[0001] In the treatment of textile material in the form of textile piece goods, particularly
in rope form or tubular form, essentially during pre-treatment, dyeing, optical brightening
or after-treatment, in aqueous liquor under such conditions that transport folds can
form in the textile substrate or abrasion can take place of substrate to adjacent
substrate or apparatus parts - in particular in jet dyeing machines and in winch becks
-, undesired phenomena are the marking of the transport folds and the formation and
marking of chafe points, which then, as unlevel features, impair the fabric appearance
and possibly also the physical properties of the treated goods and consequently of
the finished goods. In order to counter these interfering phenomena, wet-acting lubricants
(i.e. wet acting slip agents), which reduce the tendency toward the formation or stabilisation
and consequently the marking of folds, in particular transport folds, and reduce the
substrate/substrate and substrate/metal friction and consequently the tendency toward
the formation and marking of chafe points, are employed in the corresponding process
steps. It has already been proposed to employ wax dispersions of different types as
lubricants (or slip agents) for avoiding the formation of transport folds or creases,
e.g. as described in GB-A-2128202 or 2282153. In EP-A-506613 there are described for
a similar purpose compositions containing polymers of the radicalic polymerisation
of ethylenically unsaturated monomers (especially acrylic polymers) in admixture with
esters of polyols with a C
8-26-fatty acid. In WO-A-85/03959 there are described certain waterless compositions comprising
higher alkyl esters of benzene-mono- to hexa-carboxylic acid [which in that document
are designated as "polyesters" - in the examples there being illustrated trioctyl-,
triisoctyl- and tri-(2-ethyl-hexyl)-trimellitate] and some further components (monoesters,
diesters, ethoxylated alcohols and esters of ethoxylated alcohols), which may also
be diluted with water and be used as dyeing assistants. In US-A-5820982 there is described
the production of certain polyester resins from recycled polyterephthalate (in the
examples polyethyleneterephthalate) and a sulphoaryldicarboxylate (in the examples
sulphoisophthalate) with glycol and and oxyalkylated polyol, which may be terminated
with a polyacid (in the examples trimellitic acid or hypophosphoric acid), to give
a polyester resin useful for various purposes, in particular as a size for fibres
and as a levelling agent - in the sole application example (Example 8) there is illustrated
the use as a levelling agent in the dyeing of a yam package.
[0002] In the constant refinement of the processes and machines with the aim of increasing
the output and an environmentally acceptable procedure, machines and processes are
being developed which are designed for higher speeds or higher outputs and/or which
work with shorter liquor ratios. Greater demands are thus also made of the lubricants
employed. Thus, for example, they must be resistant to particularly high shear forces
while developing their action as well as possible for short liquors too. The shorter
the liquor, the greater the requisite efficacy of the respective treatment agents
since wet slippage of the goods and the achievement of a level, smooth goods appearance
without damage to the goods is made more difficult the greater the proportion of liquor
taken up by the goods.
[0003] It has now been found that certain end-capped polyesters having a certain hydrophilicity,
as is sufficient for the polyester to be dispersible or colloidally soluble in water,
in particular self-dispersible or colloidally soluble, particularly also end-capped
polyesters as otherwise used as soil release agents, surprisingly have an advantageous
action as wet-acting lubricants (i.e. as wet-acting slip agents) in the treatment
of textile piece goods in rope form or tubular form, particularly made from polyester
fibres, in jet dyeing machines, where, for example, they do not hinder or impair the
dyeing, but act surprisingly well and extremely superficially on the wet substrate
as wet-acting lubricants in surprisingly high efficiency and yield, and further with
a high degree of constancy and reproducibility of these properties, even if the products
employed come from different lots and/or have been stored for a prolonged time.
[0004] The invention relates to the use of such polyesters (P
S) as defined below, as wet-acting lubricants for the treatment of textile material
in the form of textile piece goods, particularly in rope form or tubular form, to
the corresponding wet-acting lubricants, and to their production and aqueous compositions
(W) thereof.
[0005] A first subject-matter of the invention is thus the use of
(P
S) water-dispersible or -colloidally soluble, end-capped polyesters
as wet-acting lubricants in the treatment of textile piece goods with a textile treatment
agent (T) from aqueous liquor under conditions which would otherwise in the textile
substrate favour the formation of transport folds and/or the occurrence of friction
in or on the substrate,
or respectively is
a process for the treatment of textile piece goods with a textile treatment agent
(T) by exhaust methods from aqueous liquor under conditions which would otherwise
in the textile substrate favour the formation of transport folds and/or the occurrence
of friction in or on the substrate, characterized in that the process is carried out
in the presence of a water-dispersible or -colloidally soluble end-capped polyester
(P
S) as a wet-acting lubricant.
[0006] The end-capped polyesters (P
S) are in particular end-capped polyesters that are polymers obtainable by polymerisation/polyesterification
reaction of corresponding esterifyable monomers (in particular hydroxy- substituted
monomers and/or monomers substituted with carboxy or a suitable functional derivative
of carboxy) and end-capping esterification reaction. As end-capped polyesters (P
S), it is possible to employ known polyesters or polyesters which can be produced analogously
to known polyesters. For the production of the end-capped polyesters (P
S), it is advantageous to use starting materials - in particular monomers suitable
for the formation of polyester chains by polycondensation and/or, in the case of lactones,
also polyaddition polymerisation reaction - which are suitable for the formation of
linear polyester chains, in particular difunctional compounds (D) which are monomers
suitable for polyesterification (i.e. polymerisation by esterification), and monofunctional
compounds (E) which are suitable for the end capping of the polyesters, and optionally
higher oligo-functional compounds (H) which are suitable for the branching of the
polyesters. The polyesters (P
S) to be employed in accordance with the invention are dispersible (preferably self-dispersible)
or colloidally soluble in water and contain in the respective molecule at least one
hydrophilic constituent and at least one hydrophobic constituent, so that the polyester
formed has a corresponding hydrophilicity, so as to be dispersible or colloidally
soluble, in particular self-dispersible or at most colloidally soluble, in water.
The mono-, di- and higher oligo-functional compounds are essentially carboxylic acids
or suitable functional derivatives thereof, principally esters of low-molecular-weight
alcohols which can be cleaved off by transesterification, particularly esters of C
1-4-alcohols, for example ethyl esters or preferably methyl esters, or anhydrides, on
the one hand, and hydroxyl compounds, in particular alcohols, on the other hand, which,
through esterification or transesterification, result in corresponding carboxylic
acid ester groups, or also lactones of hydroxycarboxylic acids, and may optionally
contain one or more heteroatomic bridging members, for example -O-, -CO-, -CO-O-,
-NH-CO-O-,

-CO-NH-, -NH-CO-NH- or -SO
2-.
[0007] Suitable as difunctional monomers (D) are, in particular,
(A) aliphatic or araliphatic diols, in particular
(A1) aliphatic and araliphatic diols which otherwise contain no hydrophilic constituents
or substituents, in particular alkanediols having 2 to 10 carbon atoms, where the
alkane radical may be linear or, if it contains 3 to 10 carbon atoms, alternatively
branched, or, if it contains 4 to 10 carbon atoms, alternatively cyclic, di(C1-2-hydroxyalkyl)benzenes, water-insoluble polyether-diols, polyester-diols, polycarbonate-diols,
polyurethane-diols and polyesterurethane-diols,
and (A2) aliphatic or araliphatic diols which contain at least one hydrophilic constituent
and/or at least one hydrophilic substituent, principally water-soluble polyalkylene
glycols (in particular polyethylene glycols, oligopropylene glycols and copolyethylene-propylene
glycols) and polyetherurethane-diols, aliphatic or araliphatic sulpho group-containing
diols which contain one or more, for example one or two, sulpho groups, and aliphatic
or araliphatic carboxyl group-containing diols which contain one or more, for example
one or two, carboxyl groups in alkali metal salt form;
(B) aliphatic, aromatic or araliphatic dicarboxylic acids, in particular
(B1) alkanedicarboxylic acids having 2 to 10 carbon atoms in the alkane radical, where,
if the alkane radical contains 4 to 10 carbon atoms, it may optionally be interrupted
by oxygen, aromatic dicarboxylic acids having one to three benzene rings, two of which
may optionally be fused, or araliphatic dicarboxylic acids which contain 9 to 18 carbon
atoms and contain one benzene ring or two optionally fused benzene rings, where aromatic
rings may be bonded to further aliphatic, aromatic or araliphatic parts of the molecule,
optionally via oxygen, or may be bonded to a further aromatic part of the molecule,
optionally via a sulphone group, or functional derivatives thereof (e.g. C1-4-alkyl esters of the dicarboxylic acids or optionally their anhydrides),
and (B2) aliphatic, aromatic or araliphatic dicarboxylic acids which contain at least 4 carbon
atoms and in which the hydrocarbon radical to which at least one of the two carboxyl
groups is bonded contains 1 to 14 carbon atoms, and which contain at least one hydrophilic
radical (for example a hydrophilic polyethylene glycol ether chain) and/or at least
one hydrophilic substituent (for example one or more, in particular one or two, sulpho
groups) in the molecule, or functional derivatives thereof (e.g. C1-4-alkyl esters of the dicarboxylic acids or optionally their anhydrides);
(C) aliphatic hydroxymonocarboxylic acids, in particular
(C1) aliphatic unsubstituted hydroxycarboxylic acids having 3 to 18 carbon atoms, optionally
in lactone form, or prepolymers (polyesters) thereof. e.g. on a starting diol such
as e.g. those mentioned above as (A1).
