EP1203119B1 - Erhöhung der nassgleitfähigkeit von textilmaterial - Google Patents

Erhöhung der nassgleitfähigkeit von textilmaterial Download PDF

Info

Publication number
EP1203119B1
EP1203119B1 EP00940702A EP00940702A EP1203119B1 EP 1203119 B1 EP1203119 B1 EP 1203119B1 EP 00940702 A EP00940702 A EP 00940702A EP 00940702 A EP00940702 A EP 00940702A EP 1203119 B1 EP1203119 B1 EP 1203119B1
Authority
EP
European Patent Office
Prior art keywords
acid
textile
polyester
polyesters
optionally
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired - Lifetime
Application number
EP00940702A
Other languages
English (en)
French (fr)
Other versions
EP1203119A1 (de
Inventor
Bernard Danner
Francis Palacin
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Clariant Finance BVI Ltd
Original Assignee
Clariant Finance BVI Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Clariant Finance BVI Ltd filed Critical Clariant Finance BVI Ltd
Priority to EP00940702A priority Critical patent/EP1203119B1/de
Publication of EP1203119A1 publication Critical patent/EP1203119A1/de
Application granted granted Critical
Publication of EP1203119B1 publication Critical patent/EP1203119B1/de
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

Links

Classifications

    • DTEXTILES; PAPER
    • D06TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06PDYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
    • D06P1/00General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed
    • D06P1/44General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed using insoluble pigments or auxiliary substances, e.g. binders
    • D06P1/52General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed using insoluble pigments or auxiliary substances, e.g. binders using compositions containing synthetic macromolecular substances
    • D06P1/5264Macromolecular compounds obtained otherwise than by reactions involving only unsaturated carbon-to-carbon bonds
    • D06P1/5271Polyesters; Polycarbonates; Alkyd resins
    • DTEXTILES; PAPER
    • D06TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06LDRY-CLEANING, WASHING OR BLEACHING FIBRES, FILAMENTS, THREADS, YARNS, FABRICS, FEATHERS OR MADE-UP FIBROUS GOODS; BLEACHING LEATHER OR FURS
    • D06L4/00Bleaching fibres, filaments, threads, yarns, fabrics, feathers or made-up fibrous goods; Bleaching leather or furs
    • D06L4/60Optical bleaching or brightening
    • D06L4/657Optical bleaching or brightening combined with other treatments, e.g. finishing, bleaching, softening, dyeing or pigment printing
    • DTEXTILES; PAPER
    • D06TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06LDRY-CLEANING, WASHING OR BLEACHING FIBRES, FILAMENTS, THREADS, YARNS, FABRICS, FEATHERS OR MADE-UP FIBROUS GOODS; BLEACHING LEATHER OR FURS
    • D06L4/00Bleaching fibres, filaments, threads, yarns, fabrics, feathers or made-up fibrous goods; Bleaching leather or furs
    • D06L4/60Optical bleaching or brightening
    • D06L4/671Optical brightening assistants, e.g. enhancers or boosters
    • DTEXTILES; PAPER
    • D06TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06MTREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M15/00Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
    • D06M15/19Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
    • D06M15/37Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • D06M15/507Polyesters
    • DTEXTILES; PAPER
    • D06TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06MTREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M7/00Treating fibres, threads, yarns, fabrics, or fibrous goods made of other substances with subsequent freeing of the treated goods from the treating medium, e.g. swelling, e.g. polyolefins
    • DTEXTILES; PAPER
    • D06TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06PDYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
    • D06P1/00General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed
    • D06P1/0036Dyeing and sizing in one process
    • DTEXTILES; PAPER
    • D06TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06MTREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M2200/00Functionality of the treatment composition and/or properties imparted to the textile material
    • D06M2200/20Treatment influencing the crease behaviour, the wrinkle resistance, the crease recovery or the ironing ease
    • DTEXTILES; PAPER
    • D06TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06MTREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M2200/00Functionality of the treatment composition and/or properties imparted to the textile material
    • D06M2200/40Reduced friction resistance, lubricant properties; Sizing compositions
    • DTEXTILES; PAPER
    • D06TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06PDYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
    • D06P3/00Special processes of dyeing or printing textiles, or dyeing leather, furs, or solid macromolecular substances in any form, classified according to the material treated
    • D06P3/34Material containing ester groups
    • D06P3/52Polyesters
    • D06P3/54Polyesters using dispersed dyestuffs

