EP0564346B1 - Finishing of textiles with compositions containing phosphinicosuccinic acid, phosphinicobissuccinic acid or a mixture thereof - Google Patents
Finishing of textiles with compositions containing phosphinicosuccinic acid, phosphinicobissuccinic acid or a mixture thereof Download PDFInfo
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- EP0564346B1 EP0564346B1 EP93400806A EP93400806A EP0564346B1 EP 0564346 B1 EP0564346 B1 EP 0564346B1 EP 93400806 A EP93400806 A EP 93400806A EP 93400806 A EP93400806 A EP 93400806A EP 0564346 B1 EP0564346 B1 EP 0564346B1
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- acid
- phosphinicosuccinic
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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
- D06M13/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment
- D06M13/244—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing sulfur or phosphorus
- D06M13/282—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing sulfur or phosphorus with compounds containing phosphorus
- D06M13/285—Phosphines; Phosphine oxides; Phosphine sulfides; Phosphinic or phosphinous acids or derivatives thereof
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T442/00—Fabric [woven, knitted, or nonwoven textile or cloth, etc.]
- Y10T442/20—Coated or impregnated woven, knit, or nonwoven fabric which is not [a] associated with another preformed layer or fiber layer or, [b] with respect to woven and knit, characterized, respectively, by a particular or differential weave or knit, wherein the coating or impregnation is neither a foamed material nor a free metal or alloy layer
- Y10T442/2369—Coating or impregnation improves elasticity, bendability, resiliency, flexibility, or shape retention of the fabric
- Y10T442/2393—Coating or impregnation provides crease-resistance or wash and wear characteristics
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- Engineering & Computer Science (AREA)
- Textile Engineering (AREA)
- Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
Description
La présente invention concerne un procédé d'apprêtage de textiles cellulosiques, un bain d'apprêtage pour textiles utilisant de l'acide phosphinicosuccinique, de l'acide phosphinicobissuccinique ou leurs mélanges, des textiles cellulosiques apprêtés et l'utilisation desdits acides comme apprêts et comme agents de réticulation de la cellulose.The present invention relates to a process for dressing cellulosic textiles, a dressing bath for textiles using phosphinicosuccinic acid, phosphinicobissuccinic acid or mixtures thereof, prepared cellulosic textiles and the use of said acids as finishes and as cellulose crosslinking agents.
Les apprêts textiles sont actuellement couramment utilisés pour conférer aux tissus cellulosiques des propriétés d'infroissabilité, mais la plupart contiennent du formaldéhyde libre ou combiné, qui se libère soit dans les ateliers d'apprêtage, soit lors de l'utilisation des tissus ainsi apprêtés.Textile finishes are currently commonly used to impart wrinkle-resistant properties to cellulosic fabrics, but most contain free or combined formaldehyde, which is released either in the sizing workshops or when the fabrics so finished are used.
Or, le formaldéhyde est aujourd'hui considéré comme un produit nocif dont certaines réglementations nationales limitent les doses d'exposition à de très faibles valeurs. On recherche donc activement des apprêts textiles exempts de toute trace de formaldéhyde. Au cours de ces recherches, la demanderesse a découvert avec étonnement, que l'acide phosphinicosuccinique (I) et l'acide phosphinicobissuccinique (II) présentent de très intéressantes propriétés de réticulation de la cellulose, justifiant leur utilisation comme apprêt textile.
L'acide phosphinicosuccinique (I) ainsi que l'acide phosphinicobissuccinique (II) sont décrits dans la littérature (brevet des Etats Unis d'Amérique N°5018577). Ils sont notamment obtenus par addition d'un hypophosphite de métal alcalin tel que l'hypophosphite de sodium sur l'acide maléique, un maléate de dialkyle ou l'anhydride maléique suivie, si nécessaire, d'une hydrolyse acide ou basique des fonctions esters, lorsqu'un maléate de dialkyle est utilisé comme produit de départ. Cette réaction d'addition est généralement catalysée avec un dérivé péroxydique minéral tel que le persulfate de sodium, ou organique tel que l'éthyl-2 perhexanoate de tertiobutyle, TBPEH ; elle peut être également effectuée sous un rayonnement ultraviolet au sein de l'acétone (FR-A-2356658, US-A-4138431, US-A-4590014, US-A-4632741, US-A-5023000, US-A-5018577, US-A-4088678 et Beil. IV, 4ème suppl., page 3497, 1959).Phosphinicosuccinic acid (I) as well as phosphinicobissuccinic acid (II) are described in the literature (United States patent No. 5018577). They are especially obtained by adding an alkali metal hypophosphite such as sodium hypophosphite on maleic acid, a dialkyl maleate or maleic anhydride followed, if necessary, by acidic or basic hydrolysis of the ester functions, when a dialkyl maleate is used as the starting product. This addition reaction is generally catalyzed with a mineral peroxide derivative such as sodium persulfate, or organic such as 2-ethyl tert-butyl perhexanoate, TBPEH; it can also be carried out under ultraviolet radiation within acetone (FR-A-2356658, US-A-4138431, US-A-4590014, US-A-4632741, US-A-5023000, US-A- 5018577, US-A-4088678 and Beil. IV, 4th supplement, page 3497, 1959).