[0008] Sulpho group-containing monomers (D) are difunctional in so far as sulpho groups
substantially do not undergo esterification under the reaction conditions required
for esterification of the carboxy groups or respectively for transesterification their
lower alkyl esters.
[0009] As (A
1), mention may be made, for example, of ethylene glycol, 1,3-propanediol, 2,4-dimethyl--2-ethylhexane-1,3-diol,
2,2-dimethyl-1,3-propanediol, 2-ethyl-2-butyl-1,3-propanediol, 2-ethyl-2-isobutyl-1,3-propanediol,
1,3-butanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 2,2,4-trimethyl--1,6-hexanediol,
1,2-, 1,3- or 1,4-cyclohexanedimethanol, 2,2,4,4-tetramethyl-1,3-cyclobutanediol,
para-xylytenediol, 1,2-propylene glycol, neopentyl glycol, polytetrahydrofurans, higher
propylene glycols (having > 10 monomer units), polycaprolactones from the addition
of an ε-caprolactone onto an alkanediol (for example onto one of the above-mentioned
alkanediols), or polycarbonate-diols from the above-mentioned alkanediols. Of the
diols (A
1), preference is given to C
2-4-alkanediols, in particular propylene glycol, ethylene glycol and combinations of
propylene glycol and ethylene glycol.
[0010] As (A
2), mention may be made, for example, of the following:
(A21) polyethylene glycols (for example having an average molecular weight

W in the range from 200 to 10,000, preferably 500 to 5000), water-soluble oligopropylene
glycols (having ≤ 10 monomer units),
(A22) alkanediols having 4 to 10 carbon atoms and which carry one or two sulpho groups
as substituents, and are optionally oxyethylated and/or oxypropylated, benzenedimethanols
which carry a sulpho group as substituent on the benzene ring, for example 2-sulphobutanediol
and products of the addition reaction thereof with ethylene oxide and optionally propylene
oxide, sulpho-1,2-benzenedimethanol (sulphoxylene glycol) and sulpho-1,4-benzenedimethanol,
or additionally sulphonated diepoxides of alkanediols or polyethylene glycols (for
example from the reaction of the respective alkanediols or polyethylene glycols with
epichlorohydrin and sulphonation with a bisulphite, for example with sodium bisulphite)
and sulphonated oxyalkylated alkenediols (for example from the sulphonation of the
product of the addition reaction of oxiranes - principally ethylene oxide and/or propylene
oxide - onto alkenediols with sulphite, for example with sodium sulphite),
or also (A
23) monoamidation products of di- or higher carboxylic acids [for example those of type
(B
1) or (H
2) below] with low-molecular-weight dialkanolamines, for example with diethanolamine,
dipropanolamine or diisopropanolamine, where the non-amidated carboxyl groups are
in alkali metal salt form (particularly as Na, Li or K salt).
[0011] Of the diols (A
2), those of the type (A
21) are preferred, especially polyethylene glycols.
[0012] As (B
1), mention may be made, for example, of the following: adipic acid, succinic acid,
glutaric acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, maleic acid,
fumaric acid, dimethylmalonic acid, diglycolic acid, 3,3'-oxydipropionic acid, trimethyladipic
acid, itaconic acid, orthophthalic acid, isophthalic acid, terephthalic acid, oxydibenzoic
acid, naphthalene-2,6-dicarboxylic acid, naphthalene--1,8-dicarboxylic acid, naphthalene-1,4-dicarboxylic
acid, 1,2-di-(p-carboxyphenoxy)-ethane, 1,2-di-(p-carboxyphenyl)-ethane, biphenyl-2,2'-dicarboxylic
acid, 1,4-cyclohexanedicarboxylic acid and 4,4'-dicarboxydiphenyl sulphone, and their
methyl esters. Of the aliphatic dicarboxylic acids (B
1), preference is given to the α,ω-dicarboxylic acids; of the aliphatic, aromatic and
araliphatic dicarboxylic acids (B
1), preference is given to the aromatic ones, particularly terephthalic acid.
[0013] As (B
2), mention may be made, for example, of the following: sulphosuccinic acid, methylsulphosuccinic
acid, sulphomethylsuccinic acid, 4-sulphophthalic acid, 5-sulphoisophthalic acid,
dimethylsulphoisophthalic acid, sulphoterephthalic acid, sulphomalonic acid, 1,3-dimethyl
5-(p-sulphophenoxy)-isophthalate, phenyl-3,5-dicarboxy-benzenesulphonic acid, 2,6-dimethylphenyl-3,5-dicarboxybenzenesulphonic
acid, naphthyldicarboxylic acid benzenesulphonic acid, sulpho-4-naphthalene-2,7-dicarboxylic
acid, sulphobis(hydroxycarbonyl)-4,4'-diphenyl sulphone and products of the sulphonation
of oligoesters of unsaturated dicarboxylic acids obtainable by reaction thereof, for
example, with sodium sulphite, for example on the basis of maleic acid, itaconic acid
or citraconic acid, for example with the above-mentioned alkanediols, and polyoxyalkylenedicarboxylic
acids, for example from the carboxymethylation of polyalkylene glycols or from the
catalytic or electrochemical oxidation of the terminal CH
2-OH groups of polyalkylene glycols to COOH groups, where the polyalkylene glycols
are preferably polyethylene glycols and/or polypropylene glycols, and methylesters
of the dicarboxylic acids. Of the sulpho group-containing acids (B
2), 5-sulphoisophthailc acid is especially preferred; of the acids (B
2), the sulpho group-free ones are preferred, especially the polyethylene glycol ether
chain-containing ones.
[0014] As (C
1), mention may be made, for example, of the following: glycolic acid, hydroxypropionic
acid, 12-hydroxystearic acid, 2-hydroxycaproic acid, 3- or 4-hydroxybutyric acid,
ε-caprolactone, γ-butyrolactone and 3,3-dimethyl-4-butyrolactone, and prepolymers
thereof.
[0015] Suitable monofunctional compounds (E) for the end capping of the polyesters are expediently
hydroxy- or carboxy-substituted compounds capable of esterification with a carboxy
or respectively hydroxy group of the not yet end-capped polyester, where the carboxy
group may also be in the form of a suitable functional derivative, e.g. a C
1-4-alkyl ester of the carboxylic acid; for example,
(E1) simple alcohols or carboxylic acids or their methyl esters, which do not contribute
towards the hydrophilicity of the polyester,
and (E2) hydroxyl or carboxyl compounds or their methyl esters, which may contribute towards
the hydrophilicity of the polyesters, particularly those which contain hydrophilic
polyalkylene glycol ether chains and/or carry one or two sulpho groups as substituents,
and which have a boiling point which is expediently higher than the (trans)esterification
temperature.
[0016] Suitable as (E
1) are, in particular,
(E11) simple aliphatic or araliphatic alcohols, for example C4-6-alkanols and phenylalkanols,
and (E12) simple aliphatic, araliphatic or aromatic monocarboxylic acids, for example butanoic
acid and optionally alkyl-substituted benzoic acids, or their methyl ester.
[0017] Suitable as (E
2) are, in particular,
(E21) aliphatic or araliphatic hydroxyl compounds which contain a hydrophilic moiety,
for example a polyalkylene glycol ether chain, and/or carry one or more sulpho groups
as substituents,
and (E22) aliphatic, araliphatic or aromatic, carboxyl group-containing, hydrophilic compounds
or their methyl esters, which contain a hydrophilic moiety, for example a polyalkylene
glycol ether chain, and/or carry one or more sulpho groups as substituents.
[0018] As (E
11), mention may be made, for example, of the following: cyclohexanol, benzyl alcohol
and (C
1-4-alkyl)-benzyl alcohol.
[0019] As (E
12), mention may be made, for example, of the following: benzoic acid and butyric acid.
[0020] As (E
21), mention may be made, for example, of the following: adducts of ethylene oxide and/or
propylene oxide, and optionally butylene oxide or styrene oxide, onto an aliphatic
monoalcohol having 1 to 18 carbon atoms or onto an alkylphenol having a total of 10
to 24 carbon atoms, where at least 50 mol-% of the alkyleneoxy groups present are
advantageously ethyleneoxy groups, and the incorporated polyalkylene glycol ether
chains are preferably those consisting exclusively of ethyleneoxy units (for example
up to an average molecular weight in the range from 200 to 20,000, particularly from
200 to 5000), and aliphatic and/or araliphatic hydroxyl compounds which carry one
or two sulpho groups as substituents and optionally contain oxyethylene and/or oxypropylene
groups in the molecule. Of these, adducts of ethylene oxide onto a low-molecular-weight
alkanol (in particular C
1-4-alkanol) are preferred. Sulpho group-containing compounds of type (E
21) which are particularly worthy of mention are 2-hydroxyethanesulphonic acid, 2-hydroxypropanesulphonic
acid, 4-(2-hydroxyethoxy)-benzenesulphonic acid and compounds of the average formula
H-(O-alkylene)
n-O-CH
2-(CHR)
m-CH
2-R (I),
in which alkylene denotes ethylene and/or 1,2-propylene,
- R
- denotes hydrogen or SO3H,
- m
- denotes 0 or 1
and
- n
- denotes a number in the range from 1 to 30,
where at least one of the m+1 symbols R denotes SO
3H.
