EP1043444A1 - Finishing agent for textile comprising urethane-alkylene oxide copolymers - Google Patents

Finishing agent for textile comprising urethane-alkylene oxide copolymers Download PDF

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Publication number
EP1043444A1
EP1043444A1 EP00400969A EP00400969A EP1043444A1 EP 1043444 A1 EP1043444 A1 EP 1043444A1 EP 00400969 A EP00400969 A EP 00400969A EP 00400969 A EP00400969 A EP 00400969A EP 1043444 A1 EP1043444 A1 EP 1043444A1
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finishing
finishing agents
agents according
radical
urethane
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German (de)
French (fr)
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EP1043444B1 (en
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Frédéric Pierre-Marie Durand
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Protex SAS
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Protex SAS
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    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
    • D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
    • D06M15/37—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • D06M15/564—Polyureas, polyurethanes or other polymers having ureide or urethane links; Precondensation products forming them
    • D06M15/568—Reaction products of isocyanates with polyethers

Definitions

  • the present invention relates to new finishing agents.
  • the present invention also relates to synergistic mixtures between these new finishing agents and different Classic fabric softeners.
  • the present invention aims to satisfy this need.
  • radicals R and R 'of formula (1) are well known to those skilled in the art. art and typical examples are the radicals usually associated with isocyanate groups in the case of R, the radicals generally associated polyalkylene glycols and their ethers in the case of R '.
  • radicals R can be illustrated, for example, by the radicals of the following formulas (2) to (4): wherein (d) has a value between 2.4 and 2.8; and
  • the radicals R ′ can be illustrated, for example, by the radicals methyl, ethyl, propyl, butyl, isobutyl, 2-ethylhexyl, benzyl, phenyl, tolyle, xylyl, octylphenyl, nonylphenyl, naphthyl, etc ....
  • copolymers used in the present invention are obtained by reaction of a polyisocyanate with at least one copolymer chosen from copolymers of oxyethylene and oxybutylene and monoalkyl ethers, monoarylics or monoalkylarylics thereof.
  • the molecular mass of the OE / OB copolymers and their monoethers is preferably between 600 and 20000. In the context of the invention, it is preferable to use monoethers of the OE / OB copolymers. However, it is also possible to use a mixture of monoether (s) of (s) OE / OB copolymers and of OE / OB copolymers. In this case, the OE / OB copolymer must not exceed 30% by weight of the mixture OE / OB copolymer monoether - OE / OB copolymer.
  • polyisocyanates which can be used in the invention is not not limiting.
  • polyisocyanates can be used in isolation or mixed.
  • copolymers of formula (1) are used in the form of a solution in water, generally with a dry extract content of 10 to 75%, and more particularly from 20 to 30% by weight.
  • the present invention also relates to synergistic mixtures between the copolymers of formula (1) and different finishing agents classics.
  • copolymers of formula (1) as a finishing agent in the finishing processes, in addition to improving the touch of supports, to increase the hydrophilic power, to confer a power antistatic and to improve the abrasion resistance of treated substrates without affect the degree of white, and this is also a characteristic important of this publication.
  • copolymers of formula (1) are preferably applied to the fibrous material by impregnation in a padding bath, then treated supports are expressed and dried at a temperature of the order of 100 ° C to 180 ° C.
  • the polymers of formula (1) can also be introduced into printing pastes or coating formulations.
  • the use doses of the copolymers of formula (1) may be between 2.5 g / l and 100 g / l or more, preferably between 5 and 75 g / l of padding bath, and from 2.5 to 100 g / kg, preferably from 10 to 75 g / kg of printing paste or coating formulation.
  • copolymers of formula (1) are useful for treating, in particular, a cotton, wool, polyester, nylon, acrylic fabric, knitted fabric, or nonwoven viscose, or a mixture of these different fibrous materials.
  • the softening power is evaluated by a group of 4 people and an average sweetness note is given to the sample.
  • the result of softening power is indicated by a note within a range of 1 to 5.
  • the textile to be tested is subjected to the action of a standard woolen fabric which use it by friction under a load of 500 g in a Type abrasimeter Baskerville and Lindsay.
  • the test consists in noting the number of turns necessary until wear full of the tissue to be evaluated.
  • the abrasion resistance result is calculated by averaging of 8 tests on the same textile.
  • the result is expressed by the half-discharge time in seconds.
  • the sample is 2 cm wide and 20 cm high.
  • the measurement of the mounted water is done after 2 minutes.
  • the result is expressed by measuring the degree of white Wl CIE.
  • the method of manufacturing the copolymers used in the examples is that indicated in Example 1 of French Patent No. 2,280,644 of the plaintiff.
  • the copolymer A is obtained by reaction of poly (phenylene isocyanate) on a polyalkylene glycol ether of type OE / OB (copolymer of ethylene glycol and of butylene glycol) of molar mass equal to 895 alcohol / isocyanate molar ratio: 1.8 copolymer in solution in water, adjusted to 22% of dry extract.
  • the copolymer B is obtained by reaction of poly (phenylene isocyanate) on a polyalkylene glycol ether of type OE / OB (copolymer of ethylene glycol and of butylene glycol) of molar mass equal to 895 alcohol / isocyanate molar ratio: 1.6 copolymer in solution in water, adjusted to 22% of dry extract.
  • the copolymer C is obtained by reaction of poly (phenylene isocyanate) on a polyalkylene glycol ether of type OE / OB (copolymer of ethylene glycol and of butylene glycol) of molar mass equal to 895 alcohol / isocyanate molar ratio: 1.2 copolymer in solution in water, adjusted to 22% of dry extract.
  • a 100% cotton fabric with a grammage of 125 g / m 2 is impregnated, in different padding baths, the fabrics are then expressed and dried at 120 ° C., then the softening effect of the treatment is noted.
  • a polyester / viscose fabric of grammage 105 g / m 2 is impregnated, in different padding baths, the fabrics are then expressed and dried at 120 ° C. then the softening effect of the treatment is noted.
  • polyester / viscose support With the polyester / viscose support the touch obtained is comparable to that of a silk fabric.
  • Example 13 15 acrylic binder, g / l 100 100 100 synthetic thickener, g / l 15 15 15 copolymer A, g / l 20 40 pigment, g / l 25 25 25 softening power 1 3 5
  • Example 16 17 18 disclose* copolymer A, g / l 10 20 50 0 anti-static power 1 ⁇ 2 discharge time 45 " 10 " 0 > 1 hour
  • the hydrophilic powers obtained are presented below: untreated cotton fabric (100%) 15 mm cotton fabric (100%) treated 35 mm untreated polyester / viscose fabric 20 mm treated polyester / viscose fabric 45 mm untreated acrylic fabric (100%) 8 mm acrylic fabric (100%) treated 60 mm.
  • copolymers of formula (1) make it possible to improve very clearly the hydrophilicity of textiles. In the absence of addition of copolymer A in the bath padding the samples all have a low hydrophilicity.
  • Example 20 21 22 The composition of the padding baths and the results obtained are given in the following table:
  • Example 20 21 22 Witness* copolymer A, g / l 5 10 20 0 abrasion resistance, nb. of turns 450 580 700 350
  • the product P1 applied alone from a 10 g / l bath gives on cotton 100% abrasion resistance of 750.
  • the abrasion resistance of the treated support is measured and it is equal to 850.
  • the P2 product applied alone at a rate of 10 g / l on 100% cotton gives an abrasion resistance of 1000.
  • the abrasion resistance of the textile support is measured. treated and we find it equal to 1150.
  • the product P3 is an amino-silicone emulsion whose dry extract is 25% by weight.
  • Example 25 26 27 disclose copolymer A 20 40 0 product P3 10 0 degree of white after treatment at 180 ° C, Wl CIE 133.4 133.2 122.6 133.6
  • the product P3 is considered to be a product with a slight influence on the degree of white.