US-A-4820307 décrit l'acide maléique comme réticulant possible de textiles cellulosiques en présence d'hypophosphite de sodium comme catalyseur. Au cours du traitement thermique de réticulation, l'acide polycarboxylique forme des anhydrides cycliques qui s'additionnent sur l'hypophosphite de métal alcalin pour donner des acylphosphinates et l'acylphosphinate formé réagit avec la cellulose pour donner des esters réticulés de l'acide carboxylique et régénérer le catalyseur hypophosphite.US-A-4820307 describes maleic acid as a possible crosslinking agent for cellulose textiles in the presence of sodium hypophosphite as catalyst. During the crosslinking heat treatment, the polycarboxylic acid forms cyclic anhydrides which add up on the alkali metal hypophosphite to give acylphosphinates and the acylphosphinate formed reacts with the cellulose to give crosslinked esters of the carboxylic acid. and regenerate the hypophosphite catalyst.
L'acide phosphinicosuccinique (I) et l'acide phosphinicobissuccinique (II), ainsi que leurs mélanges en proportions variables, présentent comme on l'a dit précédemment, de très intéressantes propriétés de réticulation de la cellulose, qui justifient leur application à titre d'apprêts textiles, pour donner aux tissus cellulosiques des propriétés d'infroissabilité.Phosphinicosuccinic acid (I) and phosphinicobissuccinic acid (II), as well as their mixtures in variable proportions, have, as has been said previously, very interesting properties of crosslinking of cellulose, which justify their application as 'textile finishes, to give cellulosic fabrics wrinkle-resistant properties.
La présente invention a donc pour objet un procédé pour apprêter les textiles cellulosiques caractérisé en ce que l'on imprègne le textile cellulosique à traiter à l'aide d'un bain d'apprêtage aqueux comprenant de l'acide phosphinicosuccinique (I), de l'acide phosphinicobissuccinique (II), ou un mélange de ces deux acides. Ce mélange peut être en proportions variables.The subject of the present invention is therefore a process for preparing cellulosic textiles, characterized in that the cellulosic textile to be treated is impregnated using an aqueous finishing bath comprising phosphinicosuccinic acid (I), phosphinicobissuccinic acid (II), or a mixture of these two acids. This mixture can be in variable proportions.
Dans des conditions préférentielles de mise en oeuvre de l'invention, le bain apprêtage des textiles est partiellement neutralisé avec un hydroxyde de métal alcalin afin d'obtenir un bain d'apprêtage aqueux présentant un pH de 2 à 7.Under preferential conditions for implementing the invention, the textile dressing bath is partially neutralized with an alkali metal hydroxide in order to obtain an aqueous finishing bath having a pH of 2 to 7.
Dans d'autres conditions préférentielles, les apprêts ci-dessus décrits sont caractérisés en ce qu'il ne renferment pas de catalyseur, de quelque nature que ce soit.In other preferential conditions, the finishes described above are characterized in that they do not contain catalyst, of any nature whatsoever.
La présente demande a aussi pour objet un bain d'apprêtage pour textiles cellulosiques, caractérisé en ce qu'il comprend une solution aqueuse d'acide phosphinicosuccinique (I), d'acide phosphinicobissuccinique (II), ou de leur mélange, le bain ayant été partiellement neutralisé à pH 2 à 7 à l'aide d'un hydroxyde de métal alcalin, ainsi qu'un agent mouillant, et notamment les bains décrits dans les exemples 3 et 4.The present application also relates to a finishing bath for cellulosic textiles, characterized in that it comprises an aqueous solution of phosphinicosuccinic acid (I), of phosphinicobissuccinic acid (II), or of their mixture, the bath having was partially neutralized at pH 2 to 7 using an alkali metal hydroxide, as well as a wetting agent, and in particular the baths described in examples 3 and 4.
La présente demande a aussi pour objet les textiles cellulosiques apprêtés, caractérisés en ce qu'ils sont obtenus par la mise en oeuvre du procédé ci-dessus décrit.The present application also relates to finished cellulosic textiles, characterized in that they are obtained by the implementation of the process described above.
La présente demande a aussi pour objet l'utilisation, à titre d'apprêt d'un textile cellulosique, de l'acide phosphinicosuccinique (I), de l'acide phosphinicobissuccinique (II), ou d'un de leurs mélanges.The present application also relates to the use, as a finish of a cellulosic textile, of phosphinicosuccinic acid (I), of phosphinicobissuccinic acid (II), or of a mixture thereof.