[0021] As (E
22), mention may be made, for example, of the following: carboxymethylation products
of the adducts of ethylene oxide and/or propylene oxide onto an aliphatic monoalcohol
having 1 to 18 carbon atoms, where at least 50 mol-% of the alkyleneoxy groups present
are advantageously ethyleneoxy groups and the incorporated polyalkylene glycol ether
chains preferably consist exclusively of ethyleneoxy units (for example up to an average
molecular weight in the range from 200 to 5000), or products of the catalytic or electrochemical
oxidation of the terminal -CH
2-OH groups of such addition products to give terminal -COOH groups, or aliphatic,
araliphatic or aromatic carboxylic acids having 7 to 22 carbon atoms which carry a
sulpho group as substituent, for example ortho-, meta- or parasulphobenzoic acid or
sulphonated oleic acid (for example from the reaction of oleic acid with sodium sulphite).
Of said compounds (E
22), the sulpho group-free ones are preferred.
[0022] Sulpho group-containing reactants (E
21) and (E
22) are grouped here with monofunctional compounds in so far as sulpho groups substantially
do not undergo esterification under the reaction conditions required for esterification
of the carboxy groups or respectively for transesterification their lower alkyl esters.
[0023] Of the components (E
1) and (E
2), the components (E
2) are preferred, particularly (E
21), especially the non-ionogenic ones.
[0024] Suitable as (H) are tri- and higher oligo-functional compounds which can lead to
branched products with ester formation, in particular
(H1) compounds containing 3 to 10 alcoholic hydroxyl groups,
(H2) compounds containing 3 or more, for example 3 or 4, carboxyl groups, or a functional
derivative thereof (e.g. a C1-4-alkyl ester of the carboxylic acids or optionally their anhydrides),
and (H3) hydroxycarboxylic acids containing at least 2 carboxyl groups and/or at least 2
hydroxyl groups and functional derivatives thereof (e.g. C1-4-alkyl esters of the carboxylic acids or optionally, if they contain at least 2 carboxyl
their anhydrides),.
[0025] Suitable as (H
1) are, for example, tri- to hexahydroxyalkanes, for example having 3 to 6 carbon atoms,
for example pentaerythritol, trimethylolethane, trimethylolpropane, glycerol, mannitol,
sorbitol and 1,2,3-hexanetriol, and oxyalkylation products thereof, particularly oxyethylation
and/or oxypropylation products, for example having 1 to 20 oxyethylene groups and
optionally 1 to 10 oxypropylene groups.
[0026] As oligocarboxylic acids (H
2), use can be made of aliphatic, araliphatic or preferably aromatic compounds, for
example having 6 to 15 carbon atoms, preferably benzenetricarboxylic acids (in particular
trimellitic acid, hemimellitic acid or trimesic acid) or their methyl esters.
[0027] Suitable hydroxycarboxylic acids (H
3) are aromatic compounds or also aliphatic compounds, for example aromatic benzene-based
dicarboxylic acids which carry a hydroxyl group on the benzene ring, for example hydroxy-4-
or -5-isophthalic acid, or aliphatic saturated dicarboxylic acids having 4 to 8 carbon
atoms, for example hydroxy-2-methylsuccinic acid, hydroxymethylglutaric acid and hydroxyglutaric
acid, or aliphatic saturated carboxylic acids having 3 to 8 carbon atoms, which may
carry 2 to 6 hydroxyl groups, in particular ascorbic acid, gluconic acid and glucoheptonic
acid, or methyl esters thereof, or also products of the partial amidation of tri-
or higher functional carboxylic acids [for example those of type (H
2)] with low-molecular-weight mono- or dialkanolamines, for example with mono- or diethanolamine,
-propanolamine or -isopropanolamine, or additionally products of the monoamidation
of dicarboxylic acids [for example those of type (B
1)] with low-molecular-weight dialkanolamines, for example with diethanolamine, dipropanolamine
or diisopropanolamine, where the non-amidated carboxyl groups are in the form of the
free acid.
[0028] For the production of the polyesters (P
S) to be employed in accordance with the invention, there may in particular be polymerised
(A) with (B) and optionally (C), or (C) alone optionally on a starter molecule (A)
or (B), and optionally with (A) or (B), and optionally with (H), end capping being
carried out with (E). It is advantageous to employ difunctional compounds, in particular
diols (A), which are reacted with corresponding dicarboxylic acids, in particular
of type (B) or functional derivatives thereof and optionally with hydroxycarboxylic
acids of type (C), or products of the polymerisation of hydroxycarboxylic acids (or
lactones thereof), in particular of type (C), which are optionally reacted further
with (poly)esters of diols, in particular of type (A) with corresponding dicarboxylic
acids, in particular of type (B), or functional derivatives thereof. Monofunctional
compounds of type (E) are employed in order to cap an end group (hydroxyl or carboxyl
group). If desired, higher oligo-functional compounds, for example of type (H), can
be employed in order to produce branched polyesters. The relative amounts or molar
ratios of the respective starting compounds are advantageously selected in such a
way that the polyesters produced therefrom have the desired hydrophilicity properties,
i.e. in particular in such a way that the polyesters, besides a hydrophobic moiety,
also have a hydrophilic moiety, which can be controlled, in particular, through a
suitable choice of corresponding starting compounds. Thus, for example, hydrophobic
moieties are built up by polyesterification with diols of type (A
1), with dicarboxylic acids of type (B
1) and/or respectively with hydroxymonocarboxylic acids of type (C
1), while hydrophilic moieties are introduced with components of type (A
2) or (B
2). A contribution towards the hydrophilicity of the polyesters is also made with compounds
of type (E
21) and (E
22).
[0029] The esterification reaction (or transesterification reaction if carboxylic acid esters
of alcohols, which can be cleaved off under esterification conditions, are transesterified)
can be carried out in a manner known per se, with the respective selected components
(D) and (E) and optionally (H) being reacted, with addition of suitable catalysts,
at elevated temperature, for example in the range from 150 to 280°C, preferably from
160 to 260°C. If diols (A) are employed, it is advantageous first to employ the more
volatile and not to add the less volatile for the further esterification until the
esterification of the former has begun or progressed. The esterification (or transesterification)
can initially be carried out under atmospheric pressure, for example in the presence
of inert solvents or preferably in the absence of any solvents, in which case volatile
by-products, for example unreacted starting materials and other volatile accompanying
substances, can then be removed under reduced pressure. Suitable transesterification
and condensation catalysts are, for example, conventional compounds of polyvalent
metals, for example titanium tetraisopropoxide, manganese(II) acetate, dibutyltin
oxide or antimony trioxide/calcium acetate, which can be employed in the concentrations
which are usual per se, for example in the range from 0.0005 to 1 % by weight, particularly
from 0.002 to 0.1 % by weight, based on (P
S).
[0030] The hydrophilic starting compounds may, for example, be exclusively those which contain
as hydrophilic moieties polyethylene glycol ether chains, which are suitable or preferred
for the production of non-ionogenic polyesters, or exclusively those which contain
sulpho groups as hydrophilic substituents, which are suitable or preferred for the
production of anionic polyesters, or also a combination of the two.
[0031] The respective molar ratios are advantageously selected in such a way that an excess
of hydroxyl compounds over carboxyl compounds is employed overall, depending on the
volatility of the diols employed, and advantageously in such a way that any carboxyl
groups are capped with monofunctional alcohols, preferably those of type (E
21). If higher oligo-functional compounds of type (H) are employed, their molar ratio
to the difunctional compounds (D) employed is advantageously kept low. It is in particular
advantageous to select the respective molar ratios in such a way that no significant
crosslinking takes place, principally in such a way that aqueous dilution of the product
does not form gelatinous, irreversible agglomerates, but instead a dispersion or colloidal
solution. If, for example, the starting materials are diols (A
1) and (A
2), dicarboxylic acids (B
1) (or diesters thereof), a polyol (H
1) and a monofunctional compound (E
21), it is advantageous to employ ≤ 1 mole equivalent, preferably ≤ 0.5 mole equivalent,
of (H
1), for example from 0.002 to 0.4 mole equivalent thereof, per mole of introduced diols
[(A
1) + (A
2)]. The molar ratio (E
21)/[(A
1) + (A
2)] is then advantageously in the range from 0.01 to 1, preferably in the range from
0.02 to 0.5, particularly preferably in the range from 0.04 to 0.3. One mole equivalent
of (H) is taken to mean one mole of (H) divided by the number of functional groups;
in the case of the oligohydroxyl compounds (H
1), one mole equivalent of (H
1) is thus one mole of (H
1) divided by the number of its hydroxyl groups. These molar ratios apply to the specific
non-ionic polyesters from the said starting components; if other and/or further components
are used for the production of the polyesters or oligoesters, the molar ratios should,
if necessary, be adjusted or changed correspondingly in order to obtain the corresponding
polyester or oligoester properties. Through the reaction with (H), branched or optionally
also dendromeric polyesters or oligoesters (P
S) can be produced.