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Textile Engineering (AREA)
  • Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
  • Polyurethanes Or Polyureas (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

Multifunctional finishing-dressing agents comprise urethane-oxyalkylene copolymers. The agents comprise urethane-oxy-alkoyl ene copolymers of formula: R(NH-CO-O-(C2H4-O-)a - (C4H8-O)b - R')y (N=C=O)x (I) R = aliphatic and/or aromatic structure containing biuret, urethane or isocyanurate groups, or radicals of formula (2), (3) (4); d = 2.4 - 2.8; R' = H, at least 8C linear or branched alkoxyl radical or aryl or alkylaryl radical, and preferably methyl, ethyl, propyl, butyl, isobutyl, 2-ethylhexyl, benzyl, phenyl, tolyl, xylyl, octylphenyl, nonylphenyl or naphthyl radical; x = 0-1, y = more than 2; a = at least 1; b = at least 1; (a+b) = at least 5 An Independent claim is also included for mixtures comprising classic dressing agent, preferably in form of emulsion of paraffin, low density polyethylene or high density polyethylene, and dressing-finishing agent as claimed.

Description

La présente invention a pour objet de nouveaux agents de finissage polyvalents pour textiles appartenant à la classe des copolymères uréthane-oxyalcoylène ayant un pouvoir adoucissant élevé, permettant d'améliorer l'hydrophilie et la résistance à l'abrasion, et conférant des propriétés antistatiques.The present invention relates to new finishing agents. multi-purpose for textiles belonging to the class of urethane-oxyalkylene copolymers having a high softening power, making it possible to improve hydrophilicity and abrasion resistance, and imparting properties antistatic.

La présente invention concerne également des mélanges synergiques entre ces nouveaux agents de finissage et différents adoucissants Classiques.The present invention also relates to synergistic mixtures between these new finishing agents and different Classic fabric softeners.

De nombreux adoucissants sont actuellement utilisés tels que par exemple :

  • les microémulsions d'amino-silicone,
  • les émulsions de polyéthylène,
  • les émulsions de silicone, et
  • les adoucissants cationiques (amines, amides ou imidazolines dans lesquels les molécules d'azote sont sous la forme trivalente).
Many softeners are currently used such as for example:
  • amino-silicone microemulsions,
  • polyethylene emulsions,
  • silicone emulsions, and
  • cationic softeners (amines, amides or imidazolines in which the nitrogen molecules are in the trivalent form).

Les principales propriétés de ces adoucissants sont les suivantes :

  • les microémulsions d'amino-silicone donnent un toucher doux et gonflant, mais leur influence sur l'hydrophilie est faible et elles entraínent un léger jaunissement des blancs au cours des étapes de séchage ou de thermofixation ;
  • les émulsions de polyéthylène sont spécialement recommandées dans les traitements réalisés en présence de résines afin d'en amoindrir les effets négatifs sur le toucher et la résistance à l'abrasion. Améliorant la résistance à l'abrasion, elles sont ainsi retenues pour améliorer les opérations de coupe ou de couture. Les émulsions de polyéthylène permettent d'accroítre la nervosité des fibres mais n'ont pas un pouvoir adoucissant élevé ;
  • les émulsions de silicone donnent un toucher particulièrement doux et lisse mais elles n'ont pas d'influence sur l'hydrophilie des supports textiles et n'ont aucun pouvoir antistatique ;
  • les adoucissants cationiques possèdent d'excellentes propriétés adoucissantes mais présentent un certain nombre d'inconvénients notamment :
  • un jaunissement plus ou moins important des blancs et en particulier des blancs azurés optiquement ;
  • une perte de l'hydrophilie et une instabilité en présence d'électrolyte.
The main properties of these softeners are as follows:
  • amino-silicone microemulsions give a soft and swelling feel, but their influence on hydrophilicity is weak and they cause a slight yellowing of the whites during the drying or heat-fixing steps;
  • polyethylene emulsions are specially recommended in treatments carried out in the presence of resins in order to lessen the negative effects on touch and resistance to abrasion. Improving abrasion resistance, they are thus retained to improve cutting or sewing operations. Polyethylene emulsions make it possible to increase the nervousness of the fibers but do not have a high softening power;
  • silicone emulsions give a particularly soft and smooth feel but they have no influence on the hydrophilicity of textile supports and have no antistatic power;
  • cationic softeners have excellent softening properties but have a certain number of drawbacks in particular:
  • a more or less significant yellowing of the whites and in particular of the optically azure whites;
  • loss of hydrophilicity and instability in the presence of electrolyte.

Le développement des supports textiles à traiter et l'exigence au niveau des propriétés recherchées ont fait en sorte que les produits d'apprêts ont fortement évolué au niveau technologique et que de nouvelles molécules sont recherchées pour permettre aux ennoblisseurs de proposer des nouveaux touchers, de nouvelles propriétés sur les articles traités. Malgré tous les agents de finissage disponibles sur le marché, il existe toujours un besoin pour des agents de finissage dits polyvalents apportant un nouvel ensemble de propriétés.The development of the textile supports to be treated and the requirement at the level sought after properties have resulted in the primers having strongly evolved at the technological level and that new molecules are wanted to allow ennoellers to propose new touches, new properties on treated items. Despite all finishing agents available on the market, there is still a need for so-called versatile finishing agents providing a new set of properties.

