EP0569266A1 - Application of diesters of polyalkylene glycols as formaldehyde scavengers and process of finishing the textile industry - Google Patents

Application of diesters of polyalkylene glycols as formaldehyde scavengers and process of finishing the textile industry Download PDF

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Publication number
EP0569266A1
EP0569266A1 EP93401048A EP93401048A EP0569266A1 EP 0569266 A1 EP0569266 A1 EP 0569266A1 EP 93401048 A EP93401048 A EP 93401048A EP 93401048 A EP93401048 A EP 93401048A EP 0569266 A1 EP0569266 A1 EP 0569266A1
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Prior art keywords
formaldehyde
equal
finishing
acetoacetate
hydrogen atom
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EP93401048A
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German (de)
French (fr)
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EP0569266B1 (en
Inventor
Didier Wilhelm
Antonio Gelabert
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Sanofi Aventis France
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Francaise Hoechst Ste
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Classifications

    • 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
    • D06M13/10—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 oxygen
    • D06M13/224—Esters of carboxylic acids; Esters of carbonic acid
    • 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
    • D06M13/10—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 oxygen
    • D06M13/165—Ethers
    • 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
    • D06M13/10—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 oxygen
    • D06M13/165—Ethers
    • D06M13/17—Polyoxyalkyleneglycol ethers
    • 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
    • D06M15/39—Aldehyde resins; Ketone resins; Polyacetals
    • D06M15/423—Amino-aldehyde resins
    • 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
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/29—Coated or structually defined flake, particle, cell, strand, strand portion, rod, filament, macroscopic fiber or mass thereof
    • Y10T428/2913—Rod, strand, filament or fiber
    • Y10T428/2915—Rod, strand, filament or fiber including textile, cloth or fabric
    • 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
    • Y10T442/2508—Coating or impregnation absorbs chemical material other than water
    • 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
    • Y10T442/2762—Coated or impregnated natural fiber fabric [e.g., cotton, wool, silk, linen, etc.]
    • Y10T442/277—Coated or impregnated cellulosic fiber fabric

Definitions

  • the present invention relates to the application of polyalkylene glycol diesters as formaldehyde sensors and to a finishing process for the textile industry.
  • Formaldehyde is widely used in the preparation of various aminoplast resins, in particular for obtaining resins intended for the finishing of textile fibers such as urea-glyoxal-formaldehyde resins. Despite the care taken in their preparation, these resins very often contain weak traces of formaldehyde and, under certain conditions, especially when applied to fabrics, they release formaldehyde. However, formaldehyde is a pungent, very penetrating, unpleasant odor gas; we therefore sought very early various means to fix it and / or limit its release.
  • R represents an acetoacetyl or dioxo-3,5 hexanoyl group
  • R1 represents a hydrogen atom or a methyl radical
  • m is equal to 1, 2, 3 or 4
  • n is either equal to 1 when R1 represents a methyl radical, or equal to 1, 2, 3 when R1 represents a hydrogen atom, as formaldehyde captors.
  • a more particular subject of the invention is the use, as formaldehyde sensors, of products as defined above, characterized in that in the formula (I), R and R1 have the meaning given above, n is equal to 1 and m is equal to 1 or 2.
  • the diesters of ethylene glycol, diethylene glycol, and 1,4-butanediol with acetoacetic acid are known: Beil.III, 4th supplement, page 1543 and TRPATTERSON et al, J. Amer.Chem. Soc., 1959, 81 , 4213-17. They can be prepared in particular according to the methods described by RJ CLEMENS, Chem. Rev., 1986, 86 , 250 and J. Org.chem., 1985, 50 , 2431-35.
  • polyalkylene glycol diesters of general formula (II) in which R1, m and n have the meaning given above, with acetylacetic acids and 3,5-dioxohexanoic acid can be obtained by transesterification either of ethyl acetoacetate or of 3,5-Dioxo ethyl hexanoate with the polyalkylene glycol of formula (II) corresponding according to the method cited by TRPATTERSON et al (loc. cited).
  • the products of formula (I) have very interesting properties as formaldehyde scavengers, and in particular, they make it possible to very considerably lower the doses of free formaldehyde present and / or released by the tissues based of cellulose fibers, prepared with aminoplast resins containing in the free or combined state formaldehyde.
  • the present application also relates to a process for finishing fabrics based on cellulosic fibers by means of an aminoplast resin containing in the free or combined state formaldehyde in which the fabrics are placed in a bath. finishing, characterized in that in said finishing bath, as formaldehyde sensors, a product of formula (I) as defined above, in particular ethylene bis (acetoacetate) or oxidiethylene bis (acetoacetate).
  • the wrinkle test is carried out according to the AATCC 66-1972 standard, the wrinkle is expressed by the sum of the wrinkling angles obtained in warp and weft direction.
  • the tensile strength of the samples, expressed in daN, in warp direction plus in weft direction is produced according to standard AFNOR G 07.001.
  • the yellowing of the tissues, carried out on a FIXOTEST device at 185 ° C for 30 seconds and the whiteness, expressed in Berger degree, are measured with a spectrophotometer.
  • the ethylene bis (acetoacetate) was prepared according to T.R. PATTERSON et al (loc. Cited). 11 is in the form of a liquid having a boiling point under 0.7 mbar of 150-152 ° C.
  • Oxydethylene bis (acetoacetate) was also prepared according to T.R. PATTERSON et al. It is in the form of a liquid having a boiling point at 1.2 mbar of 178-180 ° C.
  • the fabric is then dried for 45 seconds at 120 ° C, then it is subjected on a laboratory oar to a heat treatment for 35 seconds at 180 ° C.
  • Example 1 is reproduced by replacing the bis (acetoacetate) of ethylene with 200 mmol per liter of bath of 2-hydroxyethyl acetoacetate prepared according to Example 1 of PCT patent application WO88 / 09323 (Example C1 ).
  • Example 1 is reproduced by replacing the bis (acetoacetate) of ethylene with 200 mmol per liter of di (2-hydroxyethoxyethyl) malonate prepared according to Example 2 of PCT patent application WO88 / 09323 (example C2).