[0032] The reaction is advantageously controlled in such a way that the average molecular
weight
W of the polyesters produced is ≥ 1000, and is preferably in the range from 1200 to
10
6, particularly preferably in the range from 1500 to 3-10
5. The synthesis of the polyesters to be employed in accordance with the invention
is advantageously carried out in such a way that the degree of polymerisation can
be kept relatively low, in particular in such a way that oligoesters are formed.
[0033] Any anionic groups, in particular sulpho groups and/or carboxyl groups, present in
the polyester (P
S) may be in the form of the free acid and if desired can be converted into a salt
form by reaction with corresponding bases, where for the salt formation cations known
per se, preferably hydrophilising cations, come into consideration, for example alkali
metal cations (for example lithium, sodium or potassium) or ammonium cations {for
example unsubstituted ammonium, mono-, di- or tri--(C
1-2-alkyl)-ammonium, mono-, di- or tri-(C
2-3-hydroxyalkyl)-ammonium, mono-, di- or tri--[(C
1-2-alkoxy)(C
2-3-alkyl)]-ammonium or morpholinium}, for which, for example, corresponding alkali metal
hydroxides or carbonates, ammonia or the respective amines can be employed, preferably
in the form of aqueous solutions.
[0034] The hydrophilicity of the products is controlled in such a way that the polyesters
(P
S) produced are dispersible to colloidally soluble in water (preferably self-dispersible
to colloidally soluble in water), i.e. that they give, in a concentration of from
0.1 to 30 % by weight, optionally with the assistance of suitable dispersants in an
amount of up to 50 % by weight, based on (P
S) and optionally heating to above the melting point of (P
S), in water a corresponding 0.1 to 30 % (P
S) dispersion or colloidal solution or, for the self-dispersible to colloidally soluble
ones, even without the assistance of dispersants, give in water, through simple stirring-in
and optionally heating to above the melting point of (P
S), an aqueous 0.1 to 30 % (P
S) dispersion or an aqueous 0.1 to 30 % colloidal (P
S) solution. A dispersion or colloidal solution of this type may be cloudy or translucent
to transparent, but can in the latter case still be recognised through the Tyndall
effect.
[0035] In polyesters and oligoesters (P
S) produced from terephthalic acid [as (B)], ethylene glycol and/or propylene glycol
(GL) [as (A
1)] and polyethylene glycols [as (A
2)] and optionally (H) or (H
1) and end-capped with an oxyethylated alcohol [as (E
21)], the hydrophilicity can also be estimated, for example, from the (GL)/(PEG) weight
ratio, where (GL) denotes the proportion by weight of esterified ethylene glycol and/or
propylene glycol and (PEG) denotes the proportion by weight of all esterified polyoxyethylene
[from (A
2) and (E
21)]. If the polyoxyethylene chains have an average molecular weight in the range from
500 to 5000, preferably from 800 to 3000, this (GL)/(PEG) weight ratio for the corresponding
polyesters (P
S) is advantageously in the range from 1:3 to 1:60, preferably from 1:5 to 1:30. These
values apply to the specific non-ionic polyesters from the said starting components;
if other and/or further components are used for the production of the polyesters,
the values should be adjusted or changed correspondingly in order to achieve the corresponding
hydrophilicity.
[0036] Of the polyesters (P
S), preference is given to the polyesters (P
S'), i.e. those which are self-dispersible or colloidally soluble in water, of these
particularly the polyesters (P
S"), i.e. the non-ionic ones, especially (P
S"') those from the esterification or transesterification of (B
1) using (A
1), (A
21) and optionally (H
1) or (H
3) and end-capping with (E
21).
[0037] According to a particular embodiment of the invention, use is made as (P
S) of polyesters as are known as soil release agents for textile substrates (for example
in detergents).
[0038] The polyesters (P
S) produced can be handled and used directly in the form in which they have been produced.
They are advantageously used in the form of aqueous, preferably concentrated, compositions
(W). These aqueous compositions (W) are dispersions or colloidal solutions of (P
S) and advantageously contain the polyesters (P
S) in a concentration in the range from 1 to 50 % by weight, preferably from 2 to 50
% by weight, particularly preferably from 3 to 25 % by weight. The aqueous compositions(W)
can be simple aqueous dispersions or colloidal solutions of (P
S) alone or preferably contain further additives, in particular
(G) a thickening agent.
[0039] Suitable thickening agents (G) are preferably non-ionogenic and/or anionic substances
which are known per se, in particular natural, modified or synthetic polymers. Examples
of thickening agents (G) which can be employed are polysaccharides, polysaccharide
derivatives and (co)poly(meth)acrylic acids and/or (co)poly(meth)acrylamides, for
example xanthan gum, cellulose gum, guar gum, dextrins, gum arabic, carboxymethylcellulose,
hydroxyethylcellulose, hydroxypropylcellulose, acrylyl-modified polysaccharides, copoly(meth)acrylic
acids/(meth)acrylamides and optionally partially saponified poly(meth)acrylamides.
Of these, preference is given to hydrophilic resins which are viscoelastic and preferably
also pseudoplastic and non-thixotropic in aqueous solution, for example xanthan gum,
cellulose gum, guar gum, dextrins, gum arabic, hydroxyethylcellulose, hydroxypropylcellulose
and carboxymethylcellulose, or the said (meth)acrylic acid and/or (meth)acrylamide
(co)polymers, of which particular preference is given to xanthan gum, homopolyacrylamides,
copolyacrylamide-acrylic acid and partially saponified polyacrylamides. Advantageously,
at least some of the acid groups, particularly the carboxylic acid groups, are in
the form of salts (so that the respective products are water-soluble), for example
as alkali metal salts (principally sodium salts). They can be employed as dry substance
(for example as commercially available). If thickening agents (G) are employed, they
are advantageously employed in such amounts that the viscosity of the aqueous concentrated
compositions (W) [i.e. of the aqueous concentrated colloidal solutions or aqueous
concentrated dispersions (W)] is < 5000 mPa·s, in particular at values ≤ 1000 mPa·s,
preferably in the range from 50 to 1000 mPa·s. The concentration of thickening agent
(G) in (W) is advantageously low, in particular lower than that of (P
S), and is, calculated as dry substance, for example ≤ 5 % by weight, advantageously
from 0 to 4 % by weight, preferably from 0.01 to 2 % by weight, particularly preferably
from 0.1 to 1 % by weight.
[0040] If desired, the aqueous compositions (W) in addition to (P
S) and optionally (G), may contain further additives, in particular one or more of
the following components:
(X) a non-ionogenic or anionic surfactant or a mixture of non-ionogenic and/or anionic
surfactants,
(Y) an agent for setting the pH
and (Z) at least one formulation additive.
[0041] Suitable surfactants (X) are principally the following:
(X1) a non-ionogenic surfactant or a mixture of non-ionogenic surfactants, having an
HLB ≥ 7,
and (X2) an anion-active surfactant which is a carboxylic acid or sulphonic acid or a sulphuric
acid partial ester or phosphoric acid partial ester or a salt thereof, or a mixture
of such anion-active surfactants, having an HLB ≥ 7,
or mixtures of two or more of the surfactants (X
1) and (X
2), in particular at least one surfactant (X
1).
[0042] The surfactants (X
1) and (X
2) generally have dispersant character, in particular emulsifier character.