La présente invention vise à satisfaire ce besoin.The present invention aims to satisfy this need.

L'invention concerne un agent de finissage ayant un pouvoir adoucissant élevé, améliorant l'hydrophilie des supports textiles traités et conférant des propriétés antistatiques et de résistance à l'abrasion, qui est sans influence néfaste sur le degré de blanc ou la nuance des supports textiles traités et compatible avec la plupart des apprêts classiques et des résines.A finishing agent having power high softener, improving the hydrophilicity of treated textile supports and imparting antistatic and abrasion resistance properties, which is without detrimental influence on the degree of white or the shade of the supports textiles treated and compatible with most conventional finishes and resins.

Il a été trouvé de façon inattendue, que certains des polymères décrits dans FR-B-2 280 644 comme agents de thermocoagulation de latex, pouvaient être utilisés comme agent de finissage polyvalent lors des opérations d'ennoblissement de textiles.It has been unexpectedly found that some of the polymers described in FR-B-2 280 644 as latex thermocoagulation agents, could be used as a versatile finishing agent during textile finishing operations.

En effet, l'application de ces polymères sur différents supports textiles selon les procédés habituels des ennoblisseurs permet d'améliorer le toucher des supports textiles, d'augmenter le pouvoir hydrophile, de conférer un pouvoir antistatique et d'améliorer la résistance à l'abrasion des supports textiles traités.Indeed, the application of these polymers on different textile supports according to the usual processes of the ennoellers makes it possible to improve the touch textile supports, to increase the hydrophilicity, to confer a antistatic power and improve the abrasion resistance of substrates treated textiles.

La présente invention concerne des agents de finissage polyvalents pour textiles exempts de liant thermoactivable comprenant des copolymères uréthane-oxyalcoylène de la formule (1) suivante : R[NH―CO―O―(-C2H4-O-)a-(C4H8-O)b―R']y(N=C=O)x dans laquelle R représente une structure aliphatique et/ou aromatique pouvant contenir des groupements biuret, uréthanne ou isocyanurate, R' est choisi parmi l'hydrogène, un radical alcoyle de moins de 8 atomes de carbone à chaíne droite ou à chaíne ramifiée, un radical aryle ou un radical alkylaryle, x est compris entre 0 et 1, y est supérieur à 2, a vaut au moins 1, b vaut au moins 1, la somme (a+b) vaut au moins 5. Par exemple la somme (a+b) peut valoir de 5 à 100 ou plus.The present invention relates to versatile finishing agents for textiles free from heat-activatable binder comprising urethane-oxyalkylene copolymers of the following formula (1): R [NH ― CO ― O - (- C 2 H 4 -O-) a - (C 4 H 8 -O) b ―R '] y (N = C = O) x in which R represents an aliphatic and / or aromatic structure which may contain biuret, urethane or isocyanurate groups, R 'is chosen from hydrogen, an alkyl radical of less than 8 carbon atoms with a straight chain or with a branched chain, a radical aryl or an alkylaryl radical, x is between 0 and 1, y is greater than 2, a is at least 1, b is at least 1, the sum (a + b) is at least 5. For example the sum (a + b) can be from 5 to 100 or more.

Les radicaux R et R' de la formule (1) sont bien connus de l'homme de l'art et des exemples typiques en sont les radicaux habituellement liés aux groupes isocyanates dans le cas de R, les radicaux généralement associés aux polyalcoylène glycols et à leurs éthers dans le cas de R'.The radicals R and R 'of formula (1) are well known to those skilled in the art. art and typical examples are the radicals usually associated with isocyanate groups in the case of R, the radicals generally associated polyalkylene glycols and their ethers in the case of R '.

Les radicaux R peuvent être illustrés, par exemple, par les radicaux des formules (2) à (4) suivantes :

Figure 00030001
dans laquelle (d) a une valeur comprise entre 2,4 et 2,8;
Figure 00030002
et
Figure 00030003
The radicals R can be illustrated, for example, by the radicals of the following formulas (2) to (4):
Figure 00030001
wherein (d) has a value between 2.4 and 2.8;
Figure 00030002
and
Figure 00030003

Les radicaux R' peuvent être illustrés, par exemple, par les radicaux méthyle, éthyle, propyle, butyle, isobutyle, 2-éthylhexyle, benzyle, phényle, tolyle, xylyle, octylphényle, nonylphényle, naphtyle, etc.... The radicals R ′ can be illustrated, for example, by the radicals methyl, ethyl, propyl, butyl, isobutyl, 2-ethylhexyl, benzyl, phenyl, tolyle, xylyl, octylphenyl, nonylphenyl, naphthyl, etc ....

Les copolymères utilisés dans la présente invention sont obtenus par réaction d'un polyisocyanate avec au moins un copolymère choisi parmi les copolymères d'oxyéthylène et d'oxybutylène et les éthers monoalkyliques, monoaryliques ou monoalkylaryliques de ceux-ci.The copolymers used in the present invention are obtained by reaction of a polyisocyanate with at least one copolymer chosen from copolymers of oxyethylene and oxybutylene and monoalkyl ethers, monoarylics or monoalkylarylics thereof.

La masse moléculaire des copolymères OE/OB et de leurs monoéthers est préférentiellement comprise entre 600 et 20000. Dans le cadre de l'invention, il est préférable d'utiliser des monoéthers des copolymères OE/OB. Toutefois, il est possible aussi d'utiliser un mélange de monoéther(s) de(s) copolymères OE/OB et de(s) copolymères OE/OB. Dans ce cas, le copolymère OE/OB ne doit pas dépasser 30% en poids du mélange monoéther de copolymère OE/OB - copolymère OE/OB.The molecular mass of the OE / OB copolymers and their monoethers is preferably between 600 and 20000. In the context of the invention, it is preferable to use monoethers of the OE / OB copolymers. However, it is also possible to use a mixture of monoether (s) of (s) OE / OB copolymers and of OE / OB copolymers. In this case, the OE / OB copolymer must not exceed 30% by weight of the mixture OE / OB copolymer monoether - OE / OB copolymer.

