CA2090332A1

CA2090332A1 - Softening agents

Info

Publication number: CA2090332A1
Application number: CA002090332A
Authority: CA
Inventors: David Longley Connell; Kenneth Michael Huddlestone; Susan Bamford
Original assignee: Individual
Current assignee: Precision Processes Textiles Ltd
Priority date: 1990-10-15
Filing date: 1991-10-15
Publication date: 1992-04-16
Also published as: AU8661391A; GB9022305D0; DE69131905T2; EP0553217A1; AU661279B2; ES2140397T3; ATE188754T1; EP0553217B1; DE69131905D1; WO1992007132A1; JPH08505190A

Abstract

A method for the treatment of natural or synthetic fibres, such as wool, cotton, nylon or acrylic, so as to impart a softer handle comprises treating the fibres with a polymer or prepolymer as defined. The method may be performed as either a continuous process or as a batch process.

Description

2 PCT/GBi91/01792 ~' :, SQFT~ G ~ X~

This invention relates to the novel use of known polymers and prepolymers as softening agents to improve the handle of both natural and synthetic ;~ fibres.
. Traditionally employed softening agents have as their basis either fatty acid or reactive siloxane chemistry. In both cases, the use of such ayents imparts a degree of hydrophobicity to the treated fibres. While attempts have been made to overcome this effect by the incorporation of hydrophil:Lc ~ groups, such as amino, quaternary ammonium and -~ polyethylene oxide groups, these generally have the effect of reducing the softness of handle that can be ~ achieved and some hydrophobicity nevertheless remains.
.~ 20 In addition, particularly in the case of fatty amide :.
$ based softening agents, the effects are transitory and ~ tend to be readily removed upon subsequent wet :~ processing of the treated fibr~s or during domestic wasbing of the finished product. Conseguently, it has .~ 2~ been necessary either to re-soften the material by .~ re-applying a softening agent (which is inefficient :~ and uneconomic) or to tolerate a reduction in the ~! level of softness following washing of the product.
:~ 9ritish Patent Nos. 1470243 and 1533343 ., 30 describe compounds containing aziridine radicals and their use for reducing the shrinkage and felting of protein fibres. One of the compounds disclosed is that sold under the trade name Basolan S~, and which is marketed as a hydrophilic polymer that is said to :3 35 achieve a soft hydrophilic finish when applied to ~, synthetic ~ibres.
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The present invention seeks to provids improved softening agents suitable for use with hoth natural and synthetic fibres. The polymers and prepolymers employed for this purpose are the subject ~: 5 of our co-pending European Patent Application No.
9030795l.5.
The present invention relates to the use as ~ a softening agent for natural or synthetic fibres of a :
- compound of any one of ~he following ormulae:-1 t A ~ m~N (Rl ) n ) r -~~

:j 15.
! which may be expressed more simply as: ~

:~ ~t N (Rl~ n ~ r ' (II3 ~ or :~ ii) structure involving crosslinking or bridging of the above groups (I) or ~II): :

[(Rl)nNlEA~z~A~mN(Rl) !
;1 .
,~ (III) . .
~. 3o which may be expressed more simply as: :~

[ER1)nN~J~N(R1)~

~. :

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WO92/07l32 2 ~ 9 Z~ 3 3 2 PCT/GB91/01792 : - 3 .
or : iii) a low molecular weight polymeric structure foxmed from the above groups (I) or (II):
(K)~(B)y~X
(~) . wherein Z represents a residue of a polyol, preferably a di or trivalent polyol;
A represents a polyalkylene oxide residue, . that is a polyether chain produced by polymerisation :: of, for example, ethylene, propylene or butyl~ne : oxides or tetrahydrofuran;
B is the residue created by bi- or polyfunctional reaction between any polyfunctional t reactlve group and the parent amine of the title i compounds (formula (I) where R1 is hydrogen in all ~ cases)~ or is the residue of a reactive amino-acrylic i polymer (e.g. of the type described in EP-A-0129322) or a reactive polyamide polymer (e.g. of the type described in EP-A-0260017A or a Hercosett polymer), and may be taken, for example, to represent Z a group -E-(R3)pN-lD]-N(R3) l (VI) :Z
~l a group ., .