Definitions

  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • P S water-dispersible or -colloidally soluble, end-capped polyesters
  • 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.
  • end-capped polyesters (P S ) it is possible to employ known polyesters or polyesters which can be produced analogously to known polyesters.
  • end-capped polyesters P S
  • 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.
  • D difunctional compounds
  • E monomers suitable for polyesterification
  • monofunctional compounds (E) which are suitable for the end capping of the polyesters
  • optionally higher oligo-functional compounds (H) which are suitable for the branching of the polyesters.
  • 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 -.
  • esters of C 1-4 -alcohols for example ethyl esters or preferably methyl esters, or anhydrides
  • Suitable as difunctional monomers (D) are, in particular,
  • 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.
  • (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 glyco
  • diols (A 2 ) those of the type (A 21 ) are preferred, especially polyethylene glycols.
  • (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'
  • aliphatic dicarboxylic acids preference is given to the ⁇ , ⁇ -dicarboxylic acids; of the aliphatic, aromatic and araliphatic dicarboxylic acids (B 1 ), preference is given to the aromatic ones, particularly terephthalic acid.
  • (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
  • (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, ⁇ -caprolactone, ⁇ -butyrolactone and 3,3-dimethyl-4-butyrolactone, and prepolymers thereof.
  • 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,
  • Suitable as (E 1 ) are, in particular,
  • Suitable as (E 2 ) are, in particular,
  • (E 11 ) mention may be made, for example, of the following: cyclohexanol, benzyl alcohol and (C 1-4 -alkyl)-benzyl alcohol.
  • (E 12 ) mention may be made, for example, of the following: benzoic acid and butyric acid.
  • (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.
  • 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 in which alkylene denotes ethylene and/or 1,2-propylene,
  • (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).
  • 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.
  • the components (E 1 ) and (E 2 ) are preferred, particularly (E 21 ), especially the non-ionogenic ones.
  • Suitable as (H) are tri- and higher oligo-functional compounds which can lead to branched products with ester formation, in particular
  • 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.
  • 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.
  • Suitable hydroxycarboxylic acids 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
  • polyesters (P S ) 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).
  • 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).
  • 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.
  • 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 ).
  • 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 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 ).
  • 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.
  • 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.
  • 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.
  • P S dendromeric polyesters or oligoesters
  • the reaction is advantageously controlled in such a way that the average molecular weight M 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.
  • 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.
  • 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
  • polyesters and oligoesters 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 )].
  • 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.
  • 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 ).
  • polyesters as are known as soil release agents for textile substrates (for example in detergents).
  • 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
  • Suitable thickening agents (G) are preferably non-ionogenic and/or anionic substances which are known per se, in particular natural, modified or synthetic polymers.
  • 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.
  • 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.
  • the 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).
  • 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.
  • aqueous compositions (W) in addition to (P S ) and optionally (G), may contain further additives, in particular one or more of the following components:
  • Suitable surfactants (X) are principally the following:
  • the surfactants (X 1 ) and (X 2 ) generally have dispersant character, in particular emulsifier character.
  • 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 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
  • 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.
  • 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 in which