Des polyisocyanates utiles aux fins de l'invention sont :

  • a) le poly(phénylène isocyanate) de formule :
    Figure 00040001
    dans laquelle (d) a une valeur de 2,4 à 2,8.
  • b) le triphényl méthane triisocyanate de formule :
    Figure 00040002
  • c) les polyisocyanates préparés par condensation d'un diisocyanate sur un polyol dans des conditions telles qu'il y ait plus de 2 groupes - N = C = 0 libres. Un exemple choisi de cette Classe de polyisocyanates est le produit de réaction de 3 moles de toluylène diisocyanate sur une mole de triméthylol propane et dont la structure uréthane idéalisée est :
    Figure 00050001
  • d) les polyisocyanates préparés par condensation d'un diisocyanate sur l'eau avec formation de cycles isocyanurates.
  • e) les polyisocyanates préparés par condensation d'un diisocyanate sur l'eau avec formation de groupes biuret. Un exemple de cette classe de polyisocyanates est le produit de condensation avec l'eau de 3 moles de 1-6 hexaméthylène diisocyanate et dont la structure biuret idéalisée est :
    Figure 00050002
    • Polyisocyanates useful for the purposes of the invention are:
  • a) the poly (phenylene isocyanate) of formula:
    Figure 00040001
    in which (d) has a value of 2.4 to 2.8.
  • b) triphenyl methane triisocyanate of formula:
    Figure 00040002
  • c) polyisocyanates prepared by condensation of a diisocyanate on a polyol under conditions such that there are more than 2 free groups - N = C = 0. A selected example of this Class of polyisocyanates is the reaction product of 3 moles of toluylene diisocyanate with one mole of trimethylol propane and whose idealized urethane structure is:
    Figure 00050001
  • d) polyisocyanates prepared by condensation of a diisocyanate on water with the formation of isocyanurate rings.
  • e) polyisocyanates prepared by condensation of a diisocyanate on water with the formation of biuret groups. An example of this class of polyisocyanates is the condensation product with water of 3 moles of 1-6 hexamethylene diisocyanate and whose idealized biuret structure is:
    Figure 00050002
    •

    La liste d-dessus des polyisocyanates utilisables dans l'invention n'est pas limitative. D'autre part, les polyisocyanates peuvent être utilisés isolément ou en mélange.The above list of polyisocyanates which can be used in the invention is not not limiting. On the other hand, polyisocyanates can be used in isolation or mixed.

    Les copolymères de formule (1) sont utilisés sous forme de solution dans l'eau, généralement à une teneur en extrait sec de 10 à 75% , et plus particulièrement de 20 à 30% en poids.The copolymers of formula (1) are used in the form of a solution in water, generally with a dry extract content of 10 to 75%, and more particularly from 20 to 30% by weight.

    La présente invention concerne également des mélanges synergiques entre les copolymères de formule (1) et différents agents de finissage classiques.The present invention also relates to synergistic mixtures between the copolymers of formula (1) and different finishing agents classics.

    En effet, il a été observé que l'utilisation des copolymères de formule (1) en présence de divers agents classiques permettant d'augmenter la résistance à l'abrasion (émulsion de paraffine, de polyéthylène basse densité, de polyéthylène haute densité.....) permet d'accroítre la résistance à l'abrasion à une valeur supérieure à celle conférée par chacun des agents appliqués isolément. Indeed, it has been observed that the use of the copolymers of formula (1) in the presence of various conventional agents making it possible to increase the resistance abrasion (paraffin emulsion, low density polyethylene, high density polyethylene .....) increases the abrasion resistance to a value greater than that conferred by each of the agents applied isolation.

    Ces mélanges contiennent :

    • de 5 à 95% en poids et préférentiellement 10 à 30% de copolymère de formule (1), et
    • de 5 à 95% en poids et préférentiellement 70 à 90% d'agent permettant d'augmenter la résistance à l'abrasion tel que, par exemple, les émulsions de paraffine, les émulsions de polyéthylène basse densité, et les émulsions de polyéthylène haute densité.
    These mixtures contain:
    • from 5 to 95% by weight and preferably 10 to 30% of copolymer of formula (1), and
    • from 5 to 95% by weight and preferably 70 to 90% of agent making it possible to increase the resistance to abrasion such as, for example, paraffin emulsions, low density polyethylene emulsions, and high polyethylene emulsions density.

    L'utilisation des copolymères de formule (1) comme agent de finissage dans les procédés d'ennoblissement, permet outre d'améliorer le toucher des supports, d'augmenter le pouvoir hydrophile, de conférer un pouvoir antistatique et d'améliorer la résistance à l'abrasion des supports traités sans affecter le degré de blanc, et ceci constitue également une caractéristique importante de la présente publication.The use of the copolymers of formula (1) as a finishing agent in the finishing processes, in addition to improving the touch of supports, to increase the hydrophilic power, to confer a power antistatic and to improve the abrasion resistance of treated substrates without affect the degree of white, and this is also a characteristic important of this publication.

    Les copolymères de formule (1) sont appliqués préférentiellement sur la matière fibreuse par imprégnation dans un bain de foulardage, puis les supports traités sont exprimés et séchés à une température de l'ordre de 100°C à 180°C. Les polymères de formule (1) peuvent également être introduits dans des pâtes d'impression ou dans des formulations d'enduction.The copolymers of formula (1) are preferably applied to the fibrous material by impregnation in a padding bath, then treated supports are expressed and dried at a temperature of the order of 100 ° C to 180 ° C. The polymers of formula (1) can also be introduced into printing pastes or coating formulations.

    Les doses d'utilisation des copolymères de formule (1) pourront être comprises entre 2,5 g/l et 100 g/l ou plus, de préférence entre 5 et 75 g/l de bain de foulardage, et de 2,5 à 100 g/kg, de préférence de 10 à 75 g/kg de pâte d'impression ou de formulation d'enduction.The use doses of the copolymers of formula (1) may be between 2.5 g / l and 100 g / l or more, preferably between 5 and 75 g / l of padding bath, and from 2.5 to 100 g / kg, preferably from 10 to 75 g / kg of printing paste or coating formulation.

    Les copolymères de formule (1) sont utiles pour traiter, notamment, un tissu, un tricot, ou un non-tissé en coton, laine, polyester, nylon, acrylique, viscose, ou un mélange de ces différentes matières fibreuses.The copolymers of formula (1) are useful for treating, in particular, a cotton, wool, polyester, nylon, acrylic fabric, knitted fabric, or nonwoven viscose, or a mixture of these different fibrous materials.

    Les exemples donnés ci-après à titre indicatif et non limitatif permettront de mieux comprendre l'invention.The examples given below by way of indication and without limitation will allow to better understand the invention.