N~N - ~
N~1~ ~:

. 35 (VI~) ., ~Z '.' ''Z ~ ' .... ' ' WO92/07l32 PCT/GB91/01792 2 ~

- a group resulting from the reaction of a bi-or poiyfunctional species capable of reacting with amino groups, for example: epihalohydrins, alkyl di-and polyhalides, di- or polycarboxylic acids or their ; 5 acyl halides and anhydrides, dicyandiamide, urea and formaldehyde, - a group derived from low molecular weight reactive resins such as the Bisphenol A type, or a group derived fxom reaction of a cationic polymeric reactive species such as .
.. , I6 ~
~ C~2-b ~C~3r- N~ ~ _ N ~ CH2-l~-C82 where R6 and R7 are selected from C1-C5 alkyl and C2-C5 hydroxyalkyl radicals, .

l 20 Y is selected from C2-C6alkylene radicals, ::~ 2-hydroxy-1,3-propylene radicals, and the radicals:
i . -.
:l -CH2CH2NHCONHCH2CH2- and ~.

-cH2cH2c~2NHcoNHcH2cH~c~2-I and q is an integer of from 0 to 20, provided !I that when q is greater than 2, each of the symbols Y
need not necessarily have the same significance;
D represents a straight or branched chain I hydrocarbon, polysiloxane or polyalkylene oxids I residue, and which may also either bear functional groups or may contain functional groups, such as amino groups, which may in turn either bear one or more groups R1 or, where B is polyfunctional rather than bifunctional, may xepresent a further functional :, .
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Z ': ' ; - 5 -. ., reaction point of the group ~ with the rest of the molecular structure;
E represents a group resulting from the reaction of a bi- or polyfunctional species capable of : . 5 reacting with amino groups, for example:
epihalohydrins, alkyl di- and polyhalides, . dicarboxylic acids or their acyl halides and :; anhydrides, dicyandiamide, urea and formaldehyde;
J represents a residue derived from a polyfunctional polyether;
. K represents the monofunctional or polyfunctional residue derived from partial reaction of the basic prepolymers in formulae (I~ or (II), i.e.
it represents the shaded area in formul~ (III) as follows:
. '.

, 20 ~

R1 represents a fibre reactive grouping such as the residue derived from monofunctional reaction of ~ an epihalohydrin, an alkyl or alkyl aryl polyhalide or ~ 25 a methylol grouping derived from monofunetional .. 1 reaction of formaldehyde~ or is alkyl, hydroxyalkyl or hydrogen, with the proviso that at least one group R1 .~ per polyoxyalXyleneamine residue, and preferably at least one for each nitrogen, retains residual fibre reactivity;
:? R represents a fibre reactive grouping such .j 2 as the residue derived from monofunctional reaction of an epihalohydrin, an alkyl or alkyl axyl polyhalide or ~ is a methylol grouping derived from monofunctional .
4, 35 reaction of formaldehyde, or alkyl, hydroxyalkyl or hydrogen~ ~;

'':'' . .' ": ' W09~07132 P~T/~91/01792 ._ 209~332- 6 - -.
R3 represents hydrogen or C1-C4 alkyl or hydroxyalkyl;
: R~ represents halogen or ~ :
a gro~lp ~ER2)nN~J~N(R2);~

n ~VIII) . or one of alkylamino, hydroxyalkylamino, .i~ alkoxy, alkylarylamino or a group -(R3)pN-lD]-R5 ~ or a functional reaction point of the group :.~ 15 B with the rest of the molecular structure, where B is .
polyfunctional rather than bifunct.ional;
~ , R5 represents hydrogen or :~j a group -N(R2)n or -N(R3)n;
.3 20 .1 m is between 4 and 50; :;

~ n is 2 or 3, with the proviso that, where n is -~ 3, the nitrogen atom involved also bears a formal ;'! 25 positive charge; .
p is 1 or 2, with the proviso that, where p is 2, the nitrog0n atom involved also bears a formal ~ positive charge;
;i! 30 r equals the functionality of group Z;
~1 .
: ~ t is a number representing the functionality of ~I reaction of the residue B;
l 35 , s is a number between 1 and r~