  • 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.
  • R 1 contains 11 to 18 carbon atoms.
  • Suitable anion-active surfactants 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.
  • 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.
  • 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 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 ⁇ -olefins, of alkylbenzenes and of unsaturated fatty acids or alternatively formaldehyde condensates of sulphonated aromatic compounds (for example of sulphonated naphthalene).
  • 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.
  • alkali metal cations for example lithium, sodium, potassium
  • ammonium cations for example those mentioned above] or alternatively alkaline earth metal cations (for example calcium or magnesium)
  • alternatively alkaline earth metal cations for example calcium or magnesium
  • 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.
  • 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.
  • 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.
  • 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).
  • 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.
  • 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).
  • 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.
  • 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.
  • 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).
  • 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).
  • 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).
  • 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.
  • treatment agents (T) for example pre-treatment, dyeing, optical brightening or after-treatment
  • 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.
  • 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.
  • 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.
  • folds i.e. transport folds
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • synthetic fibres for example acrylic fibres or polyurethane fibres
  • optionally modified natural fibres for example of wool, silk or optionally modified cellulose (for example cotton, linen, jute, hemp, ramie, viscose rayon or cellulose a
  • 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.
  • 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.
  • the wet-acting lubricants used in the invention i.e. polyesters (P S ) or compositions (W)
  • P S polyesters
  • W compositions
  • 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.
  • 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.
  • alkali metal salt for example sodium chloride or sodium sulphate
  • alkali metal hydroxide or carbonate concentrations as used in dyeing with said dyes
  • the pH values can be as desired, as are suitable for the respective substrates, dyes and application processes.
  • 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).
  • 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).
  • polyesters or oligoesters 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.
  • the polyester substrate to be treated is a polyester made from terephthalic acid and ethylene glycol (i.e.
  • 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 ).
  • 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.
  • 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.
  • 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.
  • wet-acting lubricants (P S ) particularly in the form of their aqueous compositions (W)
  • 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.
  • 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 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).
  • 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 are commercially available products.
  • 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.
  • the transesterification 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.
  • the system is aerated with nitrogen and cooled.
  • the product solidifies on cooling to room temperature to give a solid material. Yield 730 g.
  • 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.
  • 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
  • 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.
  • melt at 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.
  • 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.
  • an anionic dispersant formaldehyde condensate of sulphonated naphthalene
  • a levelling agent mixture of sulphonated aromatic compounds
  • 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 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.
  • an anionic dispersant formaldehyde condensate of sulphonated naphthalene
  • polyester/viscose rayon 70/30 blend fabric 100 parts 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.
  • 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.
  • 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.
  • Dispersions W2 to W12 are employed in the above Application Examples A, B and C in an analogous manner to Dispersion W1.

