US8475539
US8475539
US8475539
The present invention relates to additive compositions for 15 Unexpectedly, the applicant has evidenced that some spe
the preparation of textile auxiliaries used in particular to cific components ensuring conventional functions, notably
enhance the dye affinity of textile fibres. wetting or anti-freeze agents, when combined together
showed remarkable synergy to preserve mechanical proper
BACKGROUND ties, dye affinity and level dyeing of fibres e.g. polyamide
fibres subjected to dimensional stabilisation heat treatment, at
It is frequently necessary to apply heat-setting treatments temperatures varying between 170 and 210°C., preferably
to cloth formed of textile fibres to impart dimensional stabil between 170 and 200° C.
ity that is compatible with the use thereof. This is particularly The present invention therefore concerns a composition in
true for synthetic fibres optionally associated with elastane the form of an aqueous solution or emulsion comprising:
fibres in knits. Knitted polyamide fibres are therefore treated 25 (a) one or more hydroxyalkylamines of formula: NXX
at temperatures lying between 170 and 200° C. and even (CHOH) in which X and X each independently are
above, notably depending upon the elastane content of the either hydrogen or hydroxyalkyl radicals of respective
knits. An increase in elastane content leads to increasing the formulas CH-OH and CH-OH and n, n., n are
heat-set temperature to obtain the required dimensional sta integers ranging from 2 to 6, and
bility. 30 (b) one or more anionic Surfactants chosen from among
Yet this heat setting also has the effect of deteriorating the alkyl Sulphates, alkyl Sulphonates (paraffin Sulpho
mechanical properties of yarns, notably if these are polya nates), alkylaryl Sulphonates, alkylether phosphates,
mide fibres. This mechanical deterioration in itself is detri alkyl carboxylates, and at least one compound (c) and/or
mental, but factory observations on downgraded batches or (d) such that:
laboratory observations systematically correlate this deterio 35 (c) is chosen from among one or more thioureas (thiocar
ration in mechanical properties with reduced dye affinity of bamides) having the formula RRN(CS)NRR where
the fibres, and with a problem of level dyeing. It is therefore R. R. R. Rare each independently either hydrogen or
difficult during Subsequent dyeing operations to obtain knits hydrocarbon radicals having 1 to 5 carbon atoms,
having uniform colour and the desired colour intensity. An (d) is chosen from among one or more dialkyl Sulphosuc
increase in the heat-treatment temperature generally leads to 40 cinates in combination with one more anti-freeze agents
increased deterioration of mechanical properties and dye chosen from amongst methanol, isopropanol, glycols
affinity, but the results vary greatly from one batch offibres to preferably glycerol, ethylene glycol, propylene glycol,
another. or glycol ethers preferably ethers of ethylene glycol or
It is also frequently ascertained, in one same faulty batch, propylene glycol.
that there are different types of dyeing defects (bands, light, 45 Said compositions systematically preserve good mechani
very light areas; not fully dyed...). The phenomenon is not cal fibre properties and very good dye affinity, greater than
only random but can only be ascertained a posteriori, after the those obtained with prior art textile auxiliaries, irrespective of
dyeing operation. Knits that are not uniformly dyed or too the origin of the fibres e.g. polyamides and at high treatment
pale in colour have to be corrected with a darker colour or temperatures. Without being bound by any theory, it would
dyed a second time, and are often downgraded which is a 50 appear that the phenomenon of deteriorated mechanical prop
causes of major economic loss. erties, loss of dye affinity and lack of level colouring observed
It is frequent in the textile industry to use levelling agents in fibres e.g. polyamide fibres subjected to heat treatment are
which allow better dispersion of the colouring agent in the related to a phenomenon of surface oxidation of the fibres.
dye bath, or which act either through their affinity with the Preservation of dye affinity is constant, and the uncertainties
fibre or through their affinity with the dye. These may be 55 ascertained in prior art processes are eliminated. Not only is
non-ionic Surfactants for example such as ethoxylated fatty better preservation of dye affinity ascertained, but also
alcohols, ethoxylated or non-ethoxylated fatty acids, ethoxy improved level dyeing.