La présente demande a enfin pour objet l'utilisation de l'acide phosphinicosuccinique (I), de l'acide phosphinicobissuccinique (II) ou de leurs mélanges en proportions variables, à titre d'agents de réticulation de la cellulose contenue notamment dans des fibres textiles, des copeaux de bois, de la sciure de bois.The present application finally relates to the use of phosphinicosuccinic acid (I), phosphinicobissuccinic acid (II) or their mixtures in variable proportions, as crosslinking agents for the cellulose contained in particular in fibers textiles, wood shavings, sawdust.
Les exemples suivants sont donnés à titre indicatif ; ils permettent de mieux comprendre l'invention, mais ils n'en limitent pas la portée. Sauf indications contraires, les parties et pourcentages sont donnés en poids. Le test de défroissabilité est réalisé selon la norme AATCC 66-1972 sur des échantillons tels quels et sur des échantillons soumis à trois lavages ménagers à 60°C ; la défroissabilité est exprimée par la somme des angles de défroissement obtenus en sens chaîne et en sens trame. La résistance à la traction des échantillons exprimée en daN en sens chaîne plus en sens trame est réalisée selon la norme AFNOR G 07.001. Le jaunissement des tissus, réalisé sur un appareil FIXOTEST à 200°C pendant 30 secondes et les blancheurs exprimées en degrés Berger, sont mesurés avec un spectrophotomètre. Le taux de formaldéhyde résiduel sur tissu a été déterminé selon la méthode décrite dans la loi japonaise 112-1973 ; dans les tissus des exemples, on n'a pas pu déceler de formaldéhyde.The following examples are given for information only; they allow a better understanding of the invention, but they do not limit its scope. Unless otherwise indicated, parts and percentages are given by weight. The anti-crease test is carried out according to the AATCC 66-1972 standard on samples as they are and on samples subjected to three household washes at 60 ° C; the wrinkle resistance is expressed by the sum of the wrinkle angles obtained in warp and weft direction. The tensile strength of the samples expressed in daN in the warp direction plus in the weft direction is produced according to standard AFNOR G 07.001. The yellowing of the tissues, carried out on a FIXOTEST device at 200 ° C for 30 seconds and the whiteness expressed in Berger degrees, are measured with a spectrophotometer. The residual formaldehyde level on tissue was determined according to the method described in Japanese law 112-1973; in the fabrics of the examples, no formaldehyde could be detected.
On introduit goutte à goutte, en 150 minutes, sous agitation, une solution constituée par :
- 150 g (1 mole) de maléate de diméthyle à 96%,
- 2 g (9,2 mmoles) d'éthyl-2 perhexanoate de tertiobutyle,
- 99 g d'éthanol absolu,
- 44 g (0,485 mole) d'hypophosphite de sodium à 97%,
- 60 g d'eau distillée,
- 99 g d'éthanol absolu,
- 150 g (1 mole) of 96% dimethyl maleate,
- 2 g (9.2 mmol) of 2-ethyl tert-butyl perhexanoate,
- 99 g of absolute ethanol,
- 44 g (0.485 mole) 97% sodium hypophosphite,
- 60 g of distilled water,
- 99 g of absolute ethanol,
Ce produit est ensuite chauffé à l'ébullition dans 555 g d'eau distillée et 216 g d'acide chlorhydrique concentré, d = 1,19, tout en éliminant le méthanol formé par distillation. Après 5 heures de chauffage, il n'y a plus de formation de méthanol, le milieu réactionnel est alors concentré à sec, sous pression réduite. On obtient ainsi 185 g d'une pâte visqueuse que l'on dissout à chaud dans 350 g d'acide acétique. La solution chaude ainsi obtenue est traitée avec 1 g de charbon actif, puis elle est filtrée et ensuite concentrée à sec sous pression réduite. On obtient ainsi 143,7 g d'un produit cristallisé blanc, soit un rendement de 99,4% de la théorie calculée par rapport à l'hypophosphite de sodium mis en oeuvre. Ce produit, dosé par potentiométrie, contient 15,49 meq/g de fonctions acides dont 2,756 meq/g de fonctions acides fortes, soit un rapport entre fonction acide carboxylique et fonction acide phosphinique de 4,62:1 (théorie 4:1).This product is then heated to boiling in 555 g of distilled water and 216 g of concentrated hydrochloric acid, d = 1.19, while removing the methanol formed by distillation. After 5 hours of heating, there is no more methanol formation, the reaction medium is then concentrated to dryness, under reduced pressure. 185 g of a viscous paste are thus obtained which are dissolved hot in 350 g of acetic acid. The hot solution thus obtained is treated with 1 g of activated carbon, then it is filtered and then concentrated to dryness under reduced pressure. 143.7 g of a white crystallized product are thus obtained, ie a yield of 99.4% of the theory calculated relative to the sodium hypophosphite used. This product, dosed by potentiometry, contains 15.49 meq / g of acid functions, of which 2.756 meq / g of strong acid functions, or a ratio between carboxylic acid function and phosphinic acid function of 4.62: 1 (theory 4: 1).