    Les méthodes d'évaluation suivantes ont été utilisées :The following assessment methods were used:

    Pouvoir adoucissant : Softening power :

    Le pouvoir adoucissant est évalué par un groupe de 4 personnes et une note de douceur moyenne est donnée à l'échantillon. Le résultat du pouvoir adoucissant est indiqué par une note comprise dans une fourchette de 1 à 5.The softening power is evaluated by a group of 4 people and an average sweetness note is given to the sample. The result of softening power is indicated by a note within a range of 1 to 5.

    La note 1 correspond à un échantillon non traité.Note 1 corresponds to an untreated sample.

    Résistance à l'abrasion : Abrasion resistance : Principe :Principle:

    Le textile à tester est soumis à l'action d'un tissu de laine standard qui l'use par friction sous une charge de 500 g dans un abrasimètre de Type Baskerville et Lindsay.The textile to be tested is subjected to the action of a standard woolen fabric which use it by friction under a load of 500 g in a Type abrasimeter Baskerville and Lindsay.

    Le test consiste à noter le nombre de tours nécessaires jusqu'à usure complète du tissu à évaluer.The test consists in noting the number of turns necessary until wear full of the tissue to be evaluated.

    Le résultat de résistance à l'abrasion est calculé en faisant la moyenne de 8 essais sur le même textile.The abrasion resistance result is calculated by averaging of 8 tests on the same textile.

    Plus le nombre de tours est élevé meilleure est la résistance à l'abrasion.The higher the number of turns, the better the resistance to abrasion.

    Pouvoir antistatique : Antistatic power :

    En utilisant un appareil Static-Voltmeter (Rotschild R1019), on établit une différence de charges électrostatiques entre 2 points situés à 10 cm d'un matériau à tester et on mesure le temps nécessaire pour que cette charge descende de moitié (temps de demi-décharge).Using a Static-Voltmeter (Rotschild R1019), we establish a difference in electrostatic charges between 2 points located 10 cm from a material to be tested and we measure the time necessary for this charge descends by half (half-discharge time).

    Le résultat est exprimé par le temps de demi-décharge en secondes.The result is expressed by the half-discharge time in seconds.

    Pouvoir hydrophile : Hydrophilic power :

    On mesure la hauteur d'eau montée par capillarité sur un échantillon textile placé verticalement au-dessus de l'eau, avec son extrémité inférieure baignant dans l'eau.We measure the height of water mounted by capillarity on a sample textile placed vertically above the water, with its lower end bathing in water.

    L'échantillon a une largeur de 2 cm et une hauteur de 20 cm.The sample is 2 cm wide and 20 cm high.

    La mesure de l'eau montée se fait au bout de 2 minutes.The measurement of the mounted water is done after 2 minutes.

    Le résultat est exprimé en mm.The result is expressed in mm.

    Evaluation du jaunissement : Assessment of yellowing :

    On mesure dans un spectrocolorimètre Minolta® CM-3600d le degré de blanc d'un échantillon de tissu traité avec l'agent de l'invention, comparativement à un échantillon non traité. La mesure du degré de blanc est faite sur des échantillons séchés à 120°C, puis traités à 180°C prenant 1 minute.We measure in a Minolta® CM-3600d spectrocolorimeter the degree white of a tissue sample treated with the agent of the invention, compared to an untreated sample. The measure of the white degree is made on samples dried at 120 ° C, then treated at 180 ° C taking 1 minute.

    Le résultat est exprimé par la mesure du degré de blanc Wl CIE.The result is expressed by measuring the degree of white Wl CIE.

    Le mode de fabrication des copolymères utilisés dans les exemples est celui indiqué dans l'exemple 1 du brevet français No. 2 280 644 de la demanderesse.The method of manufacturing the copolymers used in the examples is that indicated in Example 1 of French Patent No. 2,280,644 of the plaintiff.

    Le copolymère A est obtenu par réaction de poly(isocyanate de phénylène) sur un éther de polyalcoylène glycols de type OE/OB (copolymère d'éthylène glycol et de butylène glycol) de masse molaire égale à
    895
    ratio molaire alcool/isocyanate : 1,8
    copolymère en solution dans l'eau, ajusté à 22% d'extrait sec.    The copolymer A is obtained by reaction of poly (phenylene isocyanate) on a polyalkylene glycol ether of type OE / OB (copolymer of ethylene glycol and of butylene glycol) of molar mass equal to
    895
    alcohol / isocyanate molar ratio: 1.8
    copolymer in solution in water, adjusted to 22% of dry extract.

    Le copolymère B est obtenu par réaction de poly(isocyanate de phénylène) sur un éther de polyalcoylène glycols de type OE/OB (copolymère d'éthylène glycol et de butylène glycol) de masse molaire égale à 895
    ratio molaire alcool/isocyanate : 1,6
    copolymère en solution dans l'eau, ajusté à 22% d'extrait sec.    The copolymer B is obtained by reaction of poly (phenylene isocyanate) on a polyalkylene glycol ether of type OE / OB (copolymer of ethylene glycol and of butylene glycol) of molar mass equal to 895
    alcohol / isocyanate molar ratio: 1.6
    copolymer in solution in water, adjusted to 22% of dry extract.

    Le copolymère C est obtenu par réaction de poly(isocyanate de phénylène) sur un éther de polyalcoylène glycols de type OE/OB (copolymère d'éthylène glycol et de butylène glycol) de masse molaire égale à 895
    ratio molaire alcool/isocyanate : 1,2
    copolymère en solution dans l'eau, ajusté à 22% d'extrait sec.    The copolymer C is obtained by reaction of poly (phenylene isocyanate) on a polyalkylene glycol ether of type OE / OB (copolymer of ethylene glycol and of butylene glycol) of molar mass equal to 895
    alcohol / isocyanate molar ratio: 1.2
    copolymer in solution in water, adjusted to 22% of dry extract.

    EXEMPLES 1 à 6EXAMPLES 1 to 6

    On imprègne un tissu 100% coton de grammage 125 g/m2, dans différents bains de foulardage, les tissus sont ensuite exprimés et séchés à 120°C, puis on note l'effet adoucissant du traitement.A 100% cotton fabric with a grammage of 125 g / m 2 is impregnated, in different padding baths, the fabrics are then expressed and dried at 120 ° C., then the softening effect of the treatment is noted.

