EP0360248A2 - Composition for finishing textiles, and process for the treatment of cellulosic textiles - Google Patents
Composition for finishing textiles, and process for the treatment of cellulosic textiles Download PDFInfo
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- EP0360248A2 EP0360248A2 EP89117400A EP89117400A EP0360248A2 EP 0360248 A2 EP0360248 A2 EP 0360248A2 EP 89117400 A EP89117400 A EP 89117400A EP 89117400 A EP89117400 A EP 89117400A EP 0360248 A2 EP0360248 A2 EP 0360248A2
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- Prior art keywords
- textile
- finishing agent
- agent according
- textile finishing
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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
- D06M13/12—Aldehydes; Ketones
- D06M13/123—Polyaldehydes; Polyketones
-
- 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
- D06M15/21—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
- D06M15/263—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of unsaturated carboxylic acids; Salts or esters thereof
-
- 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
- D06M15/21—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
- D06M15/327—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of unsaturated alcohols or esters thereof
- D06M15/333—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of unsaturated alcohols or esters thereof of vinyl acetate; Polyvinylalcohol
-
- 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
-
- 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
- D06M15/59—Polyamides; Polyimides
-
- 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
- D06M15/643—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds containing silicon in the main chain
Definitions
- the invention relates to a textile finishing agent and process for finishing cellulose-containing textile goods.
- low-formaldehyde crosslinking agents are usually used to refine textile fabrics made from cellulose fibers.
- dimethylolurea compounds used in the past - and sometimes still today - they have the advantage that the free and bound formaldehyde on the goods could be reduced.
- Formaldehyde-free crosslinkers based on N, N′-dimethyl derivatives of glyoxal monourein are currently on the market. Compared to conventional N, N'-dimethylol compounds, these products have a much lower reactivity on the cellulose fiber and significantly higher equipment costs. Comparative equipment with low-formaldehyde reactant crosslinkers has shown that the effects achieved do not correspond to the usual standard.
- the invention is therefore based on the object of providing a formulation for the high finishing of textile goods, in the use of which no formaldehyde is split off, but the application properties of the treated textile goods are nevertheless not adversely affected.
- the dialdehyde used is preferably 1,2-ethanedial or 1,5-pentanedial, which is usually used in aqueous solution.
- the reaction product from the dialdehydes with polyols is prepared by combining the components, if appropriate in an inert solvent, preferably water.
- the pH of the mixture is adjusted to 3-4, e.g. by adding acids (HCl, H2SO4, H3PO4 and the like) or, when using strongly acidic dialdehydes, by adding inorganic or organic bases (e.g. NaOH, KOH, mono-, di- or triethanolamine).
- Dialdehyde and polyol can be used in different amounts.
- the weight ratio of dialdehyde to polyol is preferably 70:30 to 30:70.
- the polyol is preferably used in a deficit so that a mixture of dialdehyde and reaction product is obtained.
- the polyols used are preferably linear C1-C6 diols, in particular those of the formula (I) above, in which R1 and R2 represent a hydrogen atom and the polyols of the general formula (II) above, wherein x, y and z are 0 or 1 stand.
- Particularly preferred polyols are glycol, propylene glycol, 1,4-butanediol, 1,6-hexanediol, neopentyl glycol, glycerin, pentraerythritol and 2-ethyl-2-nitro-1,3-propanediol.
- polymer two types are possible, namely film-forming polymers and self-crosslinking polymers which are customary in the field in question here, and copolymers thereof which have a glass transition point of from -40 ° C. to +10 ° C.
- the polymers can be selected from polyacrylates, polyurethanes, polyamides, polyaminoamides, polyvinyl acetates and polysiloxanes.
- the film-forming polymers are drawn onto the fiber in a conventional manner without forming a chemical bond with the fiber.
- the self-crosslinking polymers are those which are capable of reacting with the textile fiber to form a chemical bond under the finishing conditions (approx. 120 to 160 o C).
- Such self-crosslinking polymers therefore generally contain functional groups, such as free ester groups, hydroxyl groups, amino groups, isocyanate groups and the like, which can react with functional groups of the textile fiber.
- Preferred polymers are: - Polyacrylates and copolymers thereof, for example butyl acrylate / vinyl acetate, ethyl acrylate / vinyl acetate, 2-ethylhexyl acrylic / vinyl acetate, butyl acrylate / vinyl acetate / maleic acid, butyl acrylate / vinyl acetate / maleic acid ester or butyl acrylate / acrylic acid polymers.
- - Polyvinyl acetates and copolymers thereof for example the polymers already mentioned and a vinyl acetate / ethylene polymer.
- the polymers serve to reduce the yellowing problems which arise in the finishing of textile fibers and to give the fibers protection, i.e. to reduce the loss of tear strength associated with the finishing.