Ces contrôles montrent que la fonction acide phosphinique est partiellement salifiée avec du sodium. Ce produit est alors traité en solution dans 1 kg d'eau distillée à la température ambiante, pendant 1 heure, avec 350 ml d'une résine échangeuse de cations sous forme acide, présentant une capacité totale d'échange de 1,4 meq par ml, puis la suspension est filtré et le filtrat est concentré à sec sous pression réduite. On obtient ainsi 135 g de produit cristallisé blanc contenant 16,28 meq/g de fonctions acides (théorie 16,77 meq/g) dont 3,39 meq/g de fonctions acides présentant un pk inférieur ou égal à 1,6 (théorie 3, 35). Ce produit contient environ 97% d'acide phosphinicobissuccinique (II), il est utilisé sous cette forme en application sous la référence A ; RMN13C(D2O), 25 MHz, γ 32,1 (s, CH2), γ 32,9 (s, CH2), γ 45,7 (d, J = 82 Hz, CH), γ 175 (2d, J = 4 Hz, CH-COOH), γ 177,4 (dd, J = 16 Hz, CH2-COOH).These checks show that the phosphinic acid function is partially salified with sodium. This product is then treated in solution in 1 kg of distilled water at room temperature, for 1 hour, with 350 ml of a cation exchange resin in acid form, having a total exchange capacity of 1.4 meq per ml, then the suspension is filtered and the filtrate is concentrated to dryness under reduced pressure. 135 g of white crystallized product are thus obtained containing 16.28 meq / g of acid functions (theory 16.77 meq / g) of which 3.39 meq / g of acid functions having a pk less than or equal to 1.6 (theory 3, 35). This product contains approximately 97% phosphinicobissuccinic acid (II), it is used in this form in application under the reference A; 13 C NMR (D 2 O), 25 MHz, γ 32.1 (s, CH 2 ), γ 32.9 (s, CH 2 ), γ 45.7 (d, J = 82 Hz, CH), γ 175 (2d, J = 4 Hz, CH- C OOH), γ 177.4 (dd, J = 16 Hz, CH 2 - C OOH).
On introduit goutte à goutte, sous agitation, une solution constituée par :
- 75 g (500 mmoles) de maléate de diméthyle à 96%,
- 2 g (9,2 mmoles) d'éthyl-2 perhexanoate de tertiobutyle,
- 99 d'éthanol absolu,
- 59 g d'eau distillée,
- 44 g (485 mmoles) d'hypophosphite de sodium à 97%,
- 99 g d'éthanol absolu,
- 75 g (500 mmol) of 96% dimethyl maleate,
- 2 g (9.2 mmol) of 2-ethyl tert-butyl perhexanoate,
- 99 of absolute ethanol,
- 59 g of distilled water,
- 44 g (485 mmol) 97% sodium hypophosphite,
- 99 g of absolute ethanol,
On imprègne au foulard un tissu de popeline 100% coton, débouilli et blanchi, d'un poids d'environ 130 g par mètre carré avec un taux d'exprimage de 75% dans un bain aqueux dont le pH a été ajusté avec de la soude à la valeur indiquée dans le tableau I, contenant en solution les quantités d'acide, ainsi que 2 g par litre de nonylphénol éthoxylé avec 10 moles d'oxyde d'éthylène comme agent mouillant. Le tissu est ensuite séché pendant 45 secondes à 120°C, puis il est soumis sur une rame de laboratoire à un traitement thermique de 90 secondes à 180°C.A 100% cotton poplin fabric, scalded and bleached, is impregnated with the scarf, weighing approximately 130 g per square meter with an expressing rate of 75% in an aqueous bath, the pH of which has been adjusted with soda at the value indicated in table I, containing in solution the amounts of acid, as well as 2 g per liter of ethoxylated nonylphenol with 10 moles of ethylene oxide as wetting agent. The fabric is then dried for 45 seconds at 120 ° C, then it is subjected on a laboratory oar to a heat treatment for 90 seconds at 180 ° C.
On détermine ensuite sur des échantillons du tissu traité après conditionnement :
- la défroissabilité sur des échantillons tels quels et sur des échantillons soumis à trois lavages ménagers à 60°C,
- la résistance à la traction, désignée Rt, exprimée en daN,
- la blancheur, désignée Bl, exprimée en degrés Berger,
- le jaunissement, désigné Ja,
- wrinkle resistance on samples as is and on samples subjected to three household washes at 60 ° C,
- the tensile strength, designated Rt, expressed in daN,
- whiteness, designated Bl, expressed in Berger degrees,
- yellowing, designated Ja,
L'exemple de comparaison C1 correspond au tissu non traité.Comparison example C1 corresponds to the untreated tissue.