:~ J

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2l~9~332 : - 7 -: x is between 2 and 30; ancl {

y is from x to x, t-1 . with the general proviso that, in any given instance, i.~ the significance of a particular group z, A, B, R, J
. or K in any given structure shall not be dictated by the significance of any other such group in the same ~ 10 formula, and further, wherever a formal positive :.~ charge is present in the structure, then an appropriate counter anion is taken to be present, for :'~ example chloride ion.
The term "fibre reactive grvuping" as used :3 15 herein is to be understood as meaning a group having residual chemlcal reactivity such that it wlll be capable of causing a molecule to be bound to the ~ surface of a fibre in such a way as not to ba readily ;~ removable therefrom. Examples include the fibre reactive dyes in which a variety of reactive halogen :~ groupings are sited on the molecule and which, during dyeing, react with hydroxy or amino functlonalities on the fibre surface to produce a chemical bond. It will ~ be understood that electrical bonding forces, rather : ~5 than chemical forces, could be involved and that a "reaction'l as such need not occur. The terminology . further includes species which will be attracted to a fibxe surface and bind themselves thereto by means of ~:
.~ cross-linking mechanisms. ~ :
:! 3o The term ~polyfunctional reactive group" as .
~ . used herein is to be understood as meaning a group ;~ which is capable of reacting with the amino ~ functional~ty of compounds of formula I or II. The i reactivity of group B needs to be complimentary to i 35 that of group R1 in those compounds.
;~ It will be understood that the polymers and l .

WO92/07132 PCT/~GB~1/01792 'J'f~ 3~

prepolymers may be derlved from mixtures of one or more polyoxyalkyleneamines and that these may be joined by bridging groups. The bridging groups serve to link the polyoxyalkyleneamines and some examples of suitable groups were mentioned above. The bridging groups themselves could, of course, bear rsactive species capable of reacting with fibres. It will also be ' appreciated that the bridging group B could be incorporated into the molecular structure, whilst the 10 prepolymer is being applied to the fibre, as a separate reactive crosslinking agent.
The present invention further provides a method for the treatment of natural or synthetic , fibres so as to impart a softer handle and which 15 comprises treating the fibres with a polymer or prepolymer compound o the aforementioned type.
~ The softening agsnts and method of this f~ invention may be applied to all types of natural and synthetic fibres, including nylon and acrylic. They f 20 are particularly suited to use with wool and cotton, -i including 100% cotton terry loop towelling, and to , cotton or wool blends with synthetic fibres.
¦ The æoftening agents of the invention may b~
AI presented for use in solution in a non aqueous '' 25 sol~ent, such 2S perchloroethylene. More preferably, f however, they are in the form of an aqueous solution, f optionally with the addition of suitable dispersing agents to reduce the viscosity of the solution. The l total amount of polymer solids applied to the fibres is j 3o generally fxom 0.005 to 10.0% by weight, most preferably from 0.05 to 2.0%.
~, The method of this invention can be performed as either a batch or continuous process j,' using conventional equipment. For sxample, the .f 35 softeninfg agent may be applied aqueously by exhaustion I on to the goods in a traditional long bath . ' . .
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WO92/07132 2 O 9 a 3 3 2 PCT/GB91/01792 : _ 9 _ method using suitable machinery, or may be padded onto fabric continuously or appli.ed in foam or by suction-slot techniques. Irs addition, the agent may be applied to piece goods or fabr.ic from a solvent such as perchloroethylene in suitable machinery.
If desired, the softening agents may be applied in combination with other resins, further softening agents, emulsifiers, pigments, binders fluorescent whitening agents or other materials to ~0 confer additional properties or benefits to the ~ material.
-~ It has surprisingly and advantageously been found that the use of polymers and prepolymers of this type as softening agents imparts rather different, and improved, properties to the treated fibres compared 'l with conventional softeners. Not only is a very soft :. handle achieved, but the finish is also extremely `~ hydrophilic and substantially more durable to subsequent washi~g or wet processing. The durable 20 softness thus imparted results also in dimensional ~-retention and elasticity in knit cotton structures i without recourse to conventional cotton resin finishes.
As will be appreciated, this results in considerable benefits for both manufacturers and users of, for ~-~
i 25 example, cotton towelling, bathrobes, underwear and ; leisurewear.
A further advantage of the softening agents i of this invention arises from their extreme water i dispersibility. Conventionally employed softening agents are emulsions which create problems of shear instability in such high shear situations as jet dyeing machiness, suction slot evacuators, and filtration problems when treating yarn in package dyeing mac~ines, when filtration effects can cause i 35 difficulties. These problems are reduced, or totally ~:
;s avoided, with the present softening agents.