lated fatty amines, alkylphenols and fatty mercaptains, or On account of their form as aqueous solution or emulsion,
products containing bisulphate anions and quaternary ammo these additives for textile auxiliaries according to the inven
nium compounds. Aside from the fact that some of these 60 tion provide hazard-free handling for operators. It is also
compounds prove to be difficult to eliminate, are scarcely possible to formulate additives according to the invention
biodegradable, even toxic, they do not systematically offset having minimum toxicity, which have best possible neutrality
the loss of dye affinity and uneven colouring of polyamide for the environment and hence can preferably be easily elimi
fibres after heat treatment. A few, specific commercial prod nated and are biodegradable. Also, these additives have good
ucts intended to overcome the loss of dye affinity observed 65 wettability with respect to polyamide fibres. On account of
after heat treatment are formulated for example with n meth their composition and notably through the presence of
ylpyrrolidone, hydroxylamine, polyglycol ether, butyl digly hydroxyalkyl amines or sequestering agents, these products
US 8,475,539 B2
3 4
can easily be stored at temperatures around 0° C. or below The introduction of a new treatment step with the compo
without any risk of precipitation of the active ingredients. sitions of the invention, having proven compatibility with the
Preferably, in the compositions of the invention (a) repre usual additives used in the chain of textile treatments, and
sents 1 to 15 weight%, preferably 2 to 10 weight%, or further contained within this chain of Successive treatments, allows
preferably 6 to 9 weight%, (b) represents 10 to 50 weight%, 5 the least possible perturbation of upstream and downstream
preferably 15 to 40 weight% or further preferably 25 to 35 processes. The compositions of the invention can be added to
weight%, (c) and/or (d) represent 3 to 15 weight%, and the the treatment line of textile knits and fabrics prior to the
quantity of water represents less than 75 weight % of the heat-setting for dimensional stabilisation which itself pre
composition, preferably 10 to 70 weight%, further preferably cedes the dyeing operation, without changing process condi
50 to 60 weight %. Preferably, in the compositions of the 10
tions. Since the compositions of the invention are in aqueous
invention, the sequestering agent(s) represent 0.2 to 2 Solution or aqueous emulsion form, they are directly diluted
weight% of the composition. Preferably, in the composition in the pad-bath upstream of the heat-setting machine.
of the invention at least one hydroxyalkylamine (a) is such
that X and X represent hydrogen, and n is an integer ranging The present invention also relates to the use of these textile
from 2 to 6. The hydroxyalkyamine (a) is chosen from among 15 auxiliaries to preserve the tenacity and tensile strength of the
monoethanolamine, diethanolamine or triethanolamine. textile fibres and yarns formed of textile fibres intended to
Preferably, in the compositions of the invention, the alkyl undergo heat treatment. A further Subject of the present inven
groups of the anionic Surfactants (b) comprise 8 to 22 carbon tion is the use of these textile auxiliaries to preserve the dye
atoms, preferably 10 to 18 carbon atoms. Preferably, in the affinity of textile fibres, and yarns, fabrics or knits of textile
composition of the invention, among the thioureas (c) at least fibres intended to undergo heat treatment. It also concerns the
one radical R. R. R. or Ra represents hydrogen, preferably use of the same textile auxiliaries as dye levelling agents for
R. R. R. and R represent hydrogen. Preferably in the com textile fibres and yarns, knits or fabrics consisting of textile
positions of the invention, the alkyl dialkylsulphosuccinate fibres.
groups of compounds (d) comprise 8 to 22 preferably 8 to 12
carbonatoms. Preferably, in the composition of the invention 25 DETAILED DESCRIPTION
the (d) compounds are chosen from among the salts of alkali
metals and alkaline-earth metals, preferably sodium, prefer Hydroxyalkylamine (a)
ably sodium dioctyl sulphosuccinate. Preferably, in the com
positions of the invention the glycol ethers of composition (d) The hydroxyalkylamines of the compositions according to
meet the formula: R-O-(CH-CH(X))-0-R where X is 30 the invention meet the formula NXX(CHOH) where X
either a hydrogen atom or a CH2 group, R. R' being carbon and X each independently are either hydrogen or hydroxy
chains comprising between 1 and 5 carbonatoms, and n is an alkyl radicals of respective formulas CH-OH and
integer between 1 and 10, preferably 1 and 5 and is preferably CH-OH and n, n., n are integers ranging from 2 to 6.
1. These compounds impart cold stability properties to the addi
According to one preferred embodiment, the composition 35 tive compositions of the invention. They can therefore be cold
of the invention comprises the compounds (a), (b), (c) and a stored (around 0°C.) without precipitation of the various
sequestering agent such as described above, or else comprises compounds in aqueous solution. The hydroxyalkylamines
the compounds (a), (b) and (d) such as described above. The also reinforce the antioxidant properties of the additive com
present invention also concerns textile auxiliaries incorporat positions and textile auxiliaries according to the invention,
ing the composition according to the invention, obtained by 40 translating as an increased capability for dye affinity preser
diluting these compositions in water. Preferably, in the textile Vation and increased mechanical properties of the textile
auxiliaries, the total quantity of water represents more than 75 fibres.
weight%, preferably 95 to 99 weight%. Further preferably, It must be possible for these compounds to be placed in
in the textile auxiliaries the total quantity by weight of active aqueous solution, and this is why compounds are preferred in
matter represented by the compounds (a), (b), (c) and/or (d) 45 which the alkyl radicals contain no more than 5 carbonatoms
ranges from 0.2% to 25%, preferably from 1% to 5%. i.e. where n and optionally in and/or n contain between 2 and
A further subject of the present invention is a process for 5 carbon atoms, preferably between 2 and 3. Monoethanola
the treatment of textile yarns, fabrics or knits intended to mine (MEA), diethanolamine, triethanolamine are preferred.