[0043] Suitable surfactants (X
1) are generally known compounds, essentially those having an emulsifier or dispersant
character. Emulsifiers or dispersants of non-ionogenic character are known in large
number in the art and are also described in the specialist literature, for example
in M.J. SCHICK "Non-ionic Surfactants" (Volume 1 of "Surfactant Science Series", Marcel
DEKKER Inc., New-York, 1967). Suitable non-ionogenic dispersants (X
1) are principally products of the oxyalkylation of fatty alcohols, fatty acids, fatty
acid mono- or dialkanolamides (in which "alkanol" stands especially for "ethanol"
or "isopropanol") or fatty acid partial esters of tri- to hexafunctional aliphatic
polyols or, further, products of the interoxyalkylation of fatty acid esters (for
example of natural triglycerides), where suitable oxyalkylation agents are C
2-4-alkylene oxides and optionally styrene oxide, and preferably at least 50 % of the
introduced oxyalkylene units are oxyethylene units; advantageously at least 80 % of
the introduced oxyalkylene units are oxyethylene units; particularly preferably all
the introduced oxyalkylene units are oxyethylene units. The starting materials for
the addition of the oxyalkylene units (fatty acids, fatty acid mono- or dialkanolamides,
fatty alcohols, fatty acid esters or fatty acid polyol partial esters) can be any
desired conventional products as used for the production of such surfactants, principally
those having 9 to 24, preferably 11 to 22, particularly preferably 16 to 22, carbon
atoms in the fatty radical. The fatty radicals may be unsaturated or saturated, branched
or linear; mention may be made, for example, of the following fatty acids: lauric
acid, myristic acid, palmitic acid, stearic acid, oleic acid, arachic acid and behenic
acid, and technical-grade fatty acids, for example tallow fatty acid, coconut fatty
acid, technical-grade oleic acid, tall oil fatty acid and technical-grade soya oil
acid, and products of the hydrogenation and/or distillation thereof; examples of fatty
acid mono- or dialkanolamides which may be mentioned are the mono- or diethanolamides
or mono- or diisopropanolamides of said acids; fatty alcohols which may be mentioned
are the derivatives of the respective fatty acids mentioned and synthetic alcohols,
for example from the oxo synthesis, from the Ziegler process and/or from the Guerbet
process [for example isotridecanols, Alfol grades (for example Alfol 10, 12 or 14)
and 2-butyloctanol]. Partial esters of said polyols which may be mentioned are, for
example, the mono- or difatty acid esters of glycerol, erythritol, sorbitol or sorbitan,
in particular sorbitan mono- or dioleates or mono- or distearates. Of the said products,
preference is given to the oxyalkylated fatty alcohols, especially the products of
the oxyethylation of linear fatty alcohols, in particular those of the following average
formula
R
1-O-(CH
2-CH
2-O)
p-H (II),
in which
- R1
- signifies an aliphatic, linear hydrocarbon radical having 9 to 22 carbon atoms
and
- p
- signifies from 4 to 40,
or mixtures of such surfactants.
[0044] The HLB value of the surfactants (X
1) is advantageously in the range from 7 to 20, preferably in the range from 8 to 16.
Of the compounds of the formula (II), particular preference is given to those in which
R
1 contains 11 to 18 carbon atoms.
[0045] Suitable anion-active surfactants (X
2) are generally acids known per se (or salts thereof) having a surfactant character,
as are usually employed as dispersants, for example as emulsifiers or as detergents.
Such surfactant anionic compounds are known in the art and are described in large
number in the specialist literature, for example in W.M. LINFIELD "Anionic Surfactants"
(Volume 7 of "Surfactant Science Series", Marcel DEKKER Inc., New-York, 1976). Suitable
anion-active surfactants are in particular those which contain a lipophilic radical
(in particular the radical of a fatty acid or an aliphatic hydrocarbon radical of
a fatty alcohol) which contains, for example, 8 to 24 carbon atoms, advantageously
10 to 22 carbon atoms, in particular 12 to 18 carbons, and may be aliphatic or araliphatic
and where the aliphatic radicals may be linear or branched, saturated or unsaturated.
In the case of carboxylic acids, the lipophilic radicals are preferably purely aliphatic,
while in the case of sulphonic acids, the lipophilic radicals are preferably saturated
purely aliphatic or araliphatic radicals. The carboxylic or sulphonic acid group may
be bonded directly to the hydrocarbon radical (in particular as fatty acid, for example
in the form of soaps, or as alkanesulphonic acid) or via a bridge which is interrupted
by at least one heteroatom and is preferably aliphatic. Carboxyl groups can be introduced,
for example, by oxidation of -CH
2-OH groups, carboxyalkylation of hydroxyl groups or monoesterification of a hydroxyl
group with a dicarboxylic anhydride, for example into such a molecule as described
above as starting material for the oxyalkylation to give non-ionogenic surfactants
or also of oxyalkylation products thereof, where the oxyalkylation can be carried
out using oxiranes, principally ethylene oxide, propylene oxide and/or butylene oxide
and optionally styrene oxide, and preferably at least 50 mol-% of the oxiranes employed
is ethylene oxide; for example, these are products of the addition of from 1 to 12
mol of oxirane onto 1 mol of hydroxyl compounds, particularly as mentioned above as
starting material for the oxyalkylation. The carboxyalkylation may be carried out
using principally haloalkanecarboxylic acids, advantageously those in which the haloalkyl
radical contains 1 to 4 carbon atoms, preferably 1 or 2 carbon atoms, halogen principally
stands for chlorine or bromine, and the acid group can optionally be in salt form.
A carboxyl group can also be introduced, for example, by monoesterification of an
aliphatic dicarboxylic acid, for example by reaction of a hydroxyl compound with a
cyclic anhydride, for example with phthalic anhydride or an aliphatic anhydride having
2 or 3 carbon atoms between the two carboxyl groups, for example succinic anhydride,
maleic anhydride or glutaric anhydride. Phosphoric or sulphuric acid partial ester
groups, for example, can also be introduced analogously by esterification. Suitable
sulphonic acids are essentially products of the sulphonation of paraffins (for example
produced by sulphochlorination or sulphoxidation), of α-olefins, of alkylbenzenes
and of unsaturated fatty acids or alternatively formaldehyde condensates of sulphonated
aromatic compounds (for example of sulphonated naphthalene). The anion-active surfactants
are advantageously employed in the form of salts, where for salt formation hydrophilizing
cations, in particular alkali metal cations (for example lithium, sodium, potassium)
or ammonium cations [for example those mentioned above] or alternatively alkaline
earth metal cations (for example calcium or magnesium), preferably come into consideration.
Of the said anion-active surfactants (X
2), the ester group-free ones are preferred, principally soaps, in particular amine
soaps, as well as the products of the carboxymethylation of oxyethylated fatty alcohols
and the sulphonic acids, preferably in salt form as mentioned above, particularly
as alkali metal salts.
[0046] The surfactants (X) are advantageously employed in amounts which are sufficient to
enable (P
S) and, if used, (G) to be well dispersed in the aqueous phase and to enable a particularly
stable aqueous colloidal solution or preferably dispersion of (P
S) and (G) to be formed.
[0047] The amount of (X) employed is advantageously ≤ 80 % by weight of (P
S), preferably ≤ 50 % by weight of (P
S), particularly preferably from 0 to 30 % by weight of (P
S). If (P
S) is self-dispersible to colloidally soluble [preferably (P
S')], (X) is not necessary.
[0048] Suitable as (Y) are any desired compounds known per se as are usually used for adjusting
the pH of textile treatment agents, for example the above-mentioned bases, or alternatively
buffer salts, such as, for example, sodium acetate or mono- or disodium phosphate,
or occasionally also acids (for example a mineral acid, in particular hydrochloric
acid or sulphuric acid, or a low-molecular-weight aliphatic acid, preferably having
1 to 4 carbon atoms, preferably formic acid, acetic acid or lactic acid).
[0049] The pH of the compositions (W) can vary widely and can optionally be adjusted, for
example in the range from 3 to 10, preferably from 4 to 9, particularly preferably
from 5 to 8, by addition of (Y).
[0050] The compositions (W) may optionally additionally contain at least one formulation
additive (Z), in particular (Z
1) an antifoam or (Z
2) an agent which inhibits bacterial growth or a microbicide, or (Z
3) a bleaching agent. As (Z
1), conventional antifoams can be employed, for example based on paraffins, mineral
oil, fatty acid bisamides and/or hydrophobic silicic acid, for example commercial
products, which can be employed in the concentrations recommended in each case. Suitable
as (Z
2) are especially fungicides and bactericides, for example commercial products, which
can be employed in the concentrations recommended in each case. As (Z
3), conventional bleaching agents can be employed, in particular reductive bleaching
agents, such as, for example, sodium bisulphite. Suitable concentrations of (Z) are,
for example, in the range from 0 to 4 % by weight, preferably from 0.001 to 2 % by
weight, particularly preferably from 0.002 to 1 % by weight, based on (W).
[0051] Particularly worth of mention are the dispersions (W'), which essentially consist
of (P
S) and water and optionally one or more of the additives (G),' (X), (Y) and/or (Z)
[for example of (P
S), (G) and water and optionally (X), (Y) and/or (Z)], particularly the dispersions
(W"), which essentially consist of (P
S'), water and preferably (G) and in addition optionally one or more of the additives
(Y) and/or (Z), particularly of (P
S") or (P
S''') and water and preferably (G) and optionally one or more of the additives (Z
1), (Z
3) and/or (Y). Particularly preferred dispersions (W") are e.g. those essentially consisting
of (P
S"), water and at least one of the components (Z
2) and (G) and optionally (Y), or, where (P
S) is other than (P
S'), those essentially consisting of water, (P
S) and (X) and (Z
2) and optionally (G) and/or (Y).
[0052] The (G)- and/or X-containing compositions (W) according to the invention, in particular
(W') and preferably (W"), can be produced in a very simple manner, by suitable mixing
of the components, in particular by mixing (P
S), for example as a melt, in the presence of water, with (G) and/or (X), and optionally
adding further additives, in particular one or more of (Y) and/or (Z).