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wo g~/07132 ~ 3 ~ 2 PCT/GB91tOl792 A still further surprising aspect of the invention is that these softening agents, when used in combination with one or more conventional softening ` agents, can result in finishes with considerably superior handle and performance than may be expected.
Wash durability, handle and fuming during fabric heat setting, for example, are much improved. In some cases the improvement may be up to or above the levels achieved with either material alone, indicating a synergistic action. Examples of suitable ~ "conventional" fabric softening agents include:
; oxidised polyethylene wax emulsions; silicone emulsions, especially emulsions of reactive organofunctional silicones, and more especially ' 15 amonosilicones; fatty amide emulsions; and quaternised fatty amine emulsions.
, The present invention will now be ; illustrated by the following Examples.
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WO 92t07132 pcr/Gs9l/ol792 21~90332 Examplè 1 solution was prepared contalnlng 881 g of a blsaminopropyl ` polytetrahydrof uran of ~tructur~
~2N ~2 . C~2 . C112 ~ O ( CH~ ) 4 ~ o CH2 0 Cl~2 . ~2 ~H2 (where ~ 1~ approxirnat~ly 28 ~rerage~ ln ~418 g of a mlxtur~ o~
70~ l~opropanol ln wa~erO To thie ~olutic~n w~ a~ded 155.3g o~
eplchloro~ ydrin wlth efflcient ~tirring at roona cem~ratur~ ln ~
reaction flask fitted wlth a water cooled xeflux conden3erO The mixtur4 wa-~ then haaS~d to boillng and reflux a~slnt~in~ for approximatsly 4 hours or untll a cl~ar or ~llghtly turbld homogeneou~ solutlon i~ produce~l wh9n 5 cm3 o~ the r~act:ion mix i9 mlxed with 30 cm3 water. The reac'clon ~nixture wa~ then allowed to cool ~nd u~ed ln subsequen~ experiment~.

~^ Example 2 ttarlous textlle sample3 were treated wlth the product of example .~ 1 a~ follow~: Bcoured good~ Were placea in ~ blank bZLt~ ~t a ll~uo~ ratlo of ~0:1 and tha bath ~et to pR 6,5 lto 't.0 ~t 25~'C, ~he ~qui~ed amount o~ so~ten~r wa~ adde~ to t!he, bath ln pr~llluted ~orso, 1:~,0 wlth wat~r~ The bath wa~ d to 3SC
and th~n allowe,d tc~ exhau~t, a~ indlcat~l by tho dl~appearance o~ ths ~l~ght turbidlty fr~, th~ bath, whlch u~3ually took between 15 ~nd 30 ,r~l~ute~,. Th~ goot913 were then re~ao~ed, 3 hydroaxtracted ~nd ~Srle~d ln a tu~ ~er at betwe,eTl 70 an~l '~ 1 C10C,.
1, lhe re~ult~ of th~ te3t~ are pre~erted ln ~a~l~ to , ExamE2le 3 (a~ Formulatlon A formulation~ wa~ produced oontaining 20 part3 pro~luct from E~xarnple 1, 20 parta nonyl phenol 8 moIe et!loxylate and 1 0 part~
nonyl phenol fi mole ethoxylate .
~b) ~~lcation 1 A Bowe P421 dry cleanlng machin~ wa3 loaids~ wlth 30 kg of 60~
r~ercerlse~ Cotton 40~ nylon predyed snen~i ~ocks~ Then 130 litre~ : .
of ~erchlorethylena wa~ char~e~ to the machlne ~nd the goods tumble~ ln ~olv~nt for 1 m~nll~e to wet out. 1.95 kS~ o~ ~che ~ :
abov~3 formulatl~n wa~i then z~dd~d to the machln~ vla the bu~ton ~raD and the goods tumbla~l for 5 ml nute3, then the ~olverlt d~alrled to the i'C~ d. centrifugQd to 100~ expre~isie~n, thien tu~ ried.
A~3llcation 2 ~he a~e was x~ated5 but u31ng 1.~13 kg of the aboYe mlxture ~na 1~,9~ )cg wat~r placed ln the button trap.
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3, -:-,1 .