- the agent according to the invention further contains a catalyst which serves to bring about a reaction (crosslinking) of the cellulose fibers with the participation of the dialdehyde or its reaction product.
- Suitable catalysts are acidic metal salts, especially magnesium and aluminum halides or mixtures thereof. If the catalysts are used in a mixture, the mixing ratio (in parts by weight) can vary within a wide range. For the particularly preferred catalyst mixture of magnesium chloride and aluminum chloride (including all basic aluminum chlorides), it is, for example, in the range from 100: 0.5 to 100: 30.
- the agent according to the invention can also be present in two or three parts which are only put together when in use.
- the agent is preferably in two parts, the first part containing the components a) and b) mentioned and the second part containing the component c).
- the catalyst is preferably combined with components a) and b) directly or in the liquor immediately before use of the agent according to the invention.
- Components a) to c) according to the invention are preferably used in the following weight ratio: a) Dialdehyde or its reaction product 10-40 parts by weight b) polymer 5-25 parts by weight c) catalyst 5-15 parts by weight
- compositions according to the invention can also contain stabilizers which serve to make the composition stable in storage and homogeneous if self-crosslinking polymers or copolymers are contained therein.
- Suitable stabilizers are, for example, polyols of the above formulas (I) and (II) and polyglycols of the formula HO (CH2-CH2-O-) K -CH2-CH2-OH, in which k stands for 100 to 6000.
- the polyols of the formula (II) and the polyglycols mentioned are preferred.
- the stabilizer is generally present in the composition in proportions of 1 to 10 parts by weight.
- the agent according to the invention can contain a hydrophobizing agent in order to make the textile material hydrophobic.
- the hydrophobizing agent is preferably added to the first part of the agent according to the invention.
- hydrophobizing agents for example paraffins in the form of an emulsion, in particular metal salts of higher fatty acids, such as aluminum or zirconium stearates, or aminoplasts.
- the hydrophobizing agent is generally contained in the composition in proportions of 1 to 15 parts by weight.
- the agents according to the invention can also contain conventional additives, e.g. Surfactants or other additives used in the fleet.
- the crosslinker component a) of the agents according to the invention has a higher reactivity to the cellulose fiber than the previously known formaldehyde-free crosslinkers, such as N, N'-dimethyldihydroxyethyleneurea, and a reactivity comparable to the dimethylolurea compounds. This also achieves comparable effects in terms of dry and wet crease recovery, tensile and tear strength as with conventional low-maintenance equipment.
- crosslinker component a) according to the invention can also be combined by the presence of a stabilizer use with self-crosslinking polymers without fear of instability and inhomogeneity of the agent or of the liquor in which the agent is dissolved.
- the invention also relates to a process for finishing cellulose-containing textile goods, which is characterized in that a liquor is prepared by dissolving the two parts of a textile finishing agent according to the invention, if appropriate together with conventional additives, in water, impregnating the textile goods with the liquor and drying them and subjected to heat treatment for condensation.
- the agents according to the invention are present in the liquor in an amount of about 0.2 to 1.5% by weight, based on the total weight of the liquor.
- the pH of the liquor is generally 2.0 to 6.0, in particular 2.5 to 4.0.
- the liquor can contain other additives customary for the finishing of cellulose-containing textile goods, such as plasticizers, surfactants, antistatic agents, additional hydrophobizing agents, anti-slip agents and the like.
- the textile goods are then impregnated in a customary manner, for example by padding and squeezing the textile goods to a liquor absorption of about 60 to 100%.
- Tables 1 and 2 below show the composition of the agents used and the fleet.
- the liquor was produced by adding the two parts of the agent according to the invention and optionally the stabilizer to the liquor.
- the goods to be equipped were padded in the liquor, squeezed to 80% liquor absorption and shock-condensed at the temperature specified.
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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)
Abstract
Die Erfindung betrifft ein Textilveredelungsmittel auf wäßriger Basis zur Ausrüstung von cellulosehaltigem Textilgut, das ein Vernetzungsmittel auf der Basis eines Dialdehyds bzw. eines Reaktionsproduktes dieses Dialdehyds mit einem Polyol, ein Polymerisat ausgewählt unter entsprechenden Polyacrylaten, Polyurethanen, Polyamiden, Polyaminoamiden, Polyvinylacetaten und Polysiloxanen oder Copolymerisaten davon und einen sauren Katalysator enthält. Mit dem erfindungsgemäßen Textilveredelungsmittel ist eine formaldehydfreie Ausrüstung von Textilien möglich, wobei die Eigenschaften der Textilfasern nicht nachteilig beeinflußt werden.The invention relates to an aqueous-based textile finishing agent for finishing cellulose-containing textile material, which comprises a crosslinking agent based on a dialdehyde or a reaction product of this dialdehyde with a polyol, a polymer selected from corresponding polyacrylates, polyurethanes, polyamides, polyaminoamides, polyvinyl acetates and polysiloxanes or copolymers thereof and contains an acid catalyst. With the textile finishing agent according to the invention, formaldehyde-free finishing of textiles is possible, the properties of the textile fibers not being adversely affected.