[0053] The above-described polyesters (P
S), preferably in the form of aqueous compositions (W), are used as wet-acting lubricants
for textile piece goods, i.e. as auxiliaries in the treatment of textile fabrics with
treatment agents (T) (for example pre-treatment, dyeing, optical brightening or after-treatment)
under conditions under which per se otherwise transport folds can form or friction
can occur in or on the substrate, in particular in rope form or tubular form, where
the compositions (W) to be employed in accordance with the invention serve particularly
for preventing the stabilisation and marking of the folds formed during the treatment
and for preventing damaging friction. Such processes are essentially exhaust processes
from short liquor (liquor/substrate weight ratio, for example, in the range from 3:1
to 40:1, mostly from 4:1 to 20:1) - in particular in jet dyeing machines or in winch
becks - under the treatment conditions and times which are usual per se (for example
in the range from 20 minutes to 12 hours) as occur in particular in winch becks and
especially in jet dyeing machines.
[0054] The aqueous compositions (W) or the polyesters (P
S), even in the presence of (G), have an optimum wet slippage behaviour, so that effective
distribution on the surface of the wet fabric is possible on their use, after which
they can be removed again, in general by discharging the liquid and/or by washing
and/or rinsing operations as required by the process.
[0055] The treatment agents (T) are in general textile chemicals (in particular textile
finishing chemicals) which can be removed from the substrate again for the part which
is not fixed to the substrate, for example by washing and/or rinsing, after the respective
treatment of the substrate.
[0056] As (T), the following sub-groups, in particular, are suitable:
(T1) pre-treatment agents (principally wetting agents and detergents),
(T2) main treatment agents (principally wetting agents, dyes, dyeing auxiliaries and
optical brighteners),
and (T3) after-treatment agents (principally finishing agents, detergents and reducing agents);
where the respective treatments are carried out in aqueous medium.
[0057] Processes in which folds (i.e. transport folds) can form in the textile substrate
are essentially taken to mean those in which the wet substrate tends to lie in folds
during its transport in the dyeing machine, due to the action and possibly interference
of various forces. The folds which form in such processes can per se result in marking
of the crease points due to stabilisation during the treatment process, which can
result in the disadvantages mentioned at the outset. In such processes, the polyesters
(P
S) or the compositions (W) serve as wet-acting lubricants, in particular as agents
for preventing transport folds, to the extent that they favour or facilitate slippage
of the wet fabric or the wet folds and thus can prevent damaging stabilisation of
the transport folds. Treatment processes which would per se cause transport folds
are principally treatments on a winder (in particular in a winch beck) or especially
in jet dyeing machines, in which the substrate is in each cycle fed over the winder
or through the nozzle, at which point the fold formation and/or the forces acting
on the folds, which can result in stabilisation of the folds, are the strongest.
[0058] Processes in which friction can take place in or on the textile substrate are essentially
taken to mean those in which the wet substrate, during its transport in the dyeing
machine, rubs against apparatus parts or adjacent substrate parts due to high running
speed, passage through nozzles and/or a change in the transport direction and/or speed.
The chafe points formed in such processes can result in marking thereof during the
treatment process and in impairment of the physical properties of the substrate. In
such processes, the polyesters (P
S) or the compositions (W) serve as wet-acting lubricants to the extent that they favour
or facilitate slippage of the wet fabric (particularly on adjacent fabric or on metal)
and thus can prevent damaging friction of the substrate. Possible treatment processes
which would per se cause chafe points are principally treatments in jet dyeing machines,
in which the substrate is in each cycle passed through the nozzle, at which point
the relative acceleration and/or the forces acting on the substrate are the greatest,
and in which the substrate is in each cycle pulled from its own position in the liquor
toward the nozzle, so that the substrate-against-substrate acceleration or substrate-against-metal
acceleration can at the respective points cause friction in places, which can result
in the said chafe points.
[0059] Suitable substrates for the process according to the invention and for the wet-acting
lubricants according to the invention are in general any desired substrates as can
be employed in the said processes, principally those which contain synthetic fibres,
especially polyester fibres, optionally in a blend with other fibres, in particular
with other synthetic fibres (for example acrylic fibres or polyurethane fibres) or
optionally modified natural fibres, for example of wool, silk or optionally modified
cellulose (for example cotton, linen, jute, hemp, ramie, viscose rayon or cellulose
acetate), where fibre blends that may be mentioned are, for example, polyester/cotton,
polyester/polyacrylic, polyester/polyamide, polyester/polyurethane and polyester/cotton/polyurethane.
The textile substrate can be employed in any desired form as piece goods, as can be
treated in the processes mentioned, for example as tubular goods, as open textile
webs or alternatively as semi-finished goods, essentially in rope form or tubular
form, as is suitable for winders or especially in jet dyeing machines; both knitted
goods and woven fabrics can be employed (for example fine to coarse simple knitted
goods or interlocks, fine to coarse woven fabrics, terry goods, velvet and open-work
and/or machine-embroidered textiles), in particular also goods made from microfibres,
principally polyester microfibres and blends thereof with other correspondingly fine
fibres.
[0060] The wet-acting lubricants used in the invention, i.e. polyesters (P
S) optionally in the form of aqueous compositions (W), in particular concentrated compositions
(W), are advantageously employed in such concentrations that fold marking and chafe
point formation are effectively prevented in the respective process. They are distinguished
by their effectiveness and yield and can exhibit a very high action in very low concentrations;
they are advantageously employed in concentrations which correspond to from 0.01 to
2 g of (P
S) per litre of liquor, preferably from 0.02 to 1 g of (P
S) per litre of liquor, particularly preferably from 0.04 to 0.5 g of (P
S) per litre of liquor.
[0061] They can be produced in a simple and readily reproducible way, in particular as described
above, and are also distinguished by the constancy of their properties - even in different
lots - and the aqueous concentrated compositions (W) are distinguished by their stability
to storage, shipment, transfer and pumping.
[0062] Since the wet-acting lubricants used in the invention, i.e. polyesters (P
S) or compositions (W), are also distinguished by their great independence from temperature
variations and are substantially electrolyte-resistant, they can also be employed
in a very wide selection of treatment conditions as occur for treatment with textile
chemicals (T) in industry, in particular for pre-treatment with (T
1), for dyeing or optical brightening with (T
2) and for after-treatment with (T
3), for example with (T
1) during desizing or during bleaching, with (T
2) during dyeing or optical brightening or with (T
3) during after-treatment, but especially during dyeing or optical brightening. The
dyeing or optical brightening can be carried out using any desired dyes or optical
brighteners (T
2') and optionally dyeing auxiliaries (T
2") which are suitable for the respective substrate and process and for the desired
effect. For the dyeing of polyester-containing substrates, any desired corresponding
dyes, for example disperse dyes, and optionally dyeing auxiliaries (for example carriers
and/or levelling agents) can be employed, where the dyeing of substrates made from
fibre blends, in particular made from cellulose fibres and synthetic fibres, can also
be carried out using corresponding additional dyes, in particular reactive dyes, direct
dyes, vat dyes or sulphur dyes (and optionally also corresponding dyeing auxiliaries).
The processes can pass through any desired temperature regions as used for the respective
substrate and the treatment agent employed and as a result of the apparatus and the
desired purpose, for example from room temperature (for example at the beginning of
dyeing) up to HT conditions (for example in the range from 102 to 180°C, in the closed
apparatus). The electrolyte content of the liquors can also be as desired, as otherwise
usually used for the respective process, for example corresponding to the alkali metal
salt (for example sodium chloride or sodium sulphate) concentrations and/or alkali
metal hydroxide or carbonate concentrations, as used in dyeing with said dyes, be
it as a blend component in commercially available dye preparations and/or as uptake
assistant in dyeing or optical brightening, or also as alkalis used in dyeing with
sulphur dyes, vat dyes or reactive dyes.
[0063] The pH values can be as desired, as are suitable for the respective substrates, dyes
and application processes. For polyester dyeings with dispersion dyes, suitable pH
values are, for example, in the acidic region (for example in the pH range from 4
to 6, preferably from 4.5 to 5.5) or alternatively - with use of corresponding disperse
dyes which are likewise suitable for alkaline dyeing - in the alkaline pH region (for
example at pH > 8, principally in the pH range from 8.5 to 10).
[0064] The polyesters (P
S) or compositions (W) are advantageously employed as wet-acting lubricants in dyeing
or optical brightening, especially in jet dyeing machines (both those with hydrodynamic
liquor transport and those with aerodynamic liquor transport), preferably for dyeing
of polyester-containing substrates, particularly preferably of those essentially consisting
only of polyester fibres (particularly also microfibres).