    La composition des bains de foulardage et les résultats obtenus sont donnés dans le tableau suivant : Exemple 1 2 3 4 5 6 Témoin Copolymère A, g/l 20 40 0 Copolymère B, g/l 20 40 0 Copolymère C, g/l 20 40 0 Pouvoir adoucissant 3 5 2 4,5 2 4 1 The composition of the padding baths and the results obtained are given in the following table: Example 1 2 3 4 5 6 Witness Copolymer A, g / l 20 40 0 Copolymer B, g / l 20 40 0 Copolymer C, g / l 20 40 0 Softening power 3 5 2 4.5 2 4 1

    On constate ainsi que les échantillons traités ont subi un traitement adoucissant fort intéressant.It can thus be seen that the treated samples have undergone a treatment very interesting softener.

    EXEMPLES 7 à 12EXAMPLES 7 to 12

    On imprègne un tissu polyester/viscose de grammage 105 g/m2, dans différents bains de foulardage, les tissus sont ensuite exprimés et séchés à 120°C puis on note l'effet adoucissant du traitement.A polyester / viscose fabric of grammage 105 g / m 2 is impregnated, in different padding baths, the fabrics are then expressed and dried at 120 ° C. then the softening effect of the treatment is noted.

    La composition des bains de foulardage et les résultats obtenus sont donnés dans le tableau suivant : Exemple 7 8 9 10 11 12 Témoin Copolymère A, g/l 20 40 0 Copolymère B, g/l 20 40 0 Copolymère C, g/l 20 40 0 Pouvoir adoucissant 4 5 3 4,5 3 4 1 The composition of the padding baths and the results obtained are given in the following table: Example 7 8 9 10 11 12 Witness Copolymer A, g / l 20 40 0 Copolymer B, g / l 20 40 0 Copolymer C, g / l 20 40 0 Softening power 4 5 3 4.5 3 4 1

    Après traitement, on enregistre des résultats comparables à ceux des exemples 1 à 6, soit un pouvoir adoucissant élevé.After treatment, results comparable to those of examples 1 to 6, ie a high softening power.

    Avec le support polyester/viscose le toucher obtenu est comparable à celui d'un tissu de soie.With the polyester / viscose support the touch obtained is comparable to that of a silk fabric.

    EXEMPLES 13 à 15EXAMPLES 13 to 15

    On imprime un tissu 100% coton de grammage 125 g/m2, avec différentes pâtes d'impression, les tissus sont ensuite séchés à 120°C et thermofixés à 160°C, puis on note l'influence du traitement sur le toucher des supports traités.We print a 100% cotton fabric with a grammage of 125 g / m 2 , with different printing pastes, the fabrics are then dried at 120 ° C and heat-set at 160 ° C, then we note the influence of the treatment on the feel of the treated supports.

    Dans cet exemple on utilise pour la formulation des pâtes :

    • un liant acrylique pour l'impression pigmentaire ayant un extrait sec de 45%,
    • un épaississant synthétique dont la viscosité à 15 g/l dans l'eau est de 230 Pa.s (viscosité à 20°C), et
    • un pigment rouge référencé dans le Color Index sous le n° Cl pigment Red 57.
    In this example we use for the formulation of pasta:
    • an acrylic binder for pigment printing having a dry extract of 45%,
    • a synthetic thickener whose viscosity at 15 g / l in water is 230 Pa.s (viscosity at 20 ° C), and
    • a red pigment referenced in the Color Index under the n ° Cl pigment Red 57.

    La composition des pâtes d'impression et les résultats obtenus sont récapitulés dans le tableau suivant : Exemple 13 14 15 liant acrylique, g/l 100 100 100 épaississant synthétique, g/l 15 15 15 copolymère A, g/l 20 40 pigment, g/l 25 25 25 pouvoir adoucissant 1 3 5 The composition of the printing pastes and the results obtained are summarized in the following table: Example 13 14 15 acrylic binder, g / l 100 100 100 synthetic thickener, g / l 15 15 15 copolymer A, g / l 20 40 pigment, g / l 25 25 25 softening power 1 3 5

    On constate ainsi que les supports imprimés avec les pâtes d'impression contenant le polymère A de formule (1) possèdent un toucher fort agréable.We can see that the supports printed with the pasta containing polymer A of formula (1) have a feel very pleasant.

    EXEMPLES 16 à 18EXAMPLES 16 to 18

    On imprègne un tissu acrylique 100% de grammage 145 g/m2, dans différents bains de foulardage, les tissus sont ensuite exprimés et séchés à 120°C, puis on note les propriétés antistatiques des tissus.An acrylic fabric 100% grammage 145 g / m 2 is impregnated, in different padding baths, the fabrics are then expressed and dried at 120 ° C., then the antistatic properties of the fabrics are noted.

    La composition des bains de foulardage et les résultats obtenus sont résumés dans le tableau ci-dessous : Exemple 16 17 18 Témoin* copolymère A, g/l 10 20 50 0 pouvoir antistatique temps de ½ décharge 45" 10" 0 >1 heure The composition of the padding baths and the results obtained are summarized in the table below: Example 16 17 18 Witness* copolymer A, g / l 10 20 50 0 anti-static power ½ discharge time 45 " 10 " 0 > 1 hour

    Les valeurs obtenues avec les exemples 16-18 permettent de constater le pouvoir antistatique des polymères de formule (1).The values obtained with examples 16-18 make it possible to observe the antistatic power of the polymers of formula (1).

    EXEMPLE 19EXAMPLE 19

    On imprègne des tissus de coton 100%, de polyester/viscose et d'acrylique 100% dans un bain de foulardage contenant uniquement 10 g/l de copolymère A, les tissus sont ensuite exprimés et séchés à 120°C, puis on mesure le pouvoir hydrophile.We impregnate fabrics of 100% cotton, polyester / viscose and 100% acrylic in a padding bath containing only 10 g / l of copolymer A, the fabrics are then expressed and dried at 120 ° C., then measures hydrophilicity.

    Les pouvoirs hydrophiles obtenus sont présentés ci-après : tissu de coton (100%) non traité 15 mm tissu de coton (100%) traité 35 mm tissu de polyester/viscose non traité 20 mm tissu de polyester/viscose traité 45 mm tissu en acrylique (100%) non traité 8 mm tissu en acrylique (100%) traité 60 mm. The hydrophilic powers obtained are presented below: untreated cotton fabric (100%) 15 mm cotton fabric (100%) treated 35 mm untreated polyester / viscose fabric 20 mm treated polyester / viscose fabric 45 mm untreated acrylic fabric (100%) 8 mm acrylic fabric (100%) treated 60 mm.