undergo heat treatment optionally followed by dyeing which, The additive compositions according to the invention prefer
upstream of the heat treatment, comprises pre-treatment of 50 ably contain 1 to 15 weight% of one or more hydroxyalky
said yarns, fabrics or knits by immersion in a pad-bath con lamines, or 2 to 15%, or 3 to 10 weight%, preferably between
taining a textile auxiliary according to the invention. During 5 and 10 weight % and further preferably between 6 and 9
the pre-treatment, said fabrics or knits are pad mangled so that weight 96 of one or more hydroxyalkylamines.
they are coated with 0.1 to 5 weight %, preferably 1 to 4%,
further preferably 2 to 4 weight % of active matter (a)+(b) 55 Anionic Surfactants (b)
and/or (d) relative to the dry weight of the yarn, fabric or knit.
Between their production and their shaping into ultimate These compounds are wetting agents notably used in vari
form in dyed, ready-to-use knits or fabrics, the fibres effec ous textile treatment operations (washing, mercerization,
tively undergo a multitude of various treatment and condi bleaching) and allow:
tioning operations during spinning, spooling, knitting, Weav 60 perfect “wetting of the textile material,
ing, dimensional stabilisation treatment, dyeing. . . . . The emulsifying of lipophilic impurities
fibres may therefore come into contact with a large quantity of dispersion of insoluble Substances and various degradation
additives e.g. wetting agents, detergents, lubricants, antistatic products.
agents, biocides, bactericides, sequestering agents, hydrogen Like the hydroxyalkylamines (a), the anionic Surfactants (b)
peroxide stabilisers, sizing agents, dispersants, pH stabilis 65 according to the invention also take part in the antioxidant
ers, anti-foaming agents, levelling agents, dyes, dye accelera properties of the additive compositions and textile auxiliaries
tors, . . . . according to the invention.
US 8,475,539 B2
5 6
Compounds (b) of the invention are chosen from among 10, preferably 1 and 5, and is preferably 1. Amongst the
alkyl Sulphates, alkyl Sulphonates, alkylaryl Sulphonates, glycol ethers, monoethylene glycol ethers or monopropylene
alkylether phosphates, alkyl carboxylates. Preferably the glycol ethers are preferred. In the compositions of the inven
alkyl groups of these Surfactants contain 8 to 22 carbonatoms, tion, compounds (d) represent 1 to 15%, preferably 2 to 12%,
preferably 8 to 18 or further preferably 10 to 18 carbonatoms. further preferably 3 to 5% by weight.
They are preferably of paraffin type. Paraffin sulphates, sul The respective proportions of dialkyl Sulphosuccinate and
phonates, and particularly lauryl, are preferred. They are pref anti-freeze may vary in the antioxidant compositions (d).
erably salts of alkali metals or alkaline-earth metals, in par Preferably, the weight percentages of these compounds in the
ticular sodium or magnesium. The compositions of the additive compositions of the invention are identical.
invention preferably contain 10 to 50 weight% of one or more 10 Active Matter and Aqueous Solution or Emulsion:
surfactants (b), or 15 to 40 weight%, or 20 to 40 weight %, The compositions of the invention, as active matter, con
most preferably 25 to 35 weight%. tain compounds (a), (b), (c) and/or (d). They may also contain
as additives any compound other than water which is Suitable
Compounds (c) for use thereof e.g. anti-foaming agents.
15 These compositions are intended to be applied in the form
The thioureas of formula RRN(CS)NRR where R. R. of an aqueous solution or aqueous emulsion. It is preferred to
R. Rare either hydrogen or hydrocarbon radicals, may play formulate the compositions of the invention with water
a part in the prevention of the oxidation phenomenon. For the soluble compounds.
compositions of the invention intended to be applied in aque The compositions of the invention are concentrates of
ous Solutions, preference is given to the thioureas in which active matter slightly diluted in water. They may for example
R. R. R. R. are either hydrogen or hydrocarbon radicals contain less than 75 weight % water, preferably 10 to 70%,
containing 1 to 5 carbon atoms, preferably the thiourea of more preferably 50 to 60% water or 55 to 60% water by
formula HN(CS)NH. weight.