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  • Engineering & Computer Science (AREA)
  • Textile Engineering (AREA)
  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
  • Phenolic Resins Or Amino Resins (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

Use, as formaldehyde scavengers, of products of formula (I> R-O-CHR1-(CH2)n-O-m-R (I> in which R denotes an acetoacetyl or 3,5-dioxohexanoyl group, R1 denotes a hydrogen atom or a methyl radical, m is equal to 1, 2, 3 or 4 and n is either equal to 1 when R1 denotes a methyl radical or equal to 1, 2 or 3 when R1 denotes a hydrogen atom, and process for finishing fabrics based on cellulose fibres by means of an aminoplastic resin containing formaldehyde in the free or combined state, using a product of formula I as formaldehyde scavenger.

Description

La présente invention concerne l'application de diesters de polyalcoylèneglycols à titre de capteurs de formaldéhyde et un procédé d'ennoblissement pour l'industrie textile.The present invention relates to the application of polyalkylene glycol diesters as formaldehyde sensors and to a finishing process for the textile industry.

Le formaldéhyde est largement utilisé dans la préparation de résines aminoplastes diverses, notamment pour l'obtention de résines destinées à l'ennoblissement des fibres textiles telles que les résines urées-glyoxal-formaldéhyde. Malgré le soin apporté à leur préparation, ces résines contiennent très souvent de faibles traces de formaldéhyde et, sous certaines conditions, notamment lors de leur application sur les tissus, elles libèrent du formaldéhyde. Or, le formaldéhyde est un gaz d'odeur piquante, très pénétrante, peu agréable ; aussi a-t-on cherché très tôt divers moyens pour le fixer et/ou limiter son dégagement. Ainsi, comme capteur de formaldéhyde, il a été proposé divers carbonylés possédant en position alpha un groupe méthyle ou méthylène tels que l'acétaldéhyde, l'acétone, l'acétylacétone, des esters éther de l'acide acétylacétique et même plus généralement des composés de méthylène actif comme les nitroalcanes, les malonates de dialcanol (brevet français N° 989465 et 2575754, demande de brevet européen N° 2596, brevet anglais N° 2058099, brevet polonais N° 72885, demande de brevet japonais N° 73-17755, demande de brevet PCT N° WO88/09323 et C.TOMASINO et al, Textile Chemists and Colorists, 1984, 16, (12), 33-38).Formaldehyde is widely used in the preparation of various aminoplast resins, in particular for obtaining resins intended for the finishing of textile fibers such as urea-glyoxal-formaldehyde resins. Despite the care taken in their preparation, these resins very often contain weak traces of formaldehyde and, under certain conditions, especially when applied to fabrics, they release formaldehyde. However, formaldehyde is a pungent, very penetrating, unpleasant odor gas; we therefore sought very early various means to fix it and / or limit its release. Thus, as a formaldehyde sensor, various carbonyls have been proposed which, in the alpha position, have a methyl or methylene group such as acetaldehyde, acetone, acetylacetone, ether esters of acetylacetic acid and even more generally compounds active methylene such as nitroalkanes, dialcanol malonates (French patent N ° 989465 and 2575754, European patent application N ° 2596, English patent N ° 2058099, Polish patent N ° 72885, Japanese patent application N ° 73-17755, PCT patent application No. WO88 / 09323 and C. TOMASINO et al, Textile Chemists and Colorists, 1984, 16 , (12), 33-38).