Description
Zur Hochveredelung von textilen Flächengebilden aus Cellulosefasern werden heutzutage üblicherweise formaldehydarme Vernetzer eingesetzt. Gegenüber den früher - und teilweise auch heute noch - verwendeten Dimethylolharnstoffverbindungen haben sie den Vorteil, daß der freie und gebundene Formaldehyd auf der Ware reduziert werden konnte.Nowadays, low-formaldehyde crosslinking agents are usually used to refine textile fabrics made from cellulose fibers. Compared to the dimethylolurea compounds used in the past - and sometimes still today - they have the advantage that the free and bound formaldehyde on the goods could be reduced.
Seit einigen Jahren wurden z.B. in Japan und den skandinavischen Ländern Gesetze erlassen, die auf bestimmten Textilien wie Babykleidung keine Ausrüstung mit formaldehydhaltigen bzw. formaldehydabspaltenden Produkten erlauben. Und auch die andauernde Diskussion über die potentielle Kanzerogenität von Formaldehyd hat die Textilhilfsmittelhersteller zur Suche nach anderen, formaldehydfreien Vernetzertypen gezwungen. Für die Entwicklung einer formaldehydfreien Ausrüstung von cellulosehaltigem Textilgut stehen im Rahmen der verfahrens- und maschinentechnischen Möglichkeiten der Textilveredelungsindustrie nur noch wenige zur Vernetzung brauchbare chemisch reaktive Gruppen zur Verfügung. Dazu zählen die Aziridingruppe, die Epoxy- und die Chlorhydroxy-Gruppierung sowie die -C=C-Doppelbindung.For example, for some years In Japan and the Scandinavian countries, laws are enacted which do not permit the use of products containing formaldehyde or products that release formaldehyde on certain textiles such as baby clothing. And the ongoing discussion about the potential carcinogenicity of formaldehyde has also forced textile auxiliary manufacturers to search for other types of formaldehyde-free crosslinkers. For the development of formaldehyde-free finishing of cellulose-containing textile goods, there are only a few chemically reactive groups that can be used for crosslinking within the process and mechanical possibilities of the textile finishing industry. These include the aziridine group, the epoxy and the chlorohydroxy group and the -C = C double bond.
Weiter wurde im Rahmen von wissenschaftlichen Arbeiten bereits die Reaktion von Dialdehyden mit Cellulosefasern unter sucht. Das Ergebnis war stets eine Verbesserung der Trockenknittererholung aber auch eine starke Einbuße in der Reißfestigkeit der Cellulosefasern sowie eine außerordentlich starke Vergilbung des Fasermaterials.Furthermore, the reaction of dialdehydes with cellulose fibers has already been researched looking for. The result has always been an improvement in the recovery of dry creases, but also a major loss in the tensile strength of the cellulose fibers and an extremely strong yellowing of the fiber material.
Aus der US-PS 4 455 416 ist die Verbesserung der Trockenknittererholung durch Anwendung cyclischer Harnstoff-Glyoxal-Polyol-Kondensate bekannt. Weiter beschreibt die US-Anmeldung 302 007 die Ausrüstung von Textilien mit Reaktionsprodukten aus Carbamaten und Glutaraldehyd.From US Pat. No. 4,455,416 it is known to improve the recovery of dry creases by using cyclic urea-glyoxal-polyol condensates. Furthermore, US application 302 007 describes the finishing of textiles with reaction products from carbamates and glutaraldehyde.
Beide genannten Patente haben den Nachteil, daß die gewohnten Ausrüstungseffekte nicht erreicht werden. Außerdem treten Vergilbungsprobleme auf Weißware auf.Both patents mentioned have the disadvantage that the usual equipment effects are not achieved. In addition, yellowing problems occur on white goods.
Zur Zeit werden formaldehydfreie Vernetzer auf Basis von N,N′-Dimethylderivaten des Glyoxalmonoureins auf dem Markt angeboten. Diese Produkte weisen im Vergleich zu konventionellen N,N′-Dimethylolverbindungen eine weitaus geringere Reaktivität auf der Cellulosefaser und deutlich höhere Ausrüstungskosten auf. Vergleichsausrüstungen mit formaldehydarmen Reaktantvernetzern haben gezeigt, daß die erreichten Effekte nicht dem üblichen Standard entsprechen.Formaldehyde-free crosslinkers based on N, N′-dimethyl derivatives of glyoxal monourein are currently on the market. Compared to conventional N, N'-dimethylol compounds, these products have a much lower reactivity on the cellulose fiber and significantly higher equipment costs. Comparative equipment with low-formaldehyde reactant crosslinkers has shown that the effects achieved do not correspond to the usual standard.