Their stabilization in aqueous solution, notably at low tem Textile Auxiliaries:
perature, requires the presence of sequestering agents how 25 The textile auxiliaries of the invention are prepared by
ever such as EDTA (ethylenediamine tetraacetic acid), NTA diluting in water the concentrated compositions of active
(nitrilotriacetic acid), DTPA (diethylene triamine pentaacetic matter described above. It is possible for example to dilute
acid), phosphonic and gluconic acids, phosphonates, glucon said compositions so that the total quantity of water repre
ates, polyacrylates. NTA, EDTA, DTPA are particularly pre sents more than 75% by weight of the textile auxiliary, pref
ferred. These sequestering agents, when present, form an 30 erably 95 to 99% by weight. Also, the textile auxiliaries of the
integral part of composition (c). In the compositions of the invention comprise a total quantity by weight of active matter
invention, compounds (c) represent 2 to 10%, preferably 3 to as represented by compounds (a), (b), (c) and/or (d) which
7%, further preferably 4 to 5% by weight. ranges from 0.2% to 25%, preferably 1% to 5%. The above
The respective proportions of sequestering agent and thio described textile auxiliaries are used as dye levelling agents
ureas may vary, notably in relation to the type of thioureas in 35 or to preserve the mechanical properties and dye affinity of
compositions (c). Preferably the content of sequestering textile fibres, yarns, fabrics or knits consisting of said fibres.
agent is of the order of 0.2 to 2% in the additive compositions Use as Dye Levelling Agent:
of the invention. In addition, for reasons of toxicity, heed of Dye levelling agents are a category of textile auxiliary well
the environment or of regulations, these thioureas may be known to a skilled person, the function of which is to ensure
fully or partly Substituted by compounds (d) as wetting and 40 uniform distribution of the dye inside the fibre. Levelling
anti-freeze agents. defects translate for example as the presence, on one same
article of dyed fabric or knit, of areas having different colour
Compounds (d) intensity, marks, bands. Uneven, approximate dyeing is of no
commercial value and difficult to correct. Visual inspection of
The wetting agents contained in these compositions (d) are 45 textiles treated with auxiliaries according to the invention has
dialkyl Sulphosuccinates of formula: shown that they all have excellent level dyeing without the
onset of any Such areas.
Use to Preserve Mechanical Properties During Heat Treat
O O ment:
RO-O-C-CH-CH-C-OR,
50 The mechanical properties with which we are concerned
here are tenacity and ultimate elongation described in detail in
the examples below, and for which it was observed that dete
o==o O
rioration during heat treatment leads to dye defects. They are
measured on yarns in accordance with standard UNIEN ISO
55 2026. The mechanical properties of textile yarns previously
where R and R, are alkyl groups containing 6 to 22 carbon treated with the textile auxiliaries of the invention are not
atoms, preferably 6 to 12 carbon atoms. affected by heat treatments, notably conducted at tempera
They are preferably salts of alkali and alkaline-earth met tures of the order of 170 to 210°C., preferably of the order of
als, preferably sodium salts. Preferably dihexyl, diheptyl, 180 to 200° C.
dioctyl, dinonyl Sodium Sulphosuccinates are used. The anti 60 Use to Preserve Dye Affinity During Heat Treatment:
freeze agents of compositions (d) are alcohols such as metha Low dye affinity of textile fibres translates as yarns, fabrics
nol or isopropanol, glycols such as glycerol, or glycol ethers or knits having a lighter shade than desired. The dye affinity
designating ethylene glycol or propylene glycol ethers. of textile fibres, yarns, fabrics, knits consisting of textile
The glycol ethers of composition (d) meet the formula: fibres previously treated with textile auxiliaries of the inven
R—O—(CH-CH(X)), O—R', X being either a hydro 65 tion is not affected by heat treatments, notably conducted at
gen atom or a CH2 group, R, R being carbon chains contain temperatures of the order of 170 to 210°C., preferably of the
ing 1 to 5 carbon atoms, and n is in integer of between 1 and order of 180 to 200° C.
US 8,475,539 B2
7 8
Textile Fibres: weight proportion of elastane commonly varies between 0.1
Textile fibres may be of natural plant origin e.g. flax, cot and 40 weight% of yarns, fabrics or knits.
ton, jute, hemp, or of natural animal origin: Alpaca, Angora, The use of textile auxiliaries according to the invention is
Cashmere, wool, silk . . . . They may also be artificial. An particularly suitable for said textiles obtained from yarns
artificial textile fibre is obtained by chemical treatment (dis containing elastane and which require heat treatment for
solution followed by precipitation) of natural materials: milk dimensional setting. Typically, the uses of the invention are
caseins for lanital, cellulose of various plants (pine bark, suitable for textiles containing up to 40% by weight of elas
bamboo, soy, birch) for viscose. This category includes cel tane, preferably up to 25%. Textiles broadly designate mate
lulose acetate, cellulose triacetate, viscose . . . . rials obtained from textile yarns: fabrics, knits, non-wovens.