Landscapes

  • Engineering & Computer Science (AREA)
  • Textile Engineering (AREA)
  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
  • Lubricants (AREA)
  • Artificial Filaments (AREA)
  • Polyesters Or Polycarbonates (AREA)
  • Detergent Compositions (AREA)
  • Paper (AREA)

Claims (11)

  1. Verwendung von (PS) in Wasser dispergierbaren oder kolloidal löslichen endverschlossenen Polyestern, als Nassgleitmittel beim Behandeln von textiler Stückware mit einem Textilbehandlungsmittel (T) aus wässriger Flotte unter solchen Bedingungen, die sonst im textilen Substrat die Bildung von Lauffalten und/oder das Auftreten von Reibungen im oder am Substrat begünstigen würden.
  2. Verwendung nach Anspruch 1, dadurch gekennzeichnet, dass (PS) ein Polyester aus difunktionellen Verbindungen (D) und monofunktionellen Verbindungen (E), die zum Endverschluss der Polyester geeignet sind, und/oder höher oligofunktionellen Verbindungen (H), die zur Verzweigung der Polyester geeignet sind, ist.
  3. Verwendung nach Anspruch 1 oder 2, dadurch gekennzeichnet, dass man als (PS) einen in Wasser selbstdispergierbaren oder selbst kolloidal löslichen Polyester (PS') einsetzt.
  4. Verwendung nach einem der Ansprüche 1 bis 3, dadurch gekennzeichnet, dass man (PS) in Form eines wässrigen, konzentrierten Präparats (W) einsetzt.
  5. Verwendung nach Anspruch 4, dadurch gekennzeichnet, dass (W) ein wässriges Präparat ist, das durch einen Gehalt an (PS) und (G) einem Verdickungsmittel gekennzeichnet ist.
  6. Verwendung nach Anspruch 4 oder 5, dadurch gekennzeichnet, dass (W) neben (PS) und gegebenenfalls (G) mindestens eine der folgenden Komponenten:
    (X) einen nichtionogenen oder anionischen Emulgator oder eine Mischung von nichtionogenen und/oder anionischen Emulgatoren,
    (Y) ein Mittel zur pH-Einstellung, und
    (Z) mindestens einen Formulierungszusatz
    enthält.
  7. Verwendung nach einem der Ansprüche 1 bis 6, dadurch gekennzeichnet, dass (T) mindestens ein Farbstoff oder mindestens ein optischer Aufheller ist.
  8. Verwendung nach einem der Ansprüche 1 bis 7 beim Färben oder optischen Aufhellen von Textilmaterial aus Polyesterfasern, gegebenenfalls in Mischung mit anderen Fasern, in Düsenfärbeapparaten.
  9. Verwendung nach einem der Ansprüche 1 bis 8 beim Färben oder optischen Aufhellen von Textilmaterial aus Polyestermikrofasern, gegebenenfalls in Mischung mit anderen Fasern vergleichbarer Feinheit.
  10. Verfahren zum Behandeln von textiler Stückware mit einem Textilbehandlungsmittel (T) aus wässriger Flotte unter solchen Bedingungen, die sonst im textilen Substrat die Bildung von Lauffalten oder das Auftreten von Reibungen im oder am Substrat begünstigen würden, dadurch gekennzeichnet, dass man in Gegenwart eines in Wasser dispergierbaren oder kolloidal löslichen endverschlossenen Polyesters (PS) gemäss einem der Ansprüche 1 bis 3, gegebenenfalls in Form eines wässrigen Präparats (W) gemäss einem der Ansprüche 4 bis 6 als Nassgleitmittel verfährt.
  11. Verfahren nach Anspruch 10, bei dem man (PS) am Ende des Behandlungsverfahrens entfernt.
EP00940702A 1999-07-19 2000-07-18 Erhöhung der nassgleitfähigkeit von textilmaterial Expired - Lifetime EP1203119B1 (de)

Priority Applications (1)

Application Number Priority Date Filing Date Title
EP00940702A EP1203119B1 (de) 1999-07-19 2000-07-18 Erhöhung der nassgleitfähigkeit von textilmaterial

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
EP99810650 1999-07-19
EP99810650A EP1070781A1 (de) 1999-07-19 1999-07-19 Erhöhung der Nassgleitfähigkeit von Textilmaterial und Nassgleitmittel dafür
EP00940702A EP1203119B1 (de) 1999-07-19 2000-07-18 Erhöhung der nassgleitfähigkeit von textilmaterial
PCT/IB2000/000981 WO2001006055A1 (en) 1999-07-19 2000-07-18 Increasing the wet slippage properties of textile material, and wet-acting lubricants for this purpose

Publications (2)

Publication Number Publication Date
EP1203119A1 EP1203119A1 (de) 2002-05-08
EP1203119B1 true EP1203119B1 (de) 2005-09-28

Family

ID=8242929

Family Applications (2)

Application Number Title Priority Date Filing Date
EP99810650A Withdrawn EP1070781A1 (de) 1999-07-19 1999-07-19 Erhöhung der Nassgleitfähigkeit von Textilmaterial und Nassgleitmittel dafür
EP00940702A Expired - Lifetime EP1203119B1 (de) 1999-07-19 2000-07-18 Erhöhung der nassgleitfähigkeit von textilmaterial

Family Applications Before (1)

Application Number Title Priority Date Filing Date
EP99810650A Withdrawn EP1070781A1 (de) 1999-07-19 1999-07-19 Erhöhung der Nassgleitfähigkeit von Textilmaterial und Nassgleitmittel dafür

Country Status (11)