Toutefois, ces divers produits quoique actifs, ne donnent pas entière satisfaction à l'homme du métier.However, these various products, although active, do not give complete satisfaction to those skilled in the art.

Or, la demanderesse a découvert avec étonnement que certains diesters des polyalcoylèneglycols avec l'acide di- ou triacétique présentent d'excellentes propriétés pour capter le formaldéhyde présent dans les tissus à base de fibres cellulosiques ennoblis avec des résines aminoplastes contenant à l'état libre ou combiné du formaldéhyde.Now, the applicant has discovered with astonishment that certain diesters of polyalkylene glycols with di- or triacetic acid have excellent properties for capturing the formaldehyde present in tissues based on cellulosic fibers ennobled with aminoplast resins containing in the free state or combined formaldehyde.

C'est pourquoi la présente invention a pour objet l'utilisation des produits de formule (I)

Figure imgb0001

dans laquelle R représente un groupement acétoacétyle ou dioxo-3,5 hexanoyle, R₁ représente un atome d'hydrogène ou un radical méthyle , m est égal à 1, 2, 3 ou 4, et n est soit égal à 1 lorsque R₁ représente un radical méthyle, soit égal à 1, 2, 3 lorsque R₁ représente un atome d'hydrogène, à titre de capteurs de formaldéhyde.This is why the subject of the present invention is the use of the products of formula (I)
Figure imgb0001
in which R represents an acetoacetyl or dioxo-3,5 hexanoyl group, R₁ represents a hydrogen atom or a methyl radical, m is equal to 1, 2, 3 or 4, and n is either equal to 1 when R₁ represents a methyl radical, or equal to 1, 2, 3 when R₁ represents a hydrogen atom, as formaldehyde captors.

L'invention a plus particulièrement pour objet, l'utilisation à titre de capteurs de formaldéhyde, des produits tels que définis ci-dessus, caractérisés en ce que dans la formule (I), R et R₁ ont la signification donnée précédemment, n est égal à 1 et m est égal à 1 ou 2.A more particular subject of the invention is the use, as formaldehyde sensors, of products as defined above, characterized in that in the formula (I), R and R₁ have the meaning given above, n is equal to 1 and m is equal to 1 or 2.

Parmi ces derniers produits, l'on peut utiliser notamment à titre de capteurs de formaldéhyde, les produits de formule générale (I) ci-dessus, caractérisés en ce que R représente le groupement acétoacétyle, R₁ représente un atome d'hydrogène ou un radical méthyle, n est égal à 1 et m est égal à 1 ou 2.Among these latter products, one can use in particular as formaldehyde sensors, the products of general formula (I) above, characterized in that R represents the acetoacetyl group, R₁ represents a hydrogen atom or a radical methyl, n is 1 and m is 1 or 2.