10 Fabrics:
Finally, synthetic textile fibres can be found; a synthetic Fabrics are obtained by weaving which results from the
textile fibre is a crystalline polymer obtained after passing interlacing, in one same plane, of yarns arranged in the warp
through a die. It is obtained by extrusion of polymer granu direction and of yarns arranged perpendicular to these warp
lates obtained from hydrocarbons or starch. It is possible for yarns in the direction of the weft.
example to obtain fibres from polylactic acid polymers, from 15 Knits:
acrylic polymers, polyamide fibres, aramid fibres (aromatic A knit (tricot or maille in French) is a stretch fabric with
polyamide) chlorofibres obtained from PVC, polyurethane interlaced loops. It differs from other textiles usually consist
fibres, elastane fibres (lycra) obtained from polyurethane ing of interlaced weft and warp yarns since it comprises a
derivatives, polyester, polyethylene, polyphenol fibres, . . . . single yarn that is wound together by looping often by means
The use of textile auxiliaries according to the invention of a knitting needle. All textile fibres can be knitted. Hosiery
concerns continuous textile fibres and yarns, more particu is another term designating some knitted fabrics.
larly synthetic textile fibres, notably those having degradation The uses of the textile auxiliaries according to the invention
problems of their mechanical properties and of dye affinity are particularly suitable for knits which, on account of their
under heat. One particularly preferred use concerns continu stretch nature, require heat treatments for dimensional set
ous textile fibres and yarns of polyamides or polyamide 25 ting, and more especially knits containing elastane. Priority is
derivatives e.g. aramid derivatives. given to those uses of the textile auxiliaries according to the
The polyamide appellation (PA) groups together all poly invention that are applied to knits combining polyamide and
mers containing "amide' groups N H C=O. This amide elastane, and in particular those containing 0.1 to 25% elas
group results from the reaction of an acid with an amine. tane.
Aliphatic polyamides are generally designated by figures 30 Pre-Treatment Process of Yarns, Fabrics or Knits:
relating to the number of carbonatoms contained in the repeat A further subject of the invention concerns treatment pro
unit of the polymer. cesses, more exactly the pre-treatment of yarns, fabrics or
For example PA6, PA 11, PA12 designate the polyamides knits which uses the textile auxiliaries according to the inven
obtained by polymerization of an amino acid or lactam tion and described in the foregoing. The purpose of the pro
respectively having 6, 11 or 12 carbon atoms in the unit, or 35 cesses of the invention is to improve the level dyeing of knits
PA6.6, PA4.6, PA6.10, PA6.12 designate the polyamides or fabrics consisting of textile fibres, or further to preserve
obtained by polycondensation of a diacid and a diamine. In their mechanical properties or dye affinity during heat treat
this second case, the first figure corresponds to the number of mentS.
carbonatoms of the diamine, whereas the second corresponds Their chief characteristic is that they are applied upstream
to the number of carbon atoms of the diacid. On the other 40 of the heat treatment operations (for example heat setting for
hand, the aromatic polyamides do not use any precise desig dimensional stabilization) and dyeing operations. They com
nation rule. Example: PAA (polyarylamide), PPA (polyphta prise:
lamide). An immersion step in a bath called a pad-bath containing
The polyamide textile fibres chiefly include nylon i.e. poly the textile auxiliaries of the invention,
hexamethylene adipamide or fibre PA 6/6. The designation 45 A pad mangling step to deposit on the Surface of the yarns,
“aramid' denotes a category of synthetic fibres obtained from fabrics or knits the required quantity of active matter
aromatic polyamides. The most known thereof is obtained (a)+(b)+(c) and/or (d).
from poly-para-phenylene diamine which can be found for Preferably this quantity of active matter lies between 0.1
example under the tradename Kevlar and Twaron. It is also and 5 weight%, preferably between 1 and 4%, further pref
possible to find other aramid textile fibres e.g. poly-meta 50 erably between 2 and 4% by weight of active matter (a)+(b)
phenylenediamine. (c) and/or (d) relative to the dry weight of the yarn, fabric or
Yarns: knit. It is also possible to characterize the mangling step by
Natural fibres which have lengths of the order 40 to 80 mm percentage expression which designates the weight percent
are made into yarn by spinning. Regarding synthetic fibres, age of textile auxiliary evacuated relative to the dry weight of
the polymers are directly extruded through dies to form yarns. 55 yarn of cloth, or its counterpart the pick-up percentage which
These yarns, on leaving the dies, can be used as such or cut represents the weight percentage of retained textile auxiliary
into pieces similar to natural fibres and then combined to form relative to the dry weight of the yarn or cloth.
rovings consisting of similar or different materials. These These processes can be batch or continuous processes
rovings are then drawn to form continuous yarns used to notably for industrial operations. For continuous processes
manufacture fabrics or knits. It is also possible to combine 60 the yarns, fabrics or knits typically travel through the pad
several continuous yarns together, these sometimes being of bath at velocities of the order of 1 to 20 metre per minute in
different type, to form the yarn which is finally used to manu tanks, or have a dwell time of the order of a few seconds to a
facture cloth e.g. fabrics or knits. few tens of seconds, typically less than 1 minute.
