention include various heat treated kaolins and various multi-layer smectites. Preferred clay softeners are smectite softener clays as described in GB 1 400 898, EP 350 288 and EP 0 297 673. Montmorillonite clays are especially preferred. Softening clays are used in the preferred compositions at levels of at least 1%, generally 1-20%, preferably 2-10% by weight.

    [0016] The fabric softening clays may be used in admixture with one or more fabric softening materials such as cationic fabric softeners or amine materials. Examples of suitable cationic fabrics softeners include substantially water insoluble quaternary ammonium compounds such as for instance dihardened tallow dimethyl ammonium chloride and similar di (long-chain) quaternaries and ester-linked quaternaries as for instance disclosed in EP 239 910, US 3 915 867 and US 4 137 180.

    [0017] Examples of amine materials include tertiary amines and those disclosed in EP 0 199 383 and EP 0 345 842.

    [0018] Compositions for use in the invention may comprise one or more detergent active materials selected from soaps, non-soap anionic, nonionic, zwitterionic and amphoteric synthetic detergent active materials and optionally one or more fabric softening materials.

    [0019] Many suitable detergent compounds are commercially available and are fully described in the literature, for example in "Surface Active Agents and Detergents", Volumes I and II, by Schwartz, Perry and Berch.

    [0020] Anionic surfactants useful in the present invention include: Linear alkyl sulphonates. Examples of suitable synthetic anionic detergent compounds are sodium and potassium alkyl sulphates, especially those obtained by sulphating higher (C₈-C₁₈) alcohols produced for example from tallow or coconut oil, sodium and potassium alkyl (C₉-C₂₀) benzene sulphonates, particularly sodium linear secondary alkyl (C₁₀-C₁₅) benzene sulphonates; sodium alkyl glyceryl ether sulphates, especially those ethers of the higher alcohols derived from tallow or coconut oil and synthetic alcohols derived from petroleum; sodium coconut oil fatty monoglyceride sulphates and sulphonates; sodium and potassium salts of sulphuric acid esters of higher (C₈-C₁₈) fatty alcohol-alkylene oxides, particularly ethylene oxide, reaction products; the reaction products of fatty acids such as coconut fatty acids esterified with isethionic acid and neutralised with sodium hydroxide; sodium and potassium salts of fatty acid amides of methyl taurine; alkane monosulphonates such as those derived by reacting alpha-olefins (C₈-C₂₀) with sodium bisulphite and those derived from reacting paraffins with SO₂ and Cl₂ and then hydrolysing with a base to produce a random sulphonate; and olefin sulphonates, which term is used to describe the material made by reacting olefins, particularly C₁₀-C₂₀ alpha-olefins, with SO₃ and then neutralising and hydrolysing the reaction product.

    [0021] Preferred anionic detergent compounds are sodium (C₁₁-C₁₅) alkyl benzene sulphonates and sodium (C₁₆-C₁₈) alkyl sulphates. Directly esterified isethionates may also be used.

    [0022] Suitable nonionic compounds which may be used include in particular the reaction products of compounds having a hydrophobic group and a reactive hydrogen atom, for example aliphatic alcohols, acids, amides or alkyl phenols with alkylene oxides, especially ethylene oxide either alone or with propylene oxide. Specific nonionic detergent compounds are alkyl (C₆-C₂₂) phenols-ethylene oxide condensates, generally up to 25 EO, i.e. up to 25 units of ethylene oxide per molecule, the condensation products of aliphatic (C₈-C₁₈) primary or secondary linear or branched alcohols with ethylene oxide, generally up to 40 EO, and products made by condensation of ethylene oxide with the reaction products of propylene oxide and ethylenediamide. Other so-called nonionic detergent compounds include alkyl polyglycosides, long tertiary amide oxides, glucamines, long chain tertiary phosphine oxides and dialkyl sulphoxides.

    [0023] Amounts of amphoteric or zwitterionic detergent compounds can also be used in the compositions of the invention but this is not normally desired due to their relatively high cost. If any amphoteric or zwitterionic detergent compounds are used it is generally in small amounts.

    [0024] Suitable fabric softening compounds to give additional fabric softening to that which may be provided by the fabric softening clay may for instance be selected from cationic fabric softening materials and nonionic fabric softening materials.

    [0025] The effective amount of the detergent active or fabric softening compound or compounds used in the composition of the present invention is generally in the range of up to 50%, preferably up to 40% by weight, most preferably not more than 30% by weight of the composition. Preferably the level is above 1%, most preferably more than 2%.