Parmi ces derniers produits, on peut citer plus particulièrement :

  • le bis(acétoacétate) d'éthylène,
  • le bis(acétoacétate) d'oxydiéthylène.
Among these latter products, there may be mentioned more particularly:
  • ethylene bis (acetoacetate),
  • oxidiethylene bis (acetoacetate).

Les diesters de l'éthylèneglycol, du diéthylèneglycol, et du butanediol-1,4 avec l'acide acétoacétique (acide diacétique) sont connus : Beil.III, 4ème supplément, page 1543 et T.R.PATTERSON et al, J.Amer.Chem. Soc., 1959, 81, 4213-17. Ils peuvent être préparés notamment selon les méthodes décrites par R.J CLEMENS,Chem. Rev., 1986, 86, 250 et J.Org.chem., 1985, 50, 2431-35. Plus généralement, les diesters des polyalcoylèneglycols de formule générale (II)

Figure imgb0002

dans laquelle R₁, m et n ont la signification donnée précédemment, avec les acides acétylacétiques et l'acide dioxo-3,5 hexanoïque peuvent être obtenus par transestérification soit de l'acétoacétate d'éthyle, soit du dioxo-3,5 hexanoate d'éthyle avec le polyalcoylèneglycol de formule (II) correspondant selon la méthode citée par T.R.PATTERSON et al (loc.citée).The diesters of ethylene glycol, diethylene glycol, and 1,4-butanediol with acetoacetic acid (diacetic acid) are known: Beil.III, 4th supplement, page 1543 and TRPATTERSON et al, J. Amer.Chem. Soc., 1959, 81 , 4213-17. They can be prepared in particular according to the methods described by RJ CLEMENS, Chem. Rev., 1986, 86 , 250 and J. Org.chem., 1985, 50 , 2431-35. More generally, the polyalkylene glycol diesters of general formula (II)
Figure imgb0002
in which R₁, m and n have the meaning given above, with acetylacetic acids and 3,5-dioxohexanoic acid can be obtained by transesterification either of ethyl acetoacetate or of 3,5-Dioxo ethyl hexanoate with the polyalkylene glycol of formula (II) corresponding according to the method cited by TRPATTERSON et al (loc. cited).

Comme on l'a dit précédemment, les produits de formule (I) présentent de très intéressantes propriétés comme capteurs de formaldéhyde, et notamment, ils permettent d'abaisser très considérablement les doses de formaldéhyde libre présent et/ou libéré par les tissus à base de fibres cellulosiques, apprêtés avec des résines aminoplastes contenant à l'état libre ou combiné du formaldéhyde.As said previously, the products of formula (I) have very interesting properties as formaldehyde scavengers, and in particular, they make it possible to very considerably lower the doses of free formaldehyde present and / or released by the tissues based of cellulose fibers, prepared with aminoplast resins containing in the free or combined state formaldehyde.

Dans leur application dans le domaine de l'ennoblissement des tissus à base de fibres cellulosiques avec des résines aminoplastes couramment utilisées pour conférer aux tissus des propriétés d'infroissabilité telles que les résines classiques urée-glyoxal-formaldéhyde, éthérifiées ou non avec un alcanol tel que le méthanol, on utilise les produits de formule (I) définie ci-dessus, en solution dans le bain d'apprêtage de préférence à la dose de 0,001 à 2 moles par litre de bain d'apprêtage (dit aussi d'ennoblissement) et l'on effectue ensuite l'apprêtage dans les conditions habituelles. Après traitement, les tissus ainsi apprêtés ne contiennent pratiquement plus de formaldéhyde libre et /ou susceptible de se libérer.In their application in the field of the finishing of fabrics based on cellulosic fibers with aminoplast resins commonly used to give fabrics wrinkle-resistant properties such as conventional urea-glyoxal-formaldehyde resins, etherified or not with an alkanol such as methanol, the products of formula (I) defined above are used, in solution in the dressing bath preferably at a dose of 0.001 to 2 moles per liter of dressing bath (also called finishing) and then the priming is carried out under the usual conditions. After treatment, the tissues thus prepared practically no longer contain free formaldehyde and / or likely to be released.