Therefore yarns can often be found which are made of The mangling operation is conducted using two squeeze
various materials among those listed above, notably various 65 rolls spaced apart by a distance that is adjusted so as to deposit
synthetic fibres including polyamide fibres in combination the desired quantity of active matter on the yarns, fabrics and
with elastane fibres to impart the advantage of elasticity. The knits. The fibres, fabrics or knits thus pre-treated are then
US 8,475,539 B2
10
subjected to heat treatment optionally followed by dyeing. The phenomenon of loss of dye affinity observed in some
The pre-treatment process of the invention does not perturb parts of the heat-treated batches is systematically observed in
conventional treatment processes and does not require any those parts having lesser tenacity and elongation properties.
specific modifications.
Example 2
EXAMPLES
Influence of Pre-Treatment According to the
Example 1 Invention on Mechanical Properties and Dye Affinity
Degradation of the Mechanical Properties of 10 No Pre-Treatment:
Polyamide Yarns after Heat-Set Treatment for A batch of PA6-6 polyamide yarn knit was considered, 44
Dimensional Stabilisation, Correlation with Loss of decitex, consisting of 48 filaments. This yarn was knitted with
Dye Affinity a 3-filament elastane yarn to form a knit containing 20%
elastane (batch 6).
Several batches of polyamide yarn knits (Nylon 6) consist 15 This batch had been returned by a customerfor dye defects,
ing of 12 filaments were considered having a weight per unit the dye being an acid dye of dark purple colour for which it is
length of yarn of 44 decitex (or 44 grams/1000 metres of particularly difficult to obtain sustained, uniform colour
yarn). depth on polyamide knits Subjected to heat treatment.
Each batch was subjected to heat treatment for dimensional The customer return concerned part of batch 6 which had
stabilization at 185°C. and was then dyed with a same dye of undergone the following operations:
metal type. Heat Treatment:
For each batch, part of the knit having a major dye defect The knit is passed through a pad-bath solely containing
(lighter) was isolated from the part of the knit dyed to the water and is then mangled between two squeeze rolls.
required shade (reg: regular). The two parts were then unrav It is then attached to pins to prevent the formation of
elled and the mechanical properties (tenacity and elongation) 25 creases and is passed through a heat-setting machine at 188°
of the respective corresponding polyamide yarns were mea C. in which the dwell time is about 30 seconds.
Sured. Dyeing:
Tenacity and ultimate elongation are measured in accor The knit is then dyed using JET equipment.
dance with standard UNI EN ISO 2026 using a Hounsfield In that part of batch 6 which had been subjected to the
H5KS dynamometer. 30 above treatment, the heterogeneity of dyeing could be ascer
The tenacity of a yarn represents the force that needs to be tained, the colouring being globally too pale compared with
applied to cause rupture. It is expressed in centiNewton/tex (1 the shade which should have been obtained. The knit there
tex=1 g/1000 m of yarn). fore showed three types of areas:
Elongation is measured simultaneously and represents P A very light area
relative elongation before rupture: (=If-Ii)/If. If being the 35 > A medium light area with bands
maximum length before rupture, Ii the initial length. The P An area containing very pale parts and dark parts
results are grouped together in Table 1 below. (bands)
TABLE 1.
Mechanical properties of heat-treated yarns and
correlation with dye affinity
Batch 1 Batch 2 Batch 3 Batch 4 Batch 5
Dyeing Reg Light Reg Light Reg Light Reg Light Reg Light
dtex count 4.48 452 45.7 46 46.2 46.5 45.5 45.2 46.1 45.9
g/10000m
Tenacity 27.9 26.8 26.S. 23.4 26.1 22.6 28.9 25 29.3 24.7
cNitex
Elongation 96 29.8 26.8 31.4 28.4 27.6 24.1 30.9 24.5 35.2 26.4
The value in decitex of the yarn is evidently not affected by On the unravelled polyamide yarn of each of these areas,
heat treatment; the minimal variations correspond to the the decitex value and elongation and tenacity were measured
repeatability of the method and to fluctuations in the produc in accordance with UNI EN ISO 2062. The values are
tion process.
55 grouped together in Table 2 below.
It is ascertained on the other hand that yarn tenacity and TABLE 2
elongation are systematically lower, within one same batch,
for those yarn parts which gave a “lighter colour under the Batch 6, no pre-treatment before heat setting
60
same dyeing conditions. decitex Elongation % Tenacity cN/tex
Therefore the tenacities of the “regular yarns are higher by Dark bands 45.6 25.3 32.7
4%, 13%, 15%, 15.5%, 19% to those of the “lighter' yarns for stol. deviation: stol. deviation: stol. deviation:
the respective batches 1, 2, 3, 4 and 5. Medium light bands
O.1
45.3
1.1
23.6
2.6
31.0
Similarly, the elongations of “regular yarns are higher by 65 stol. deviation: stol. deviation: stol. deviation:
11%, 10.5%, 14.5%, 26% and 33% respectively than those of O.2 1.4 2.9
“lighter' yarns in batches 1, 2, 3, 4 and 5.