    Après séchage on constate donc une grande hydrophilie des textiles traités. Les copolymères de formule (1) permettent d'améliorer très nettement l'hydrophilie des textiles. En l'absence d'addition du copolymère A dans le bain de foulardage les échantillons présentent tous une faible hydrophilie.After drying there is therefore a great hydrophilicity of the textiles treated. The copolymers of formula (1) make it possible to improve very clearly the hydrophilicity of textiles. In the absence of addition of copolymer A in the bath padding the samples all have a low hydrophilicity.

    EXEMPLES 20 à 22EXAMPLES 20 to 22

    On imprègne un tissu coton 100%, dans différents bains de foulardage, les tissus sont ensuite exprimés et séchés à 120°C, puis on note la résistance à l'abrasion des tissus.We impregnate a 100% cotton fabric in different padding baths, the fabrics are then expressed and dried at 120 ° C., then the resistance is noted tissue abrasion.

    La composition des bains de foulardage et les résultats obtenus sont donnés dans le tableau suivant : Exemple 20 21 22 Témoin* copolymère A, g/l 5 10 20 0 résistance à l'abrasion, nb. de tours 450 580 700 350 The composition of the padding baths and the results obtained are given in the following table: Example 20 21 22 Witness* copolymer A, g / l 5 10 20 0 abrasion resistance, nb. of turns 450 580 700 350

    Les valeurs obtenues permettent de constater une nette amélioration de la résistance à l'abrasion par les copolymères de formule (1).The values obtained show a clear improvement abrasion resistance by the copolymers of formula (1).

    EXEMPLE 23EXAMPLE 23

    On imprègne un tissu coton 100%, dans différents bains de foulardage, les tissus sont ensuite exprimés et séchés à 120°C, puis on note la résistance à l'abrasion des tissus.We impregnate a 100% cotton fabric in different padding baths, the fabrics are then expressed and dried at 120 ° C., then the resistance is noted tissue abrasion.

    On réalise un bain ayant la composition suivante :
       10 g/l d'une solution aqueuse contenant :

  • 25% de copolymère A
  • 75% de produit P1
    • produit P1 : émulsion de polyéthylène oxydé dont l'extrait sec est de 24% en poids.A bath is produced having the following composition:
    10 g / l of an aqueous solution containing:
  • 25% of copolymer A
  • 75% of product P1
    • product P1: emulsion of oxidized polyethylene, the dry extract of which is 24% by weight.

    Le produit P1 appliqué seul à partir d'un bain à 10 g/l donne sur le coton 100% une résistance à l'abrasion de 750.The product P1 applied alone from a 10 g / l bath gives on cotton 100% abrasion resistance of 750.

    Après séchage on mesure la résistance à l'abrasion du support traité et elle est égale à 850.After drying, the abrasion resistance of the treated support is measured and it is equal to 850.

    Les résultats obtenus s'avèrent supérieurs à ceux pouvant être enregistrés dans les mêmes conditions, avec chacun des agents de finissage appliqués séparément, voire à une concentration relativement plus élevée telle que par exemple 10 g/l de copolymère A ou 10 g/l de produit P1.The results obtained prove to be superior to those that can be registered under the same conditions, with each of the finishing agents applied separately or even at a relatively higher concentration such as for example 10 g / l of copolymer A or 10 g / l of product P1.

    EXEMPLE 24EXAMPLE 24

    On opère dans les conditions identiques à celles de l'exemple 23, mais en utilisant un bain ayant la composition suivante :
       10 g/l d'une solution aqueuse contenant :

  • 25% de copolymère A
  • 75% de produit P2
    • produit P2 : émulsion de polyéthylène oxydé haute densité dont l'extrait sec est de 24%.The operation is carried out under the conditions identical to those of Example 23, but using a bath having the following composition:
    10 g / l of an aqueous solution containing:
  • 25% of copolymer A
  • 75% of P2 product
    • product P2: high density oxidized polyethylene emulsion with a dry extract of 24%.

    Le produit P2 appliqué seul à raison de 10 g/l sur le coton 100% donne une résistance à l'abrasion de 1000.The P2 product applied alone at a rate of 10 g / l on 100% cotton gives an abrasion resistance of 1000.

    Après séchage on mesure la résistance à l'abrasion du support textile traité et on la trouve égale à 1150.After drying, the abrasion resistance of the textile support is measured. treated and we find it equal to 1150.

    Les résultats obtenus s'avèrent supérieurs à ceux pouvant être enregistrés dans les mêmes conditions, avec chacun des agents de finissage appliqués séparément, voire à une concentration relativement plus élevée telle que par exemple 10 g/l de polymère A ou 10 g/l de produit P2.The results obtained prove to be superior to those that can be registered under the same conditions, with each of the finishing agents applied separately or even at a relatively higher concentration such as for example 10 g / l of polymer A or 10 g / l of product P2.

    EXEMPLE 25EXAMPLE 25

    On imprègne un tissu 100% coton azuré optiquement, dans différents bains de foulardage, les tissus sont ensuite exprimés et séchés à 120°C, puis traités thermiquement 1 minute à 180°C.We impregnate an optically azure 100% cotton fabric in different padding baths, the fabrics are then expressed and dried at 120 ° C, then heat treated for 1 minute at 180 ° C.

    On note ensuite le degré de blanc des supports traités.The degree of white of the treated supports is then noted.

    Le produit P3 est une émulsion d'amino-silicone dont l'extrait sec est de 25% en poids.The product P3 is an amino-silicone emulsion whose dry extract is 25% by weight.

    La composition des bains de foulardage et les résultats obtenus sont résumés dans le tableau ci-dessous: Exemple 25 26 27 Témoin copolymère A 20 40 0 produit P3 10 0 degré de blanc après traitement à 180°C, Wl CIE 133,4 133,2 122,6 133,6 The composition of the padding baths and the results obtained are summarized in the table below: Example 25 26 27 Witness copolymer A 20 40 0 product P3 10 0 degree of white after treatment at 180 ° C, Wl CIE 133.4 133.2 122.6 133.6

    Le produit P3 est considéré comme un produit ayant une légère influence sur le degré de blanc. The product P3 is considered to be a product with a slight influence on the degree of white.

    Les résultats ci-dessus permettent de constater que les copolymères de formule (1) appliqués à haute température ne modifient pas le degré de blanc des textiles blancs azurés optiquement ou non.The above results show that the copolymers of formula (1) applied at high temperature does not change the degree of white optically brightened or not white textiles.