    [0026] Compositions of the invention may include detergency builder to improve the efficiency of the detergent active, in particular to remove calcium hardness ions from the water. The builder material may be selected from inorganic precipitating builders materials (such as alkali metal carbonates, bicarbonates, borates, orthophosphates and silicates), sequestering builder materials (such as alkali metal pyrophosphates, polyphosphates, amino polyacetates, phytates, polyphosphonates, aminopolymethylene phosphonates and polycarboxylates), ion-exchange builder materials (such as zeolites and amorphous alumino-silicates), organic precipitating builder materials (such as those having the formula (I):


    wherein: R₁ is C₁₀-C₂₄ alkyl or alkenyl, or an arylalkyl or alkylaryl group of equivalent chain length; X is CH, CR₂, N or CON; R₂ is C₁-C₃ alkyl; Z is COOY or SO₃Y; Y is hydrogen or a solubilising cation, preferably alkali metal and especially sodium; and n and m, which may be the same or different, are O or integers from 1 to 4, or mixtures of any one or more of these materials. Preferred examples of builder materials include sodium tripolyphosphate, mixtures thereof with sodium orthophosphate, sodium carbonate, mixtures thereof with calcite as a seed crystal, citrates, zeolite and the sodium salt of nitrilitriacetic acid. Among the Zeolites that find application in the present invention there may be mentioned: Zeolite A and X and mixtures thereof, particularly Zeolite 4A. Also of interest is Zeolite P described and claimed in EP0384070.

    [0027] The level of such builder material in the compositions of the invention may from 2 to 80% by weight, preferably from 7% to 70% by weight and most preferably from 14% to 60% by weight.

    [0028] Compositions comprising a detergent active according to the invention preferably are neutral or slightly alkaline when added to water at a concentration of 1% by weight at 25°C. Neutral compositions are especially preferred for wool wash use.

    [0029] Apart from the components already mentioned, a composition of the invention can contain any of the conventional additives in the amount in which such additives are normally employed in fabric washing detergent compositions. Optional additives include the lather boosters such as alkanolamides, particularly the monoethanolamides derivatives from palm kernel fatty acids and coconut fatty acids, lather depressants, oxygen-releasing bleaching agents such as sodium perborate and sodium percarbonate, peracid bleach precursors, chlorine-releasing bleaching agents such as trichloroisocyanuric acid, inorganic salts such as sodium sulphate, and, usually present in very minor amounts, fluorescent agents, perfumes including deodorant perfumes, enzymes such as cellulases, lipases, proteases and amylases, germicides and colourants.

    [0030] The compositions may be in any convenient form such as bars, powders, flakes, pastes or liquids which may be aqueous or non-aqueous and structured or unstructured.

    [0031] The detergent compositions may be prepared in any way appropriate to their physical form such as by dry-mixing the components, co-agglomerating them or dispersing them in a liquid carrier.

    [0032] For use in the rinse cycle of the fabric washing process, compositions for use in the present invention are preferably liquid and comprise an aqueous base, which may constitute from 5 to 97% by weight of the composition. The compositions may also include optional ingredients conventionally included in rinse compositions.

    [0033] The pH of fabric treatment compositions for use in the rinse is preferably less than 8.0 when added to water at a concentration of 1% by weight of the composition.

    [0034] The invention will now be illustrated in the following non-limiting examples:

    Example 1



    [0035] Test cloths of non shrink resist treated two-fold, 25's worsted count, 100% lambswool of plain-knit construction with 27 stitches per cm² were washed in a liquid detergent composition comprising:



    [0036] The cloths were washed in a tergotometer at 30 rpm under the following conditions:
    Wash time: 15 minutes
    Wash temperature
    40°C
    Water hardness
    26°FH
    Cloth: Liquor
    1:20
    Dosage
    5 g/l


    [0037] Half of the test cloths were washed in compositions and under conditions as described above except that 0.5 g/l of Prassa Clay a bentonite ex CSM was added to the wash liquor.

    [0038] After washing the test cloths were subjected to wear in an Atlas Randon Tumble Pilling Tester according to ASTM D3512-82. The Pilling Tester is intended to mimic the effects of light abrasive wear. The test cloths were then visually assessed for pilling by paired comparison using a panel of assessors. The results of the assessment were as follows, a high score indicating low pilling.
      Panel Score
    Time in tester (minutes) Cloths washed with clay Cloths washed without clay
    5 12 0
    20 11 1
    30 12 0


    [0039] A difference of 7 between panel scores indicates a significant difference at the 95% confidence level.

    [0040] These results show that fabrics treated by use of a fabric softening clay according to the invention are prevented from pilling caused by rubbing of the fibres during wear.

    Example 2



    [0041] Wool blend socks of 57% lambswool and 43% nylon were washed in a granular detergent composition comprising:



    [0042] The washing was carried out using an AEG Lavamat 970 at 60°C under the following conditions:
    Dosage:
    120g granular detergent + 12g clay granules sprayed with a nonionic detergent active ethoxylated with 3 moles of ethylene oxide to give a granular composition of 80% clay, 20% nonionic by weight.
    Wash Time:
    50 minutes main wash, 85 minutes total.