On constate que les produits selon la présente invention améliorent considérablement les qualités d'infroissabilité des tissus traités même après lavage, sans pour autant abaisser trop nettement leur résistance à la traction.It is found that the products according to the present invention considerably improve the wrinkle-resistant qualities of the treated fabrics even after washing, without however reducing their tensile strength too clearly.
On mélange sous agitation, à la température ambiante, 625 g d'eau distillée, et 490,3 g (5 moles) d'anhydride maléique. La suspension obtenue est chauffée à 60°c jusqu'à l'obtention d'une solution. On introduit alors 220 g (2,5 moles) d'hypophosphite de sodium, puis en 5 heures, en maintenant l'agitation et la température à 60°C, une solution de 45,2 g (0,19 mole) de persulfate de sodium dans 78 g d'eau distillée. L'introduction terminée, on maintient la solution réactionnelle deux heures à 60°C puis on la refroidit à la température ambiante.625 g of distilled water and 490.3 g (5 moles) of maleic anhydride are mixed with stirring at room temperature. The suspension obtained is heated to 60 ° C. until a solution is obtained. Then introduced 220 g (2.5 moles) of sodium hypophosphite, then in 5 hours, maintaining stirring and the temperature at 60 ° C, a solution of 45.2 g (0.19 mole) of persulfate sodium in 78 g of distilled water. When the introduction is complete, the reaction solution is kept for two hours at 60 ° C. and then cooled to ambient temperature.
On obtient ainsi 1435 g d'une solution aqueuse limpide, légèrement colorée, contenant environ 2,5 moles d'acide phophinicobissuccinique monosodique, présentant une acidité de 7,0 meq/g (théorie 6,97 meq/g)et ne contenant plus d'anhydride maléique. Cette solution, désignée D, est utilisée sous cette forme dans l'exemple 8.1435 g of a clear, slightly colored aqueous solution are thus obtained, containing approximately 2.5 moles of phosinicobissuccinic acid monosodium, having an acidity of 7.0 meq / g (theory 6.97 meq / g) and no longer containing maleic anhydride. This solution, designated D, is used in this form in Example 8.
On reproduit l'exemple 5 en remplaçant le persulfate de sodium par une quantité équivalente de persulfate d'ammonium. On obtient ainsi environ 1464 g d'une solution aqueuse, limpide, incolore, contenant environ 2,5 moles d'acide phosphinicobissuccinique monosodique, présentant une acidité de 6,96 meq/g (théorie 6,83 meq/g) et ne contenant plus d'anhydride maléique déterminée par l'analyse RMN du proton et du carbone treize. Cette solution désignée E, est utilisée sous cette forme dans l'exemple 9.Example 5 is repeated, replacing the sodium persulfate with an equivalent quantity of ammonium persulfate. This gives about 1464 g of a clear, colorless aqueous solution containing about 2.5 moles of phosphinicobissuccinic acid monosodium, having an acidity of 6.96 meq / g (theory 6.83 meq / g) and no longer containing maleic anhydride determined by NMR analysis of the proton and carbon thirteen. This solution, designated E, is used in this form in Example 9.
On mélange sous agitation, à la température ambiante, 763 g d'eau distillée et 327,5 g (3,34 moles) d'anhydride maléique. La suspension obtenue est ensuite chauffée à 60°C jusqu'à l'obtention d'une solution. En maintenant l'agitation et la température de la solution à 60°C, on introduit en 3 heures, séparément et simultanément, d'une part une solution de 28,6 g (0,12 mole) de persulfate de sodium dans 52 g d'eau distillée, et d'autre part, une solution de 147 g (1,67 mole) d'hypophosphite de sodium dissous dans 300 g d'eau distillée. Les introductions terminées, on abandonne la solution réactionnelle deux heures à 60°C.763 g of distilled water and 327.5 g (3.34 moles) of maleic anhydride are mixed with stirring at room temperature. The suspension obtained is then heated to 60 ° C until a solution is obtained. Maintaining the stirring and the temperature of the solution at 60 ° C., a solution of 28.6 g (0.12 mole) of sodium persulfate in 52 g is introduced over 3 hours, separately and simultaneously distilled water, and on the other hand, a solution of 147 g (1.67 mole) of sodium hypophosphite dissolved in 300 g of distilled water. Once the introductions are complete, the reaction solution is left for two hours at 60 ° C.