US 8,475,539 B2
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TABLE 2-continued The corresponding polyamide yarn was unravelled and its
tenacity and ultimate elongation were measured as per UNI
Batch 6, no pre-treatment before heat Setting EN ISO 2062. The results are grouped in Table 5.
decitex Elongation % Tenacity cN/tex
5 TABLE 5
Very light 45.0 22.7 3O.O
stol. deviation: stol. deviation: stol. deviation: Batch. 7
0.4 1.6 3.2
decitex Elongation % Tenacity cN/tex
Upstream Pre-Treatment: 10
Very light
decitex
45.4
Elongation %
26.8
Tenacity cN/tex
33.5
Further to the customer return, an additional test was con (with treatment stand. stand. stand.
ducted with the remaining part of the same knit of batch 6 on yarn
which had not yet undergone any heat treatment or dyeing. heated on texturing) Deviation: 0.3 deviation: 2.3 deviation: 1.6
This remaining part of the knit was pre-treated and dyed
under the same conditions as those described above. How 15
ever, in this test a 10 weight% aqueous composition C1 of the It is ascertained that the mechanical properties are poor,
being comparable with those of the “very light sample in
invention was added to the water of the pad-bath, this com batch 6. The rise intemperature during the prior texturing step
position containing: had most probably already oxidized the fibres causing degra
(a) 8 weight % triethanolamine dation of mechanical properties and of dye affinity.
(b) 30 weight% paraffin sulphonate
(c) 8 weight% thiourea and 1% EDTA QS water The compositions of the invention do not therefore allow
The spacing of the squeeze rollers placed after the pad-bath restoration of the mechanical properties and dye affinity of
was adjusted so that the pick-up percentage of knit was in the polyamide fibres already heat-treated. Treatment with these
order of 60% which represents a deposit of active matter compositions must be applied in the form of a pre-treatment
(excluding water) of the order of 3.5 g/100g dry knit. 25 upstream of the heat treatment.
The sample thus treated was of industrial size. It repre Example 3
sented about 500kg of treated yarn. The entirety of the sample
showed a uniform appearance and colour having the required
intensity after dyeing (regular). Type of Pre-Treatment Solutions
The elongation and tenacity of the corresponding unrav 30
The pre-treatment in Example 2 was reproduced with a
elled polyamide yarn were measured as per UNI EN ISO composition C2 according to the invention containing:
2062. The values are grouped together in Table 3 below. (a) 12 weight% triethanolamine
TABLE 3
(b) 25 weight% paraffin sulphonate
35 (c) 8 weight% Sulphosuccinate and 6% propylene glycol
Batch 6 with pre-treatment according to the invention ether QS water
An improvement was similarly observed in the mechanical
decitex Elongation 96 Tenacity cN/tex properties of the yarn which had undergone pre-treatment
Regular 45.4 26.8 33.5 with the composition of the invention.
(with pre- stand. Deviation: stand. Deviation: stand. Deviation: 40
treatment) O.3 2.3 1.6 The invention claimed is:
1. A textile auxiliary composition consisting of
It is observed that the mechanical properties of the yarn a. one or more hydroxyalkylamines of formula: NXX
which underwent pre-treatment according to the invention are (CHOH) where X and X2 each independently are
systematically greater than those measured on non-pretreated 45 either hydrogen or hydroxyalkyl radicals of respective
yarns given in Table 2, and in particular are significantly formulas CH2OH and C2H22OH. and n, n, n, are
greater than those of the light and very light samples (respec integers ranging from 2 to 6 and
tively 13 and 18% greater for elongation, and 8 and 11% b. one or more anionic Surfactants chosen from among
greater for tenacity). alkyl Sulphates, alkyl Sulphonates, alkylaryl Sulpho
The effect of pre-treatment is confirmed visually by 50 nates, alkylether phosphates, alkyl carboxylates, and at
improved uniformity of dyeing and better colour depth. least one compound (c) and/or (d) Such that:
Therefore pre-treatment with the compositions of the c. is chosen from among one or more thioureas (thiocarba
invention allows the dye affinity of fibres to be preserved and mides) of formula RRN(CS)NRR where R. R. R.