    [0043] Ballast Load 2kg mixed cotton.

    [0044] After washing the socks were assessed for pilling by a paired comparison technique. The socks washed with clay showed significantly less pilling at a 95% confidence level when compared with socks washed in granular detergent alone.

    [0045] This shows that fabrics treated by use of a fabric softening clay according to the invention show less wash cycle pilling than fabrics not treated by use of a fabric softening clay.

    Example 3



    [0046] This example shows the lessening of colour change due to reduced pill formation when a fabric softening clay is used.

    [0047] A pair of wool blend socks comprising 57% lambswool and 43% nylon were washed in a granular detergent composition comprising:



    [0048] Washes were carried out under the following conditions in an AEG Lavamat 970 at 60°C.
    Dosage:
    120g granular detergent + and - 12g clay granules sprayed with a nonionic detergent active ethoxylated with 3 moles of ethylene oxide to give a granular composition of 80% clay, 20% nonionic by weight.
    Wash Time:
    50 minutes main wash, 85 minutes total.
    Ballast load:
    2kg mixed cotton.


    [0049] After washing, the socks were presented to 12 panellists who were asked to select the sock which, to them, appeared the least faded in colour. The results were as follows:
    Sock Votes
    Sock washed in clay composition. 12
    Sock washed in clay-free composition. 0


    [0050] In a panel of this size, a difference of 7 between the scores indicates significance at the 95% level. Clearly, the clay-washed socks are perceived as significantly less faded in colour than the socks washed in clay-free variant and it can be concluded that the wash cycle colour damage has been reduced.

    Example 4



    [0051] This demonstrates that pilling on garments that are already old and pilled can be controlled.

    [0052] Test cloths of untreated two-fold, 25's worsted count 100% lambswool knitted into a full cardigan construction of areal density 640 g m⁻² were prepared. The cloths were tumbled for 5 minutes in the Atlas Random Tumble Pilling tester using methodology detailed in ASTM Standard D3512-82 so as to induce heavy fuzzing and some pilling on the cloths. These were then washed in a granular detergent composition comprising:



    [0053] Washes were carried out under the following conditions in a tergotometer at 30 rpm:
    Wash time: 15 minutes
    Wash temperature: 40°C
    Water Hardness: 26°FH
    Cloth to liquor ratio: 1:20
    Product Dosage: 5g/l

    [0054] Half of the cloths were washed in compositions and under conditions as described above, except that 0.5 g/l of Prassa clay (a bentonite clay ex. CSM) was added to the wash liquor.

    [0055] After washing, the cloths were subjected to further wear in the Atlas device for periods of 5, 15, and 25 minutes. Cloths washed in the presence and absence of clay which had experienced the same length of time in the Atlas Pilling Tester were then visually assessed for pilling using a paired comparison technique. The results of this assessment are as follows, a high score indicating low pilling:
    Time in Tester after washes Cloths washed with clay Cloths washed without clay
    5 minutes 12 0
    15 minutes 12 0
    25 minutes 12 0


    [0056] A difference of 7 between the panel scores indicates a significant difference at the 95% confidence level.

    [0057] These results show that further development of pills and fuzz on already pilled and fuzzed fabrics can be controlled by treatment according to the invention.


    Claims

    1. Use of a fabric softening clay on keratin containing fibres for controlling pilling and for preventing pilling .
     
    2. Use of a fabric softening clay in a composition comprising a detergent active for controlling pilling and for preventing pilling of fabrics made from or including keratin containing fibres.
     
    3. Use of a fabric softening clay in a composition comprising an aqueous base for controlling pilling and for preventing pilling of fabrics made from or including keratin containing fibres.
     
    4. Use of a fabric softening clay in a composition comprising an aqueous base according to claim 3 wherein the composition further comprises a fabric softener selected from cationic ammonium materials and amines.
     
    5. Use of a fabric softening clay according to any preceding claim in which the clay is selected from the group comprising heat treated kaolins and multi-layer smectites.
     
    6. Use of a fabric softening clay according to any preceding claim in which the clay is selected from the group comprising Montmorillonite and Hectorite.
     
    7. Use of a fabric softening clay according to any preceding claim in which the keratin containing fibre is selected from the group comprising common mammalian keratin containing fibres used in the textile industry.
     
    8. Use of a fabric softening clay according to any preceding claim in which the keratin containing fibre is selected from the group comprising lambswool, shetland wool, botany wool, merino wool, mohair, cashmere, or fibres from: llama, vicuna, camel, angora and alpaca and yak.