[0065] For use in the treatment of polyester fibres, particularly preferred polyesters or
oligoesters (P
S) are polyesters or oligoesters (P
S"') in which the hydrophobic part originates from starting compounds (A
1) and (B
1) or is built up from monomer units which are directly homologous to (particularly
± 1 to 2 carbon atoms) or preferably identical with those originating or built up
from the fibre polymer to be treated. Thus, if, for example, the polyester substrate
to be treated is a polyester made from terephthalic acid and ethylene glycol (i.e.
a polyethylene terephthalate), the hydrophobic part of (P
S) or (P
S"') preferably essentially consists of ester units made from terephthalic acid and
ethylene glycol and/or propylene glycol, while the hydrophilic part then preferably
essentially consists of (A
2), in particular a polyethylene glycol, and/or (E
21), which is then preferably a product of the addition of ethylene oxide onto a C
1-18-aliphatic alkohol, preferably a low-molecular-weight alkanol (particularly C
14-alkanol), and the polyester or oligoester (P
S) or (P
S"') optionally also contains as a constituent a copolymerised compound (H
1).
[0066] Due to the high resistance to temperature variations even at relatively high temperatures,
the wet-acting lubricants according to the invention, i.e. polyesters (P
S) or respectively compositions (W), can be employed under the said conditions and
optimally display their activity, without their action being impaired. Due to the
high shear force stability of the wet-acting lubricants (W), particularly those which
consist only of (P
S) and (G) and optionally (X), (Y) and/or (Z), in aqueous dispersion or colloidal solution,
these are also particularly suitable as wet-acting lubricants in jet dyeing machines,
especially also in those in which the goods or the liquor are subjected to extremely
high dynamic stress, or in which very high shear forces develop in the liquor.
[0067] The compositions (W) or the polyesters (or oligoesters) (P
S) [in particular (P
S') or (P
S") or even (P
S"')] have, even in very short liquors, for example at liquor/goods ratios of ≤ 15/1,
particularly also ≤ 10/1, a very good, extremely superficial wet slippage action,
in particular to the extent that they cause the lubricant to accumulate at the goods
surface and the liquor to accumulate in the immediate vicinity of the lubricant and,
as a flowing liquor layer, facilitates wet slippage of the goods to a surprisingly
high degree.
[0068] Through the use of the wet-acting lubricants (P
S) according to the invention, particularly in the form of their aqueous compositions
(W), in particular optimally dyed and/or optically brightened materials may be obtained,
in which the action of the respective treatment agent (pre-treatment agent, dye, optical
brightener or after-treatment agent) is not impaired and an optimum goods appearance
is obtained, even on use of very short liquors, even if almost all the liquor is on
the goods during the process and almost no liquor remains over in the apparatus base.
[0069] The effectiveness of the polyesters (P
S) and the preparations (W) as wet-acting lubricants (or slip agents) can be determined,
for example, as follows by measurement of the coefficient of friction: a first piece
of fabric is tensioned in contact with the inside base of a shallow, flat trough,
fixed at one end with a clamp and covered with an amount of liquor which corresponds
to the liquor ratios which are usual in practice; a 200 g weight with a smooth, flat,
rectangular base on which a second piece of the same fabric is tensioned and fixed
is placed horizontally on top. The laid-on weight covered with the second piece of
fabric (= "sledge") is then pulled in the longitudinal direction of the trough and
of the first tensioned piece of fabric (= "track") until it starts moving and until
it reaches a constant speed, and the traction force necessary to set the "sledge"
in motion horizontally on the "track", starting from the end fixed with the clamp,
and to move it horizontally in the traction direction at constant speed is determined.
Both the static friction and the kinetic friction and thus both the static coefficient
of friction and the kinetic coefficient of friction can thus be determined.
[0070] If N
0 denotes the normal force (i.e. the weight of the "sledge" on the "track"), Z
S denotes the horizontal traction force which is necessary to set the "sledge" in motion
on the "track", and Z
K denotes the horizontal traction force which is necessary to keep the "sledge" moving
at a constant speed on the "track", the static coefficient of friction µ
S can be expressed by the following formula

and the kinetic coefficient of friction µ
K by the following formula

[0071] Use of (P
S) allows not only µ
K but also µ
S to be reduced to very low values.
[0072] The overall effectiveness of the wet-acting lubricants can be observed visually by
checking the correspondingly treated goods in order to determine chafe points (or
chafe marks) or transport fold marks (for example on a dyeing).
[0073] In the following examples, parts denote parts by weight and percentages denote percentages
by weight; the temperatures are given in degrees Celsius. The products additionally
added to the oligoesters in the examples (production, dispersion and application examples)
are commercially available products. In the application examples, the dyes are employed
in commercially available dry form with a pure dye content of about 25 % , the concentrations
given relate to this form and are based on the substrate weight. C.I. stands for Colour
Index.
Example 1
[0074] 194.2 g of dimethyl terephthalate, 39.8 g of ethylene glycol, 96.6 g of 1,2-propylene
glycol, 9.2 g of glycerol, 0.37 g of anhydrous sodium acetate and 0.19 g of titanium
tetraisopropoxide are introduced into a four-necked flask with a capacity of 1 litre
which is provided with stirrer, internal thermometer, gas-inlet tube and a 20 cm Vigreux
column with Claisen bridge. The system is then rendered inert with nitrogen and heated
to 165-167°C over the course of half an hour. The temperature is increased to 215-220°C
over the course of a further 2.5 hours. The transesterification, and thus the distillation
of methanol, commences at an internal temperature of about 165°C. After about 5 hours,
more than 98 % of the expected amount of methanol has distilled off. The batch is
cooled to 80°C, 72 g of methylpolyethylene glycol 750, 91.2 g of methylpolyethylene
glycol 1820 and 387.5 g of polyethylene glycol 1500 are then added. The flask is again
rendered inert and heated to 200-220°C, the pressure is then lowered to 1-5 mbar over
the course of 1 hour, and the condensation is carried out at 220-240°C for a further
2-5 hours, during which a mixture of ethylene glycol and 1,2-propylene glycol distils
off. After termination of the condensation, the system is aerated with nitrogen and
cooled. The product solidifies on cooling to room temperature to give a solid material.
Yield 730 g.
[0075] Further oligoesters are produced analogously to Example 1 using the following starting
materials:
Example 2
[0076]
| 194.2 g |
of dimethyl terephthalate |
| 39.8 g |
of ethylene glycol |
| 96.6 g |
of 1,2-propylene glycol |
| 1.4 g |
of pentaerythritol |
| 0.37 g |
of anhydrous sodium acetate |
| 0.19 g |
of titanium tetraisopropoxide |
| 72.0 g |
of methylpolyethylene glycol 750 |
| 91.2 g |
of methylpolyethylene glycol 1820 |
| 387.0 g |
of polyethylene glycol 1500. |
Yield 725 g.
Example 3
[0077]
| 145.6 g |
of dimethyl terephthalate |
| 109.0 g |
of 1,2-propylene glycol |
| 1.4 g |
of mannitol |
| 0.28 g |
of anhydrous sodium acetate |
| 0.14 g |
of titanium tetraisopropoxide |
| 82.2 g |
of methylpolyethylene glycol 750 |
| 581.3 g |
of polyethylene glycol 3000. |
Yield 800 g.
Example 4
[0078]
| 194.2 g |
of dimethyl terephthalate |
| 39.8 |
g of ethylene glycol |
| 96.6 g |
of 1,2-propylene glycol |
| 6.0 g |
of trimethylolethane |
| 0.37 |
g of anhydrous sodium acetate |
| 0.19 g |
of titanium tetraisopropoxide |
| 54.0 g |
of methylpolyethylene glycol 750 |
| 68.4 g |
of methylpolyethylene glycol 1820 |
| 68.9 g |
of polyethylene glycol 1500 |
| 129.2 g |
of polyethylene glycol 800 |
| 258.3 g |
of polyethylene glycol 3000. |
Yield 760 g.
Example 5
[0079]
| 223.3 g |
of dimethyl terephthalate |
| 45.7 g |
of ethylene glycol |
| 111.1 g |
of 1,2-propylene glycol |
| 1.6 g |
of pentaerythritol |
| 0.42 g |
of anhydrous sodium acetate |
| 0.22 g |
of titanium tetraisopropoxide |
| 28.2 g |
of methylpolyethylene glycol 750 |
| 35.7 g |
of methylpolyethylene glycol 1820 |
| 445.6 g |
of polyethylene glycol 1500. |
Yield 720 g.
Example 6
[0080]
| 213.5 g |
of dimethyl terephthalate |
| 43.7 g |
of ethylene glycol |
| 106.2 g |
of 1,2-propylene glycol |
| 4.5 g |
of pentaerythritol |
| 0.41 g |
of anhydrous sodium acetate |
| 0.21 g |
of titanium tetraisopropoxide |
| 39.6 g |
of methyl polyethylene glycol 750 |
| 50.2 g |
of methylpolyethylene glycol 1820 |
| 426.3 g |
of polyethylene glycol 1500. |
Yield 720 g
Example 7
[0081]
| 174.7 g |
of dimethyl terephthalate |
| 19.0 g |
of ethylene glycol |
| 107.5 g |
of 1,2-propylene glycol |
| 3.3 g |
of trimethylolethane |
| 0.33 g |
of anhydrous sodium acetate |
| 0.17 g |
of titanium tetraisopropoxide |
| 83.8 g |
of methylpolyethylene glycol 750 |
| 174.4 g |
of polyethylene glycol 1500 |
| 348.8 g |
of polyethylene glycol 3000. |
Yield 765 g.