Après refroidissement à la température ambiante, on obtient environ 1618 g environ d'une solution aqueuse limpide et incolore, contenant environ 1,67 mole d'acide phosphinicobissuccinique monosodique et ne contenant plus d'anhydride maléique, déterminée par analyses RMN du proton et du carbone treize. Cette solution présente une acidité de 4,11 meq/g (théorie 4,13 meq/g). Cette solution, désignée F, est utilisée sous cette forme dans l'exemple 10.
Claims (10)
- Process for finishing a cellulose textile characterized in that the cellulose textile to be treated is impregnated with an aqueous finishing bath containing phosphinicosuccinic acid (I), phosphinicobisuccinic acid (II) or a mixture of phosphinicosuccinic acid (I) and phosphinicobisuccinic acid (II).
- Process according to claim 1, characterized in that the finishing bath has a pH of 2 to 7 obtained with an alkali metal hydroxide.
- Process according to any one of claims 1 or 2, characterized in that the finishing bath does not contain a catalyst.
- Finishing bath for textiles, characterized in that it contains an aqueous solution of phosphinicosuccinic acid (I), phosphinicobisuccinic acid (II), or their mixture, the bath having been partially neutralized to pH 2 to 7 with an alkali metal hydroxide, as well as a wetting agent.
- Finishing bath according to calim 4, characterized in that the wetting agent is a nonylphenol ethoxylated with 10 moles of ethylene oxide.
- Finished cellulose textile, characterized in that it is obtained by implementing the process of the invention according to claim 1, 2 or 3.
- Use of phosphinicosuccinic acid (I) as a finish for cellulose textiles.
- Use of phosphinicobisuccinic acid (II) as a finish for cellulose textiles.
- Use of a phosphinicosuccinic acid (I) and phosphinicobisuccinic acid (II) mixture as a finish for cellulose textiles.
- Use as cross-linking agents for cellulose, of phosphinicosuccinic acid (I), phosphinicobisuccinic acid (II) or a mixture of phosphinicosuccinic acid (I) and phosphinicobisuccinic acid (II).
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
FR9204076A FR2689529B1 (en) | 1992-04-03 | 1992-04-03 | TEXTILE PRIMING PROCESS, TEXTILE PRIMING BATH USING PHOSPHINICOSUCCINIC ACID, PHOSPHINICOBISUCCINIC ACID OR THEIR MIXTURES. |
FR9204076 | 1992-04-03 |
Publications (2)
Publication Number | Publication Date |
---|---|
EP0564346A1 EP0564346A1 (en) | 1993-10-06 |
EP0564346B1 true EP0564346B1 (en) | 1997-01-15 |
Family
ID=9428441
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP93400806A Expired - Lifetime EP0564346B1 (en) | 1992-04-03 | 1993-03-29 | Finishing of textiles with compositions containing phosphinicosuccinic acid, phosphinicobissuccinic acid or a mixture thereof |
Country Status (12)
Country | Link |
---|---|
US (2) | US5300240A (en) |
EP (1) | EP0564346B1 (en) |
JP (1) | JP3217894B2 (en) |
KR (1) | KR100257986B1 (en) |
AT (1) | ATE147805T1 (en) |
CA (1) | CA2091656A1 (en) |
DE (1) | DE69307375T2 (en) |
DK (1) | DK0564346T3 (en) |
ES (1) | ES2096235T3 (en) |
FR (1) | FR2689529B1 (en) |
GR (1) | GR3022662T3 (en) |
TR (1) | TR26711A (en) |
Cited By (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US6841198B2 (en) | 2001-10-18 | 2005-01-11 | Strike Investments, Llc | Durable press treatment of fabric |
US6989035B2 (en) | 2001-10-18 | 2006-01-24 | The Procter & Gamble Company | Textile finishing composition and methods for using same |
US7008457B2 (en) | 2001-10-18 | 2006-03-07 | Mark Robert Sivik | Textile finishing composition and methods for using same |
US7018422B2 (en) | 2001-10-18 | 2006-03-28 | Robb Richard Gardner | Shrink resistant and wrinkle free textiles |
US7144431B2 (en) | 2001-10-18 | 2006-12-05 | The Procter & Gamble Company | Textile finishing composition and methods for using same |
US7169742B2 (en) | 2001-10-18 | 2007-01-30 | The Procter & Gamble Company | Process for the manufacture of polycarboxylic acids using phosphorous containing reducing agents |
Families Citing this family (18)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