C'est pourquoi la présente demande a aussi pour objet un procédé d'ennoblissement des tissus à base de fibres cellulosiques au moyen d'une résine aminoplaste contenant à l'état libre ou combiné du formaldéhyde dans lequel on place les tissus dans un bain d'ennoblissement, caractérisé en ce que l'on utilise dans ledit- bain d'ennoblissement, à titre de capteurs de formaldéhyde, un produit de formule (I) tel que défini ci-dessus, notamment le bis(acétoacétate) d'éthylène ou le bis (acétoacétate) d'oxydiéthylène.This is why the present application also relates to a process for finishing fabrics based on cellulosic fibers by means of an aminoplast resin containing in the free or combined state formaldehyde in which the fabrics are placed in a bath. finishing, characterized in that in said finishing bath, as formaldehyde sensors, a product of formula (I) as defined above, in particular ethylene bis (acetoacetate) or oxidiethylene bis (acetoacetate).

Les exemples suivants sont donnés à titre indicatif ; ils permettent de mieux comprendre l'invention mais ils n'en limitent pas la portée.The following examples are given as indicative; they allow a better understanding of the invention but they do not limit its scope.

Sauf indications contraires, les parties et pourcentages sont donnés en poids. Le test de défroissabilité est réalisé selon la norme AATCC 66-1972, 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 185 °C pendant 30 secondes et les blancheurs, exprimées en degré Berger, sont mesurées avec un spectrophotomètre.Unless otherwise indicated, parts and percentages are given by weight. The wrinkle test is carried out according to the AATCC 66-1972 standard, the wrinkle is expressed by the sum of the wrinkling angles obtained in warp and weft direction. The tensile strength of the samples, expressed in daN, in warp direction plus in weft direction is produced according to standard AFNOR G 07.001. The yellowing of the tissues, carried out on a FIXOTEST device at 185 ° C for 30 seconds and the whiteness, expressed in Berger degree, are measured with a spectrophotometer.

Les taux de formaldéhyde, exprimés en ppm, sont déterminés selon la norme AATCC 112-1984, désignée ci-après AATCC 112.The formaldehyde levels, expressed in ppm, are determined according to standard AATCC 112-1984, hereinafter referred to as AATCC 112.

Le bis (acétoacétate) d'éthylène, a été préparé selon T.R.PATTERSON et al (loc. citée). 11 se présente sous la forme d'un liquide présentant un point d'ébullition sous 0,7 mbar de 150-152°C. Le bis (acétoacétate) d'oxydiéthylène a également été préparé selon T.R.PATTERSON et al. Il se présente sous la forme d'un liquide présentant un point d'ébullition sous 1,2 mbar de 178-180°C.The ethylene bis (acetoacetate) was prepared according to T.R. PATTERSON et al (loc. Cited). 11 is in the form of a liquid having a boiling point under 0.7 mbar of 150-152 ° C. Oxydethylene bis (acetoacetate) was also prepared according to T.R. PATTERSON et al. It is in the form of a liquid having a boiling point at 1.2 mbar of 178-180 ° C.

EXEMPLES 1-4EXAMPLES 1-4

On imprègne au foulard un tissu de popeline 100% coton, débouilli et blanchi, d'un poids d'environ 130g par mètre carré avec un taux d'exprimage de 75 % dans un bain aqueux, dont le pH est indiqué dans le tableau I, contenant en solution :

  • 55g/l d'une résine commerciale vendue par la demanderesse sous la désignation ARKOFIXR NFL Conc. qui est une résine urée-glyoxal-formaldéhyde faiblement éthérifiée au méthanol,
  • 15 g/l d'un catalyseur commercialisé par la demanderesse sous la désignation catalyseur 3282,
  • 2 g/l d'un agent mouillant : le nonylphénol éthoxylé avec 10 moles d'oxyde d'éthylène,
  • 100 mmoles/l soit de bis (acétoacétate) d'éthylène (exemple 1), soit de bis (acétoacétate) d'oxydiéthylène (exemple 2).
A 100% cotton poplin fabric, scalded and bleached, is impregnated with the scarf, weighing approximately 130 g per square meter with a rate of expression of 75% in an aqueous bath, the pH of which is indicated in table I , containing in solution:
  • 55g / l of a commercial resin sold by the applicant under the designation ARKOFIX R NFL Conc. which is a urea-glyoxal-formaldehyde resin weakly etherified with methanol,
  • 15 g / l of a catalyst sold by the applicant under the designation catalyst 3282,
  • 2 g / l of a wetting agent: nonylphenol ethoxylated with 10 moles of ethylene oxide,
  • 100 mmol / l either of bis (acetoacetate) of ethylene (example 1), or of bis (acetoacetate) of oxydiethylene (example 2).