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- l2 (d ) Re~ult3 Example Wett1 ng t~ me~ Handle ~an~le ater 7xHLCC5 3b 8 siec very ~o~t ~oft 3c 1 ~eic ~ery ~oft 00f~

In addi~lon to thQ a~ov~ ? the change~ lrn later~ r~chlng o$
the sock a~t~r wa~hlng were ~a~asured ~ d compared with an untreated ~oc~.
" .
~i ~ercent ch~n~e in later2lL ~tr-~tch i -, . oot RnXl~s leg welt Ex~mpl~ 3c-';2 o 8 -2 ~ 2 ~1 . 3 -1 . 3 Untreated -8 ~ 9 -8 . 5 -7 . 5 -2 . 3 Thl8 further indilcate~ r~tentlorl of ~oft~:nes~ ancl ~pringness o~
th~ knitted structurs elft-r washing, '`,1 ';~ . "

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~rticle A~nt o Wettir~ dle Washiny ~andle ated Pro~l~t of t~t ~ t ~ after ~? Was~lng (o~

'~00~ ttc~n ten:y lo~ 1073~ instantax~ ~ery sc~t 7 ~a~s very scd~t y to }~XS

60~ tton 3,46% ~ se~nd~s ~ry sot 10 ~9~ y saEt 40~ Dylcn ~ ~
inta~sla in73S~S 3 ~ 3 soft ~oft ~ , ~
- -- ~
60~ ~n 4~ nyl~ 3.4~ not ~ sct 10 wa~ vesy saft p J 1~0% C~
1.73P~ 3 ~ ~lary s~t î~ y ~Et ~iC 3.46Dd 5 8~0~ ~ ~ ~5~re~y ~~

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* time WcE~ 0.1 Q3 d~p ssf ~aater to sink ~to the fa~ric ** in a Wascator ~ 7 acoor~ o ~ ering Oonsultatl~ ~uncil ;,', ".
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W092/07132 2 ~ ~ o 3 3 2 PCT/GBgl/0l792 ,,~

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Example 4 The product of Example 1 can bs prepared as an aqueous ~olution by distilling out the i~opropanol and replacin~ it with water, thereby miniml~in~ fire ha~ard. 79~ part:~ of the product of ~xample 1 ~ distllled at atmospheric pressure until 391 parts of an isopropanol: water ~lstillate Ig collected~ Then, 7~0 parts of water ~nd ~0 part~ monoethyl~ne glycol i3 added to the fla~k and stirred. The rssulting product contains about 20~ w/w active ~olid~ and only 4~5~ lsopropanol, The product wa~ applied to wool and acryllc ~ocks by an ~xhaustion method as in Example 2. Excellent handle and good durablllty was a~hieved.

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~xam~l~ 5 The s~ftenlng agent can b~ m~xed with con~entional fatty quaternary ammonium-type soften2rs ~o gi~e a product which has , excellent handle, good durability and superlor hydrophlllc~ty to ;~ conventlonal softeners. Such a product i~ particularly u~eful 1 for softening cotton/nylon ~ocka.
~, a) Formulatlon ~ 797 parts o~ the product .... ~ ~xample t were dl~tilled at i atmospharic pressure untll 391 parts of an isopropanol: water ~ distillate were collected. 391 parts o~ water were added to :, th1s, stlrred and this product blended with 341 parts of a , commerclal fatty ~uaternary aTnmonlum softener (PPT ~td).
:~! b~ APpllcatlon The perfor~ance of th~s softener wa~ compared against . conventional types on cotton/nylon ~ocks~ The Gofteners were applled as descr~ed in ~xample 2. ~he resu~ts are presented in ~ablo Z.

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Wog~/07132 2 0 9 Q 3 3 2 PCT/GB9l/01792 .

Table 2 Softener~- appl~ed to cotton/nylon ~oak~

Handle APplicatlon ~ettlnq ~afore wa~h ~ x MSB III
2~ Example 5 13 sec 3 2~ Ceranin~ pNpl1~0 sec 4 4 Permavel R235 ~ec 1 3 ~ PermaYel ~ 270 sec 2 2 Scour only 60 seo 5 5 1. Fatty amide ~obætener, Sando~ Product~ Ltd.
2~ Durable ~illco~ne softener~, PPT Ltd, prepared a~ described ln Europe~ ~a~nt Applloatlon No. 89312306.7.