FR2689529B1 (en) * | 1992-04-03 | 1995-06-23 | Hoechst France | TEXTILE PRIMING PROCESS, TEXTILE PRIMING BATH USING PHOSPHINICOSUCCINIC ACID, PHOSPHINICOBISUCCINIC ACID OR THEIR MIXTURES. |
US5496477A (en) * | 1992-12-21 | 1996-03-05 | Ppg Industries, Inc. | Non-formaldehyde durable press finishing for cellulosic textiles with phosphinocarboxylic acid |
US5496476A (en) * | 1992-12-21 | 1996-03-05 | Ppg Indutstries, Inc. | Non-formaldehyde durable press finishing for cellulosic textiles with phosphonoalkylpolycarboxylic acid |
FR2781821B1 (en) | 1998-07-31 | 2000-11-10 | Clariant France Sa | PROCESS FOR PRIMING A TEXTILE AND PRIMING BATHS |
US7169293B2 (en) * | 1999-08-20 | 2007-01-30 | Uop Llc | Controllable space velocity reactor and process |
US6585780B2 (en) | 2000-01-14 | 2003-07-01 | Rhodia Inc. | Crosslinking agents for textile finishing baths and process for using same |
JP2008504459A (en) * | 2004-06-24 | 2008-02-14 | ダウ グローバル テクノロジーズ インコーポレイティド | Stretchable fiber with wrinkle resistance |
JP4248466B2 (en) * | 2004-09-03 | 2009-04-02 | 株式会社島精機製作所 | Textile dyeing method |
JP2006316372A (en) * | 2005-05-11 | 2006-11-24 | Tokai Senko Kk | Method for carrying out preventive processing of discoloration of cellulosic fiber by washing |
TW200835742A (en) * | 2006-11-30 | 2008-09-01 | Dow Global Technologies Inc | Olefin block compositions for stretch fabrics with wrinkle resistance |
US9752105B2 (en) | 2012-09-13 | 2017-09-05 | Ecolab Usa Inc. | Two step method of cleaning, sanitizing, and rinsing a surface |
US8748365B2 (en) | 2012-09-13 | 2014-06-10 | Ecolab Usa Inc. | Solidification matrix comprising phosphinosuccinic acid derivatives |
US9023784B2 (en) | 2012-09-13 | 2015-05-05 | Ecolab Usa Inc. | Method of reducing soil redeposition on a hard surface using phosphinosuccinic acid adducts |
US9994799B2 (en) | 2012-09-13 | 2018-06-12 | Ecolab Usa Inc. | Hard surface cleaning compositions comprising phosphinosuccinic acid adducts and methods of use |
US8871699B2 (en) | 2012-09-13 | 2014-10-28 | Ecolab Usa Inc. | Detergent composition comprising phosphinosuccinic acid adducts and methods of use |
US20140308162A1 (en) | 2013-04-15 | 2014-10-16 | Ecolab Usa Inc. | Peroxycarboxylic acid based sanitizing rinse additives for use in ware washing |
US11149202B1 (en) | 2016-12-13 | 2021-10-19 | Ecolab Usa Inc. | Tetracarboxylic acid combinations for corrosion inhibition |
CN109137526B (en) * | 2018-08-30 | 2021-01-29 | 常州大学 | Preparation method and application of formaldehyde-free crease-resistant finishing agent |
Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4088678A (en) * | 1976-07-01 | 1978-05-09 | Nalco Chemical Company | Substituted succinic acid compounds and their use as chelants |
US4820307A (en) * | 1988-06-16 | 1989-04-11 | The United States Of America As Represented By The Secretary Of Agriculture | Catalysts and processes for formaldehyde-free durable press finishing of cotton textiles with polycarboxylic acids |
US5018577A (en) * | 1990-08-02 | 1991-05-28 | Nalco Chemical Company | Phosphinate inhibitor for scale squeeze applications |
US5023000A (en) * | 1990-05-10 | 1991-06-11 | Nalco Chemical Company | Oligomer-containing phosphate scale inhibitors |
Family Cites Families (10)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3300337A (en) * | 1960-10-06 | 1967-01-24 | Stauffer Chemical Co | Anti-static coated textile fiber |
US3535073A (en) * | 1967-10-25 | 1970-10-20 | Us Agriculture | Crosslinking cotton with haloalkyl phosphine oxides |
US3979533A (en) * | 1972-12-04 | 1976-09-07 | The United States Of America As Represented By The Secretary Of Agriculture | α,α'-Bis-(phosphono)dicarboxylic acid derivatives |
US4138431A (en) * | 1978-06-29 | 1979-02-06 | Nalco Chemical Company | Reaction of α-phosphorus containing carboxylic acids with phosphorous acid to prepare scale and corrosion inhibitors |
SE451857B (en) * | 1980-03-14 | 1987-11-02 | Wool Dev Int | KEEP FLAME PROTECTING KERATE CONTENT TEXTILE PRODUCTS |
US4590014A (en) * | 1984-09-06 | 1986-05-20 | Economics Laboratory, Inc. | Synthesis of alkyl phosphinate salts |