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 35 secondes à 180°C.The fabric is then dried for 45 seconds at 120 ° C, then it is subjected on a laboratory oar to a heat treatment for 35 seconds at 180 ° C.

On détermine ensuite sur des échantillons du tissu traité :

  • la défroissabilité,
  • la résistance à la traction, désignée ci-après Rt,
  • la blancheur, désignée ci-après B,
  • le jaunissement, désigné ci-après J,
  • le taux de formaldéhyde libre, exprimé en ppm, désigné ci-après F.
Next, samples of the treated fabric are determined:
  • wrinkle resistance,
  • the tensile strength, hereinafter referred to as Rt,
  • whiteness, hereinafter referred to as B,
  • yellowing, hereinafter referred to as J,
  • the level of free formaldehyde, expressed in ppm, designated below F.

Les résultats obtenus sont donnés dans le tableau I en comparaison avec un tissu non traité (exemple 3) et un tissu traité de manière conventionnelle en l'absence d'un capteur de formaldéhyde (exemple 4).The results obtained are given in Table I in comparison with an untreated fabric (Example 3) and a fabric treated in a conventional manner in the absence of a formaldehyde sensor (Example 4).

L'examen du tableau I permet de constater que les tissus apprêtés en présence d'un capteur de formaldéhyde selon la présente invention ne contiennent pratiquement plus de formaldéhyde.Examination of Table I shows that the fabrics primed in the presence of a formaldehyde sensor according to the present invention contain practically no more formaldehyde.

EXEMPLES DE COMPARAISON C1 ET C2COMPARISON EXAMPLES C1 AND C2

On reproduit l'exemple 1 en remplaçant le bis (acétoacétate) d'éthylène par 200 mmoles par litre de bain d'acétoacétate d'hydroxy-2 éthyle préparé selon l'exemple 1 de la demande de brevet PCT WO88/09323 (exemple C1).Example 1 is reproduced by replacing the bis (acetoacetate) of ethylene with 200 mmol per liter of bath of 2-hydroxyethyl acetoacetate prepared according to Example 1 of PCT patent application WO88 / 09323 (Example C1 ).

De même, on reproduit l'exemple 1 en remplaçant le bis (acétoacétate) d'éthylène par 200 mmoles par litre de bain de malonate de di(hydroxy-2 éthoxyéthyle) préparé selon l'exemple 2 de la demande de brevet PCT WO88/09323 (exemple C2).Similarly, Example 1 is reproduced by replacing the bis (acetoacetate) of ethylene with 200 mmol per liter of di (2-hydroxyethoxyethyl) malonate prepared according to Example 2 of PCT patent application WO88 / 09323 (example C2).

Les résultats obtenus dans ces deux exemples de comparaison sont donné dans le tableau I. On constate que les produits selon la présente invention donnent de bien meilleurs résultats en ce qui concerne les taux de formaldéhyde dosés sur les tissus ainsi traités.