    Claims (10)

    Agents de finissage polyvalents pour textiles exempts de liant thermoactivable comprenant des copolymères uréthane-oxyalcoylène de la formule (1) suivante : R[NH―CO―O―(-C2H4-O-)a-(C4H8-O)b―R']y(N=C=O)x dans laquelle R représente une structure aliphatique et/ou aromatique pouvant contenir des groupements biuret, uréthanne ou isocyanurate, R' est choisi parmi l'hydrogène, un radical alcoyle de moins de 8 atomes de carbone à chaíne droite ou à chaíne ramifiée, un radical aryle ou un radical alkylaryle, x est compris entre 0 et 1, y est supérieur à 2, a vaut au moins 1, b vaut au moins 1, la somme (a+b) vaut au moins 5.Multipurpose finishing agents for textiles free from heat-activatable binder comprising urethane-oxyalkylene copolymers of the following formula (1): R [NH ― CO ― O - (- C 2 H 4 -O-) a - (C 4 H 8 -O) b ―R '] y (N = C = O) x in which R represents an aliphatic and / or aromatic structure which may contain biuret, urethane or isocyanurate groups, R 'is chosen from hydrogen, an alkyl radical of less than 8 carbon atoms with a straight chain or with a branched chain, a radical aryl or an alkylaryl radical, x is between 0 and 1, y is greater than 2, a is at least 1, b is at least 1, the sum (a + b) is at least 5. Agents de finissage selon la revendication 1, caractérisés en ce que R représente un radical des formules (2) à (4) suivantes :
    Figure 00150001
    dans laquelle (d) a une valeur comprise entre 2,4 et 2,8 ;
    Figure 00150002
    et
    Figure 00150003
    Finishing agents according to claim 1, characterized in that R represents a radical of the following formulas (2) to (4):
    Figure 00150001
    wherein (d) has a value between 2.4 and 2.8;
    Figure 00150002
    and
    Figure 00150003
         Agents de finissage selon la revendication 1, caractérisés en ce que R' représente un radical méthyle, éthyle, propyle, butyle, isobutyle, 2-éthylhexyle, benzyle, phényle, tolyte, xylyle, octylphényle, nonylphényle ou naphtyle. Finishing agents according to claim 1, characterized in that R 'represents a methyl, ethyl, propyl, butyl, isobutyl, 2-ethylhexyl radical, benzyl, phenyl, tolyte, xylyl, octylphenyl, nonylphenyl or naphthyle. Agents de finissage selon l'une quelconque des revendications 1 à 3, caractérisés en ce que les copolymères de formule (1) sont sous forme d'une solution dans l'eau présentant un extrait sec de 10 à 75% en poids.Finishing agents according to any one of claims 1 to 3, characterized in that the copolymers of formula (1) are in the form of a solution in water with a dry extract of 10 to 75% by weight. Agents de finissage selon la revendication 4, caractérisés en ce que l'extrait sec est de 20 à 30% en poids.Finishing agents according to claim 4, characterized in that the dry extract is 20 to 30% by weight. Agents de finissage selon l'une quelconque des revendications 1 à 5, caractérisés en ce qu'ils sont appliqués par imprégnation dans un bain de foulardage, par impression ou par enduction.Finishing agents according to any one of claims 1 to 5, characterized in that they are applied by impregnation in a bath of padding, printing or coating. Agents de finissage selon l'une quelconque des revendications 1 à 5, caractérisés en ce qu'ils sont utilisés à une concentration de 2,5 à 100 g/litre de bain de foulardage ou de 2,5 à 100 g/kg de pâte d'impression ou de formulation d'enduction.Finishing agents according to any one of claims 1 to 5, characterized in that they are used at a concentration of 2.5 to 100 g / liter of padding bath or 2.5 to 100 g / kg of printing paste or coating formulation. Agents de finissage selon la revendication 7, caractérisés en ce que la concentration est de 5 à 75 g/litre de bain de foulardage.Finishing agents according to claim 7, characterized in that the concentration is from 5 to 75 g / liter of padding bath. Mélanges comprenant un agent de finissage classique, caractérisés en ce qu'ils comprennent en outre un agent de finissage tel que défini à l'une quelconque des revendications 1 à 8.Mixtures comprising a conventional finishing agent, characterized in that they further comprise a finishing agent as defined in one any of claims 1 to 8. Mélanges selon la revendication 9, caractérisés en ce que l'agent de finissage classique est une émulsion de paraffine, de polyéthylène basse densité ou de polyéthylène haute densité.Mixtures according to claim 9, characterized in that the agent classic finishing is an emulsion of paraffin, of low polyethylene density or high density polyethylene.
    EP00400969A 1999-04-07 2000-04-07 Finishing agent for textile comprising urethane-alkylene oxide copolymers Expired - Lifetime EP1043444B1 (en)

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    FR9904323A FR2792009B1 (en) 1999-04-07 1999-04-07 NOVEL VERSATILE FINISHING AGENTS MADE OF URETHANE-OXYALCOYLENE COPOLYMERS AND MIXTURES CONTAINING THEM
    FR9904323 1999-04-07

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    BE831629A (en) * 1974-08-02 1975-11-17 HEAT SENSITIVE LATEX COMPOSITIONS
    US4164535A (en) * 1976-10-19 1979-08-14 Manufacture De Produits Chimiques Protex S.A. Antistatic textile materials
    EP0445077A2 (en) * 1990-03-02 1991-09-04 Ciba-Geigy Ag A method and compositions for textile finishing
    US5692936A (en) * 1992-06-19 1997-12-02 Komatsu Seiven Co., Ltd. Moisture-permeable waterproof fabric and process for producing the same

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    CH389566A (en) * 1961-04-03 1965-07-15 Deering Milliken Res Corp Process for obtaining fabrics provided with a flexible synthetic resin finish
    BE831629A (en) * 1974-08-02 1975-11-17 HEAT SENSITIVE LATEX COMPOSITIONS
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    US4164535A (en) * 1976-10-19 1979-08-14 Manufacture De Produits Chimiques Protex S.A. Antistatic textile materials
    EP0445077A2 (en) * 1990-03-02 1991-09-04 Ciba-Geigy Ag A method and compositions for textile finishing
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    FR2834523A1 (en) * 2002-01-04 2003-07-11 Protex Production of polymer-based treatment agent for improving the antistatic and hydrophilic properties of textiles involves reacting polyisocyanate with ethoxylated fatty amine

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    FR2792009A1 (en) 2000-10-13

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