Country Link
EP (2) EP1070781A1 (de)
JP (1) JP2003505610A (de)
AT (1) ATE305531T1 (de)
BR (1) BR0012579A (de)
DE (1) DE60022888T2 (de)
ES (1) ES2246866T3 (de)
HK (1) HK1046939B (de)
MX (1) MXPA02000631A (de)
TR (1) TR200200130T2 (de)
WO (1) WO2001006055A1 (de)
ZA (1) ZA200110148B (de)

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1734063A1 (de) * 2005-06-16 2006-12-20 Clariant International Ltd. Polymere für die Erhöhung der Nassgleitfähigkeit von textilmaterialen
CN105925358A (zh) * 2016-04-26 2016-09-07 东莞市剑鑫电子材料有限公司 一种光学蓝宝石水性磨削液

Family Cites Families (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE2737260A1 (de) * 1977-08-18 1979-07-12 Cassella Ag Egalisiermittel und verfahren zum gleichmaessigen faerben von materialien aus synthesefasern
DE3066352D1 (en) * 1979-05-04 1984-03-08 Ciba Geigy Ag Dyeing composition and processes for dyeing fabrics made of polyester or a polyester blend with cotton or wool
JPS61501577A (ja) * 1984-02-27 1986-07-31 ウイルソン,ロバ−ト ブチヤナン 染料組成物及びこれを用いて熱可塑性樹脂材料を着色する方法
DE4107283A1 (de) * 1991-03-07 1992-09-10 Henkel Kgaa Spinnpraeparationen fuer synthetische filamentfasern
ES2086710T3 (es) * 1991-03-25 1996-07-01 Ciba Geigy Ag Preparaciones acuosas de copolimeros, que contienen lubricante.
WO1998000449A1 (en) * 1996-06-28 1998-01-08 Eastman Chemical Company Waterborne polymer composition having a small particle size
US5820982A (en) * 1996-12-03 1998-10-13 Seydel Companies, Inc. Sulfoaryl modified water-soluble or water-dispersible resins from polyethylene terephthalate or terephthalates

Also Published As

Publication number Publication date
HK1046939A1 (en) 2003-01-30
HK1046939B (zh) 2005-11-18
ES2246866T3 (es) 2006-03-01
BR0012579A (pt) 2002-07-02
MXPA02000631A (es) 2002-08-30
ZA200110148B (en) 2003-03-10
ATE305531T1 (de) 2005-10-15
EP1070781A1 (de) 2001-01-24
TR200200130T2 (tr) 2002-05-21
EP1203119A1 (de) 2002-05-08
DE60022888D1 (de) 2006-02-09
JP2003505610A (ja) 2003-02-12
WO2001006055A1 (en) 2001-01-25
DE60022888T2 (de) 2006-07-13

Similar Documents

Publication Publication Date Title
CA1071227A (en) Propylene oxide reaction products, process for their manufacture and their use
US4427557A (en) Anionic textile treating compositions
KR101017641B1 (ko) 폴리에스테르계 섬유재료용 올리고머 제거제
KR101045365B1 (ko) 폴리에스테르계 섬유 재료용 염색성 향상제
JPS595713B2 (ja) 染色用組成物
EP1203119B1 (de) Erhöhung der nassgleitfähigkeit von textilmaterial
US4273554A (en) Process for dyeing textile cellulose material which has not been pre-cleaned
JP5369253B1 (ja) ポリエステル系繊維用のオリゴマー除去剤及びその利用
US5601746A (en) Wet-slippage of textile material and wet lubricant therefor
JP3745872B2 (ja) 防汚性共重合ポリエステルおよびそれからなるポリエステル繊維
CN1231617C (zh) 改质聚酯纤维及其制法
EP1090179B1 (de) Wässrige dispersionen, ihre herstellung und verwendung
CA1117708A (en) Process for preventing oligomer deposits on dyed polyester textile material
US6858044B1 (en) Increasing the wet slippage properties of textiles material, and wet-acting lubricants for this purpose
CA1051614A (en) Process for dyeing materials which contain synthetic fibres
TWI465486B (zh) 織品處理劑組成物、清潔劑及軟化劑,及經彼處理之織品物件
JPH0892819A (ja) 改質ポリエステル
GB1601586A (en) Process for the production of copolyesters
JPS602434B2 (ja) ポリエステル系合成繊維の染色方法
JPS6021977A (ja) 湿時柔軟剤
JPH043448B2 (de)