also improves level dyeing. Reach independently are either hydrogen or hydrocar
Downstream Treatment with a Composition of the Inven 55 bon radicals having 1 to 5 carbon atoms, one or more
tion: sequestering agents, and mixtures thereof,
Under the same conditions, a knit of polyamide yarn PA d. is chosen from among one or more dialkyl Sulphosucci
6-6, 44 decitex consisting of 48 filaments in every way iden nates or the salts of alkali and alkaline earth metals
tical to the one in batch 6 was pre-treated and dyed. thereof in combination with one or more anti-freeze
This latter knit (batch 7) was fabricated using a polyamide 60 agents chosen from among methanol, isopropanol, gly
yarn derived from the same spool as for batch 6, but contrary cols, or glycol ethers and
to the yarn from batch 6 it previously underwent heat treat wherein (a) represents 1 to 15 weight%, (b) represents 20
ment at the time of forming (texturing). to 40 weight%, at least one of: (c) and (d) represent 3 to
The result after dyeing is a knit whose shade is much too 15 weight% of the composition, and
light (very light) despite treatment with the composition of 65 wherein the composition is diluted in water and the total
the invention applied before heat setting for dimensional sta quantity by weight of active matter represented by com
bilization but after heating at the time of texturing. pounds (a), (b), (c) and/or (d) ranges from 0.2% to 25%.
US 8,475,539 B2
13 14
2. The textile auxiliary according to claim 1, wherein the 14. A method to treat textile fibres, textile yarns, fabrics or
total quantity of water represents more than 75 weight%. knits which comprises the following steps: pre-treatment by
3. The textile auxiliary according to claim 1, wherein the immersion of the textile fibres, textile yarns, fabrics or knits in
sequestering agents are chosen from EDTA (ethylene a textile auxiliary comprising:
diamine tetraacetic acid), NTA (nitrilotriacetic acid), DTPA 5 (a) one or more hydroxyalkylamines of formula: NXX
(diethylene triamine pentaacetic acid), phosphonic acids, glu (CHOH) where X and X each independently are
conic acids, phosphonates, gluconates and polyacrylates. either hydrogen or hydroxyalkyl radicals of respective
4. The textile auxiliary according to claim 3, wherein the formulas CH-OH and CH-OH, and n, n., n are
integers ranging from 2 to 6, and
sequestering agent(s) represent 0.2 to 2 weight '% in the 10 (b) one or more anionic Surfactants chosen from among
composition. alkyl Sulphates, alkyl Sulphonates such as paraffin sul
5. The textile auxiliary according to claim 1, wherein at phonates, alkylaryl Sulphonates, alkylether phosphates,
least one hydroxyalkylamine (a) is such that X and X rep alkyl carboxylates, and at least one compound (c) and/or
resent hydrogen and n is an integer ranging from 2 to 6. (d) such that:
6. The textile auxiliary according to claim 5, wherein at 15
(c) is chosen from among one or more thioureas (thiocar
least one hydroxyalkylamine (a) is chosen from monoetha bamides) of formula RRN(CS)NRR, where R. R.
nolamine, diethanolamine and triethanolamine. Rs. Reach independently are either hydrogen or hydro
7. The textile auxiliary according to claim 1, wherein the carbon radicals having 1 to 5 carbon atoms,
alkyl groups of the anionic surfactants (b) contain 8 to 22 (d) is chosen from among one or more dialkyl sulphosuc
carbon atoms. cinates in combination with one or more anti-freeze
8. The textile auxiliary according to claim 1, wherein agents chosen from among methanol, isopropanol, gly
among the thioureas (c) at least one radical R.R.R. or R cols, or glycol ethers,
represents hydrogen. wherein said textile fibres, textile yarns, fabrics or knits,
9. The textile auxiliary according to claim 1, wherein the after the pre-treatment step, are then pad mangled so that
alkyl dialkylsulphosuccinate groups of compounds (d) con 25
they are coated with 0.1 to 5 weight% of active matter
tain 8 to 22 carbon atoms. (a)+(b)+(c) and/or (d) relative to the dry weight of the
10. The textile auxiliary according to claim 1, wherein textiles fibres, yarn, fabric or knit, followed by heat
treatment to ensure the dimensional stabilization of the
compounds (d) are the salts of alkali and alkaline-earth metals
of dialkyl sulphosuccinates. textiles fibres, yarns, fabrics or knits.
11. The textile auxiliary according to claim 1, wherein the 30
15. The method according to claim 14, wherein the textile
glycol ethers of composition (d) meet the formula R-O- fibres are synthetic fibres.
(CH CH(X)), O R' with X being either a hydrogen 16. The method according to claim 14, wherein the textile
atom or a CH2 group, R. R' being carbon chains comprising yarns, fabrics or knits contain elastane fibres in combination
with other textile fibres.
between 1 and 5 carbonatoms, and n is an integer of between 17. The method according to claim 14, wherein the heat
1 and 10. 35
12. The textile auxiliary according to claim 1, consisting of treatment is conducted at a temperature between 170° C. and
210° C.
(a), (b) and (c) wherein (c) is a mixture of a thiourea and a 18. The method according to claim 14, further comprising
sequestering agent. a dyeing step.
13. The textile auxiliary according to claim 1, consisting of
(a), (b) and (d).