. ~ ', 1 . - . ~
. ;~
e 6 ~:. A 3t~bl~ product can be formulated by t~X.~.ng 1~0 parts of the : product o~ ~xa~pile 4 and blending thls w~th 30 parts of a sillcone emulsl ~. (eg Finish VP1445E, Wack~r Chamlcal~ Ltd).
Thl8 product ~a~s co~pared for handl~ on knltted lambswool . I ~watches ~gainst a sillcone softe~er ~Wacker VP1445E). The o~teners w~re ap~plie~ ~y exhaustlon, ~9 ~e~cribQd ~n Example 2 u81ng 1-2S produc~ on we~ght o~ wool. The ne~ ~oftener gave a supsr-soft handl~, le~s ~lippy and more natural than wlth the illcone. The hy~rophillclty was al~o noticeably uperlor.
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WO92/07132 pcr/GB9l/ol792 ~ 209~3~2 - l6 - ~
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Ex~mple 7 a) To a solution of 254g bisaminopropyl polytetrahydrofuran (of the ~tructure ln Example 1~ ln 700g t~f a mlxture of 70%
isopropanol in water wa~ added 39g DER732 (Dow ChemLcal Cv.) and 7.8g eplchlorohydrin. ~he mixture was refluxed Eor 4 hour~ or until a clear or ~lightly turbid ~olution lwa~ obtalned when Scm3 ~, of the product was added to 30cm3 of water~
b) A solutlon contalning :238g bisaminopropyl polytetrahydrofuran ~of the ~tructure irl ~xa~ple 1~ in 712g ~sopropanol was preparedO To this was added 27g DER732 (Dow Chemlcal CoO3, 16.6g Tego OF3010 (Th. Goldschmldt Ltd! and 7.3g epichlorohydr~n. The ~ixture was refluxed for 4 hour3 or until a homogeneous, but ~urbld, solution wa~ obtalned wh~n 5cm3 of the product was added ~o 30cm3 o~ water.

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~ Exam~le 8 i The products o~ Example 4 and Example~ 7a and 7b were applied to a varlsty of knitted cotton abr~c~ (dou~le ~ersey, slngle l ~er~y, loopback interlock and plque). Tha softener~ were applled by a) padding: the ~o~teners were applied wet-on-wet to th~ ~abrlcs from a ~olution contalnlng 25g/1 produc~, pH7, 2SC
~, at 100~ plc~-up and b~ exhaustlon: as given ln Exampl~ ; uslng 2.5% o.w.g. pr~duct. ~he fabric~ were stenter dried and comm~rcla~ly finlshed then col~parsd for handle and durabillty to washing again~t a ~tandard ~atty amide soft~ner. A co-applied ~ mlxt~re 4~ th~ product of Example 4 and a polyethylene wax `I ~mu}3ion ~Brad~yn ~, ~ick~on & W~lch ~td) was al~o ~valuated.
~he relatl~e handl~ and durabll~ty asye~sMent~ wer~ a~ follow~.
jlj In gan~ralt the handle be~or~ and after wa~h was superlor when 3 soften~r i wexe applled by a pad~ng teehnlque compared with 1 exha~tlo~. Before washlng the softener~ were comparable ln i ~oftnQ~3 to the ~tandard silicone sot~ner ~dunlne S~, ICI
Colours ~ Fine Chemicals); after wash, ~3 x H~CC4), the ~tandard ~oft~ner could b~ re~dlly dis~ln~u~hed by ~t~ har~her handl2.
i The ~xample 4/polyethylene wax mixture perform~d particularly ~ well on all fabrlc types, giv~ng a cool, ~oft handle and :j exoellent ~rape.

2~0332 Exam~le 9 The ~oftenln~ agents of the lnvention are partlcularly ~uited to u~e on towels and to~elling fabr~c a~ a consequence of the~r ~uperlor hydrophlliclty~ The product3 were applled by a wet-on-wet continuous pad treatment at 80% plck-up, from ~olutlon containlng 20-40g/l softener to Egyptian comb~d cotton towelllng. The fabrics were tumble t~l~d and finl~hed a~
towel~. A war~, soft handle is achlev~d with excellent rewettability, as compared with sillcone- and fatty amlde-type softeners, Ths new ~oftener~ lmpart a f~ller, ~ors luxurious feel to towelling and a ~ ier handle. ~he durability of the ~ .
softeners wa~ assessed by ~ub~ectlng the towels to seven :i domestlc wa~he~, wlthout addltional fabrlc condltioner and l~ne dried, The towel~ txeated w~th the new ~oftener~ retain thelr origlnal appearancr,, wlth ~ full, ~oft handle.