Legal Events

Date Code Title Description
PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

Free format text: ORIGINAL CODE: 0009012

17P Request for examination filed

Effective date: 20020219

AK Designated contracting states

Kind code of ref document: A1

Designated state(s): AT BE CH CY DE DK ES FI FR GB GR IE IT LI LU MC NL PT SE

17Q First examination report despatched

Effective date: 20050113

GRAP Despatch of communication of intention to grant a patent

Free format text: ORIGINAL CODE: EPIDOSNIGR1

RTI1 Title (correction)

Free format text: INCREASING THE WET SLIPPAGE PROPERTIES OF TEXTILE MATERIAL

GRAS Grant fee paid

Free format text: ORIGINAL CODE: EPIDOSNIGR3

GRAA (expected) grant

Free format text: ORIGINAL CODE: 0009210

AK Designated contracting states

Kind code of ref document: B1

Designated state(s): AT BE CH CY DE DK ES FI FR GB GR IE IT LI LU MC NL PT SE

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: NL

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20050928

Ref country code: FI

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20050928

Ref country code: BE

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20050928

Ref country code: AT

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20050928

REG Reference to a national code

Ref country code: GB

Ref legal event code: FG4D

REG Reference to a national code

Ref country code: CH

Ref legal event code: EP

REG Reference to a national code

Ref country code: IE

Ref legal event code: FG4D

REG Reference to a national code

Ref country code: CH

Ref legal event code: NV

Representative=s name: CLARIANT INTERNATIONAL LTD.

REG Reference to a national code

Ref country code: HK

Ref legal event code: GR

Ref document number: 1046939

Country of ref document: HK

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: SE

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20051228

Ref country code: GR

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20051228

Ref country code: DK

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20051228

REF Corresponds to:

Ref document number: 60022888

Country of ref document: DE

Date of ref document: 20060209

Kind code of ref document: P

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: PT

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20060228

NLV1 Nl: lapsed or annulled due to failure to fulfill the requirements of art. 29p and 29m of the patents act
REG Reference to a national code

Ref country code: ES

Ref legal event code: FG2A

Ref document number: 2246866

Country of ref document: ES

Kind code of ref document: T3

ET Fr: translation filed
PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: IE

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20060718

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: MC

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20060731

PLBE No opposition filed within time limit

Free format text: ORIGINAL CODE: 0009261

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: NO OPPOSITION FILED WITHIN TIME LIMIT

26N No opposition filed

Effective date: 20060629

REG Reference to a national code

Ref country code: IE

Ref legal event code: MM4A

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: LU

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20060718

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: CH

Payment date: 20080623

Year of fee payment: 9

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: DE

Payment date: 20080620

Year of fee payment: 9

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: CY

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20050928

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: FR

Payment date: 20080612

Year of fee payment: 9

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: GB

Payment date: 20080630

Year of fee payment: 9

REG Reference to a national code

Ref country code: FR

Ref legal event code: ST

Effective date: 20090331

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: FR

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20080731

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: ES

Payment date: 20090702

Year of fee payment: 10

REG Reference to a national code

Ref country code: CH

Ref legal event code: PL

GBPC Gb: european patent ceased through non-payment of renewal fee

Effective date: 20090718

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: CH

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20090731

Ref country code: LI

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20090731

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: IT

Payment date: 20090708

Year of fee payment: 10

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: GB

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20090718

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: DE

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20100202

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: IT

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20100718

REG Reference to a national code

Ref country code: ES

Ref legal event code: FD2A

Effective date: 20110818

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: ES

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20100719