US4632741A (en) * | 1984-09-06 | 1986-12-30 | Economics Laboratory, Inc. | Synthesis of alkyl phosphinate salts and bis(alkyl) phosphinate salts |
US4936865A (en) * | 1988-06-16 | 1990-06-26 | The United States Of America As Represented By The Secretary Of Agriculture | Catalysts and processes for formaldehyde-free durable press finishing of cotton textiles with polycarboxylic acids |
FR2668506B1 (en) * | 1990-10-30 | 1993-02-12 | Hoechst France | APPLICATIONS OF DERIVATIVES OF ALKANEPOLYCARBOXYLIC ACIDS AS CELLULOSE CROSSLINKING AGENTS, NEW DERIVATIVES AND TEXTILE PRIMERS. |
FR2689529B1 (en) * | 1992-04-03 | 1995-06-23 | Hoechst France | TEXTILE PRIMING PROCESS, TEXTILE PRIMING BATH USING PHOSPHINICOSUCCINIC ACID, PHOSPHINICOBISUCCINIC ACID OR THEIR MIXTURES. |
-
1992
- 1992-04-03 FR FR9204076A patent/FR2689529B1/en not_active Expired - Fee Related
-
1993
- 1993-03-15 CA CA002091656A patent/CA2091656A1/en not_active Abandoned
- 1993-03-29 AT AT93400806T patent/ATE147805T1/en active
- 1993-03-29 EP EP93400806A patent/EP0564346B1/en not_active Expired - Lifetime
- 1993-03-29 ES ES93400806T patent/ES2096235T3/en not_active Expired - Lifetime
- 1993-03-29 DE DE69307375T patent/DE69307375T2/en not_active Expired - Lifetime
- 1993-03-29 DK DK93400806.1T patent/DK0564346T3/en active
- 1993-04-01 TR TR93/0260A patent/TR26711A/en unknown
- 1993-04-02 US US08/041,463 patent/US5300240A/en not_active Expired - Lifetime
- 1993-04-02 JP JP10017593A patent/JP3217894B2/en not_active Expired - Fee Related
-
1994
- 1994-01-24 US US08/185,149 patent/US5385680A/en not_active Expired - Lifetime
-
1997
- 1997-02-26 GR GR970400349T patent/GR3022662T3/en unknown
-
1998
- 1998-03-31 KR KR1019980032558A patent/KR100257986B1/en not_active IP Right Cessation
Patent Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4088678A (en) * | 1976-07-01 | 1978-05-09 | Nalco Chemical Company | Substituted succinic acid compounds and their use as chelants |
US4820307A (en) * | 1988-06-16 | 1989-04-11 | The United States Of America As Represented By The Secretary Of Agriculture | Catalysts and processes for formaldehyde-free durable press finishing of cotton textiles with polycarboxylic acids |
US5023000A (en) * | 1990-05-10 | 1991-06-11 | Nalco Chemical Company | Oligomer-containing phosphate scale inhibitors |
US5018577A (en) * | 1990-08-02 | 1991-05-28 | Nalco Chemical Company | Phosphinate inhibitor for scale squeeze applications |
Cited By (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US6841198B2 (en) | 2001-10-18 | 2005-01-11 | Strike Investments, Llc | Durable press treatment of fabric |
US6989035B2 (en) | 2001-10-18 | 2006-01-24 | The Procter & Gamble Company | Textile finishing composition and methods for using same |
US7008457B2 (en) | 2001-10-18 | 2006-03-07 | Mark Robert Sivik | Textile finishing composition and methods for using same |
US7018422B2 (en) | 2001-10-18 | 2006-03-28 | Robb Richard Gardner | Shrink resistant and wrinkle free textiles |
US7144431B2 (en) | 2001-10-18 | 2006-12-05 | The Procter & Gamble Company | Textile finishing composition and methods for using same |
US7169742B2 (en) | 2001-10-18 | 2007-01-30 | The Procter & Gamble Company | Process for the manufacture of polycarboxylic acids using phosphorous containing reducing agents |
US7247172B2 (en) | 2001-10-18 | 2007-07-24 | The Procter & Gamble Company | Shrink resistant and wrinkle free textiles |
Also Published As
Publication number | Publication date |
---|---|
GR3022662T3 (en) | 1997-05-31 |
KR100257986B1 (en) | 2000-06-01 |
JPH0633374A (en) | 1994-02-08 |
FR2689529B1 (en) | 1995-06-23 |
JP3217894B2 (en) | 2001-10-15 |
ATE147805T1 (en) | 1997-02-15 |
EP0564346A1 (en) | 1993-10-06 |
TR26711A (en) | 1995-05-15 |
US5385680A (en) | 1995-01-31 |
DE69307375T2 (en) | 1997-05-15 |
DE69307375D1 (en) | 1997-02-27 |
KR930021876A (en) | 1993-11-23 |
FR2689529A1 (en) | 1993-10-08 |
CA2091656A1 (en) | 1993-10-04 |
US5300240A (en) | 1994-04-05 |
DK0564346T3 (en) | 1997-07-07 |
ES2096235T3 (en) | 1997-03-01 |
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