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Example 10 i The product of ~xample 4 was co~pared ~or yellowing at hlgh ' te~peratures agaln~t standard silicone- and fatty amlde-type :' ~o~tener~, The products were applied to 50/S0 polyesterlcotton I by pa~din~ ~rom solutions containlng 1 g/l wettlng agent l ~ullwet PPT ~td~ and 10-40 g~l so~tener. The ~abrlcs were padded to 100~ plck-up ~hen dried~ Yellowlng of th~ fabrlcs wa~
a~se~ed ~y heating th~ fabr~c~ on an electrically-heated press for up to 3 mi~ute~. .

', Temperature Co~ment~
., 180C Llttle diff~rencs bet~een products :~ 200C ~xampl~ 4 ~howed no yellowLng at 1~2,3 min~
i at all level~. Other pro~uct~ yellowed lightly, ~ 220C 511ght yellowln~ of ~xample 4. Oth~r ~ product~ w~re mark0dly yellowed.

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Claims

1. A method for the treatment of natural or synthetic fibres so as to impart a softer handle and which comprises treating the fibres with a polymer or prepolymer having one of the following structural formulae:
i) J[N(R1)n]r or ii) or (K)x-(B)y-K
iii) wherein J represents a residue derived from a polyfunctional polyether;
K represents the monofuctional or polyfunctional residue derived from partial reaction of a prepolymer of the formula:

Z-([A]m-N(R1)n)r or J[N(R1)n]r (I) (II) that is, it represents the shaded area in the following formula:

B is the residue created by bi- or polyfunctional reaction between any polyfunctional reactive group and the parent amine of the title compound (formula (I) where R1 is hydrogen in all cases) or is the residue of a reactive amino-acrylic polymer or a reactive polyamide polymer;
Z represents a residue of a polyol;
A represents a polyalkylene oxide residue;
R1 represents a fibre reactive grouping such as the residue derived from monofunctional reaction of an epihalohydrin, an alkyl or alkyl aryl polyhalide or a methylol grouping derived from monofunctional reaction of formaldehyde, or is alkyl, hydroxyalkyl or hydrogen, with the proviso that at least one group R1 per polyoxyalkyleneamine residue, and preferably at least one for each nitrogen, retains residual fibre reactivity;
m is between 4 and 50;
n is 2 or 3, with the proviso that, where n is 3, the nitrogen atom involved also bears a formal positive charge;

p is 1 or 2, with the proviso that, where p is 2, the nitrogen atom involved also bears a formal positive charge;
r equals the functionality of group Z;
t is a number representing the functionality of reaction of the residue B;
s is a number between 1 and r-1;
x is between 2 and 30; and y is from to x, with the general proviso that, in any given instance, the significance of a particular group Z, A, B, R, J
or K in any given structure shall not be dictated by the significance of any other such group in the same formula, and further, wherever a formal positive charge is present in the structure, then an appropriate counter anion is taken to be present.

2. A method as claimed in claim 1, wherein the total amount of polymer solids applied to the fibres is from 0.005% to 10.0% by weight.

3. A method as claimed in claim 1, wherein the total amount of polymer solids applied to the fibres is from 0.05% to 2.0% by weight.

4. A method as claimed in any one of claims 1 to 3, wherein the polymer or prepolymer is presented for use in the form of an aqueous solution.

5. A method as claimed in any one of claims 1 to 3, wherein the polymer or prepolymer is presented for use as a solution in a non-aqueous solvent or is applied from a non aqueous solvent of an aqueous solution.

6. A method as claimed in any one of claims 1 to 5, wherein the fibres being treated comprise cotton or wool.

7. A method as claimed in any one of claims 1 to 5, wherein the fibres being treated comprise nylon or acrylic.

8. A method as claimed in any one of claims 1 to 5, wherein the fibres being treated comprise a cotton or wool blend with synthetic fibres.

9. A method as claimed in any one of claims 1 to 8, wherein the polymer or prepolymer is applied in conjunction with one or more other softening agents.

10. A method as claimed in any one of claims 1 to 9, and which is carried out as a continuous process.

11. A method as claimed in any one of claims 1 to 9, and which is carried out as a batch process.

12. Use as a softening agent for natural or synthetic fibres of a polymer or prepolymer of the type defined in claim 1.

13. A formulation for the treatment of fibres comprising a polymer or prepolymer of the type defined in claim 1 together with one or more other softening agents.