Figure imgb0003
The results obtained in these two examples of Comparison are given in Table I. It can be seen that the products according to the present invention give much better results with regard to the levels of formaldehyde assayed on the tissues thus treated.
Figure imgb0003

Claims (9)

Utilisation des produits de formule (I)
Figure imgb0004
 dans laquelle R représente un groupement acétoacétyle ou dioxo-3,5 hexanoyle, R₁ représente un atome d'hydrogène ou un radical méthyle, m est égal à 1, 2, 3 ou 4 et n est soit égal à 1 lorsque R¹ représente un radical méthyle soit égal à 1, 2 ou 3 lorsque R₁ représente un atome d'hydrogène, à titre de capteurs de formaldéhyde.Use of the products of formula (I)
Figure imgb0004
 in which R represents an acetoacetyl or dioxo-3,5 hexanoyl group, R₁ represents a hydrogen atom or a methyl radical, m is equal to 1, 2, 3 or 4 and n is either equal to 1 when R¹ represents a radical methyl is equal to 1, 2 or 3 when R₁ represents a hydrogen atom, as formaldehyde sensors. Utilisation selon la revendication 1, caractérisée en ce que l'on utilise des produits de formule (I) dans laquelle R représente un groupement acétoacétyle ou dioxo-3,5 hexanoyle, R₁ représente un atome d'hydrogène ou un radical méthyle, m est égal à 1 ou 2 et n est égal à 1.Use according to claim 1, characterized in that products of formula (I) are used in which R represents an acetoacetyl or dioxo-3,5 hexanoyl group, R₁ represents a hydrogen atom or a methyl radical, m is equal to 1 or 2 and n is equal to 1. Utilisation selon la revendication 2, caractérisée en ce que l'on utilise des produits de formule (I) dans laquelle R représente le groupement acétoacétyle, R₁ représente un atome d'hydrogène ou un radical méthyle, m est égal à 1 ou 2 et n est égal à 1.Use according to claim 2, characterized in that products of formula (I) are used in which R represents the acetoacetyl group, R₁ represents a hydrogen atom or a methyl radical, m is equal to 1 or 2 and n is equal to 1. Utilisation du bis (acétoacétate) d'éthylène à titre de capteur de formaldéhyde.Use of ethylene bis (acetoacetate) as a formaldehyde sensor. Utilisation du bis (acétoacétate) d'oxydiéthylène à titre de capteur de formaldéhyde.Use of oxiethylene bis (acetoacetate) as a formaldehyde sensor. Procédé d'ennoblissement des tissus à base de fibres cellulosiques au moyen d'une résine aminoplaste contenant à l'état libre ou combiné du formaldéhyde dans lequel on place les tissus dans un bain d'ennoblissement, caractérisé en ce que l'on utilise dans ledit bain d'ennoblissement, à titre de capteur de formaldéhyde, un produit selon l'une quelconque des revendications 1 à 5.Process for finishing fabrics based on cellulose fibers by means of an aminoplast resin containing in the free or combined state formaldehyde in which the fabrics are placed in a finishing bath, characterized in that it is used in said finishing bath, as a formaldehyde sensor, a product according to any one of claims 1 to 5. Procédé selon la revendication 6, caractérisé en ce que l'on utilise de 0,001 à 2 moles par litre de bain d'ennoblissement, à titre de capteur de formaldéhyde, un produit selon l'une quelconque des revendications 1 à 5.Method according to claim 6, characterized in that from 0.001 to 2 moles per liter of finishing bath is used, as formaldehyde sensor, a product according to any one of the claims 1 to 5. Procédé selon la revendication 7, caractérisé en ce que l'on utilise, à titre de capteur de formaldéhyde, le bis (acétoacétate) d'éthylène.Process according to Claim 7, characterized in that ethylene bis (acetoacetate) is used as the formaldehyde sensor. Procédé selon la revendication 7, caractérisé en ce que l'on utilise, à titre de capteur de formaldéhyde, le bis (acétoacétate) d'oxydiéthylène.Process according to Claim 7, characterized in that the bis (acetoacetate) of oxydiethylene is used as the formaldehyde sensor.
EP93401048A 1992-05-07 1993-04-22 Application of diesters of polyalkylene glycols as formaldehyde scavengers and process of finishing the textile industry Expired - Lifetime EP0569266B1 (en)

Applications Claiming Priority (2)

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FR929205653A FR2690933B1 (en) 1992-05-07 1992-05-07 APPLICATION OF POLYALCOYLENEGLYCOLS DIESTERS AS FORMALDEHYDE SENSORS AND ENCLOSURE METHOD FOR THE TEXTILE INDUSTRY.
FR9205653 1992-05-07

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