Example 8
[0082]
| 194.2 g |
of dimethyl terephthalate |
| 39.8 g |
of ethylene glycol |
| 96.6 g |
of 1,2-propylene glycol |
| 1.0 g |
of glycerol |
| 0.37 g |
of anhydrous sodium acetate |
| 0.19 g |
of titanium tetraisopropoxide |
| 226.5 g |
of the adduct of 80 mol of ethylene oxide onto 1 mol of tallow fatty alcohol |
| 387.5 g |
of polyethylene glycol 1500. |
Yield 800 g.
Example 9
[0083]
| 233.0 g |
of dimethyl terephthalate |
| 47.7 g |
of ethylene glycol |
| 115.9 g |
of 1,2-propylene glycol |
| 8.1 g |
of 1,2,3-hexanetriol |
| 0.44 g |
of anhydrous sodium acetate |
| 0.23 g |
of titanium tetraisopropoxide |
| 22.8 g |
of n-butylpolyethylene glycol 200 |
| 465.0 g |
of polyethylene glycol 1500 |
Yield 700 g.
Example 10
[0084]
| 291.2 g |
of dimethyl terephthalate |
| 59.7 g |
of ethylene glycol |
| 144.9 g |
of 1,2-propylene glycol |
| 310.0 g |
of polyethylene glycol 800 |
| 123.3 g |
of methylpolyethylene glycol 750 |
| 0.6 g |
of anhydrous sodium acetate |
| 0.3 g |
of titanium tetraisopropoxide |
Yield 710g.
Dispersion W1
[0085] 337 parts of water are initially introduced, and 2.0 parts of xanthan gum ("Kelzan"
polysaccharide gum from Kelco Biopolymers) are added with stirring. After 6 hours,
a colloidal solution is present, which is further diluted with 120 parts of water.
40 parts of the oligoester produced in accordance with Example 1, in molten form (65-70°C),
are then drawn in under reduced pressure (residual pressure 300 mbar). A homogeneous,
white, viscous dispersion forms which is stirred for a further I hour. The vacuum
is then broken using nitrogen, and 1 part of biocide (1.5 % aqueous solution of a
1/1 mixture of 5-chloro-2-methyl-4-isothiazolin-3-one hydrochloride and 2-methyl-4-isothiazolin-3-one
hydrochloride) is then added, the pH is adjusted to 7 (using sodium hydroxide solution
or glacial acetic acid, depending on the water quality), and the product is then discharged.
Dispersion W2
[0086] The procedure is as described for dispersion W1, with the difference that instead
of the oligoester from Example 1, the same amount of the oligoester from Example 2
is employed.
Dispersion W3
[0087] 458.5 parts of water are initially introduced, and 0.5 parts of a partially hydrolyzed
polyacrylamide (having an average molecular weight
W = 20·10
6, with 27 ± 3 mol-% of CH
2-CH-COONa monomer units) are added with stirring. As soon as a homogeneous solution
is present (after about 12 hours), the mixture is heated to 50°C, and 50 parts of
the oligoester produced in accordance with Example 2 are added. A homogeneous, fine
dispersion forms which is cooled to room temperature, and 1 part of the same biocide
as in dispersion W1 is added. The product is subsequently discharged.
Dispersion W4
[0088] An 8 % aqueous dispersion of the oligoester produced in accordance with Example 3
is produced by initially introducing the water, drawing in the oligoester in molten
form, and heating the mixture to 80°C with stirring, and, as soon as a homogeneous
dispersion is present, cooling the dispersion to room temperature. Before discharge,
0.2 % of the same biocide as in dispersion W1 are added.
Dispersions W5 to W11
[0089] The procedure is as described for dispersion W1, with the difference that instead
of the oligoester from Example 1, the same amount of the oligoester from each of Examples
4 to 10 is employed.
Dispersion W12
[0090] 320.7 parts of ethylene glycol, 13.6 parts of diethanolamine and 12.9 parts of succinic
anhydride are allowed to react at 60°C for 3 hours. 7.2 parts of potassium hydroxide
and 334.5 parts of dimethyl terephthalate and 0.7 parts of manganese(II) acetate as
catalyst are then added. The mixture is heated to 180°C under nitrogen, during which
methanol and water distil off. The reaction melt obtained is cooled to 120°C, reacted
with 646.5 parts of polyethylene glycol 750 monomethyl ether and re-heated to 180°C
under reduced pressure. After 2 hours at 180°C, about 206.9 g of distillate are obtained.
The mixture is then cooled to 120°C. About 1000 parts of melt at 120°C are obtained,
which are added to a mixture of 3750 parts of water and 250 parts of the adduct of
10 mol of ethylene oxide onto 1 mol of oleyl alcohol at from 50 to 60°C. The mixture
is subsequently cooled to room temperature. 5000 parts of aqueous dispersion W 12
are obtained.
Application Example A [Dyeing of polyester in the jet (Mathis laboratory jet)]
[0091] A piece of polyester automobile velour is dyed as follows in a Mathis laboratory
jet: 90 parts of polyester velour are introduced into the jet, which contains 900
parts of aqueous liquor and 1 g/l of dispersion W1. 0.62 % of C.I. Disperse Yellow
52, 2.3 % of C.I. Disperse Red 86, 0.5 % of C.I. Disperse Blue 77, 0.5 g/l of an anionic
dispersant (formaldehyde condensate of sulphonated naphthalene) and 0.5 g/l of a levelling
agent (mixture of sulphonated aromatic compounds) are added to the liquor, the pH
is adjusted to from 4.5 to 5 with acetic acid, and the liquid is heated from room
temperature to 130°C at a rate of 1°C/min, and dyeing is continued at 130°C for 30
minutes. The mixture is then cooled to 70°C, and the bath is discharged. 2 g/l of
sodium hydrosulphite and 4 ml/l of 36°Bé sodium hydroxide are added in a fresh bath
of 900 parts of water, the mixture is heated to 80°C and treatment is carried out,
for reductive purification, at this temperature for a further 20 minutes. This is
followed by re-cooling and rinsing twice with cold water. The liquor is then discharged,
the goods are unloaded and dried in free air at room temperature. Dark-red, uniformly
dyed goods having a homogeneous nap state and having a very attractive goods appearance
are obtained.
Application Example B [Dyeing of polyester microfibre tricot in the jet (Mathis laboratory jet)]
[0092] A piece of polyester microfibre tricot is dyed as follows in a Mathis laboratory
jet: 90 parts of polyester microfibre tricot are introduced into the jet, which contains
900 parts of aqueous liquor and 1 g/l of dispersion W1. 0.11 % of C.I. Disperse Yellow
52, 0.46 % of C.I. Disperse Red 86, 0.095 % of C.I. Disperse Blue 77 and 0.5 g/l of
an anionic dispersant (formaldehyde condensate of sulphonated naphthalene) are added
to the liquor, the pH is adjusted to from 4.5 to 5.0 with acetic acid, the liquor
is heated from room temperature to 130°C at a rate of 1°C/min and dyeing is continued
at 130°C for 15 minutes. This is followed by re-cooling and rinsing twice with water.
The liquor is then discharged, the goods are unloaded and dried in free air at room
temperature. Mouse-grey, uniformly dyed goods having a soft hand and a very attractive
goods appearance are obtained.
Application Example C [Dyeing of polyester/viscose rayon blend fabric with dispersion dyes and reactive
dyes in the jet (Mathis laboratory jet)]
[0093] 100 parts of polyester/viscose rayon 70/30 blend fabric are introduced into 900 parts
of an aqueous liquor, warmed to 50°C, which contains 1 parts of dispersion W1 and
60 parts of sodium sulphate (Glauber's salt). A solution of 0.35 parts of C.I. Reactive
Blue 41 and 0.73 parts of C.I. Reactive Green 12 in 50 parts of water are added to
the bath. After 20 minutes, a solution of 1.5 parts of soda in 50 parts of water are
added, and dyeing is continued at 50°C for 20 minutes. A dispersion of 0.073 parts
of C.I. Disperse Yellow 54 and 0.53 parts of C.I. Disperse Blue 60 in 50 parts of
water is then added to the bath, and the pH of the bath is adjusted to 4.5-5.0 with
acetic acid. The mixture is then heated from 50°C to 120°C at a rate of 1.5°C/min.
The dyeing is carried out at 130°C for a further 45 minutes, and the bath is then
cooled to 60°C at a rate of 2°C/min. After finishing in a conventional manner (rinsing,
washing, drying), a very level green dyeing having a perfect goods appearance is obtained.
[0094] The other Dispersions W2 to W12 are employed in the above Application Examples A,
B and C in an analogous manner to Dispersion W1.
[0095] The results obtained in the above Application Examples A, B and C agree with the
respective µ
S and µ
K values and their differences Δµ
S and Δµ
K against those of the blanks [i.e. with the same substrate and liquor, but without
(W)].