Auf der Suche das alternativen Lösungen hat man versucht, die gewohnten Ausrüstungseffekte durch Einsatz von reaktiven Polymeren aller Art zu imitieren. Auf dieser Basis werden Ausrüstungsmittel bestehend aus Polyacrylaten, Polyurethanen, Polyamiden, Polyaminamiden und Polysiloxan angeboten, z.B. auf Basis von Filmbildnern aus selbstvernetzenden Polymeren. Die Ausrüstung mit Silikonelastomeren ist in der EP-A-136 069 beschrieben.In the search for alternative solutions, attempts have been made to imitate the usual equipment effects by using reactive polymers of all kinds. On this basis, equipment consisting of polyacrylates, polyurethanes, polyamides, polyamine amides and polysiloxane is offered, for example based on film formers made from self-crosslinking polymers. The finishing with silicone elastomers is described in EP-A-136 069.
Pflegeleichtausrüstungen von cellulosehaltigen Textilien mit selbstvernetzenden Copolymeren haben den Nachteil, daß lediglich ein mehr oder minder elastischer Film um die Faser gebildet wird. Eine Reaktion zwischen Polymer und Faser wie zwischen herkömmlichen N,N′-Methylolvernetzern und der Cellulosefaser tritt nicht auf. Dadurch werden die gewohnten Effekte in bezug auf Trockenknittererholung, Waschkrumpf und Selbstglättungsverfahren in der Praxis nicht erreicht.Easy-care finishes of cellulose-containing textiles with self-crosslinking copolymers have the disadvantage that only a more or less elastic film is formed around the fiber. A reaction between polymer and fiber as between conventional N, N'-methylol crosslinkers and the cellulose fiber does not occur. As a result, the usual effects in terms of dry crease recovery, washing shrinking and self-smoothing processes are not achieved in practice.
Die Anwendung der bekannten Methoden ist daher mit einer Reihe von Nachteilen behaftet, die sich wie folgt zusammenfassen lassen: Die toxikologischen Probleme beim Einsatz von Aziridin- und Chlor-Hydroxy-Verbindungen sind vergleichbar mit denjenigen von Dimethylolharnstoffverbindungen. Weiter entstehen neue Probleme hinsichtlich der Reaktivität, weil Epoxy- und Chlorhydroxygruppen in alkalischem Medium vernetzen, Vernetzer mit Doppelbindungen dagegen radikalisch gestartet werden. Ferner ist der Preis der zur Anwendung kommenden alternativen Materialien im Vergleich zu Dimethylolharnstoffverbindungen deutlich höher. Schließlich treten erhebliche Vergilbungsprobleme auf.The use of the known methods is therefore associated with a number of disadvantages, which can be summarized as follows: The toxicological problems when using aziridine and chloro-hydroxy compounds are comparable to those of dimethylolurea compounds. Furthermore, new problems arise in terms of reactivity because epoxy and chlorohydroxy groups crosslink in an alkaline medium, whereas crosslinkers with double bonds are started radically. Furthermore, the price of the alternative materials used is significantly higher compared to dimethylol urea compounds. Finally, there are significant yellowing problems.
Der Erfindung liegt daher die Aufgabe zugrunde, eine Formulierung zur Hochveredelung von Textilgut zur Verfügung zu stellen, bei deren Anwendung kein Formaldehyd abgespalten wird, die Anwendungseigenschaften des behandelten Textilgutes aber dennoch nicht nachteilig beeinflußt werden.The invention is therefore based on the object of providing a formulation for the high finishing of textile goods, in the use of which no formaldehyde is split off, but the application properties of the treated textile goods are nevertheless not adversely affected.
Überraschenderweise wurde nun gefunden, daß diese Aufgabe gelöst wird durch die Verwendung bestimmter Dialdehyde bzw. eines Reaktionsproduktes aus diesen Dialdehyden mit Polyolen zusammen mit bestimmten Copolymeren.Surprisingly, it has now been found that this object is achieved by using certain dialdehydes or a reaction product of these dialdehydes with polyols together with certain copolymers.
Gegenstand der vorliegenden Erfindung ist daher ein Textilveredelungsmittel auf wäßriger Basis zur Ausrüstung von cellulosehaltigem Textilgut, das dadurch gekennzeichnet ist, daß es
- a) wenigstens einen Dialdehyd der Formel:
OHC-(CH₂)n-CHO
worin
n für 0 bis 10, vorzugsweise 0 bis 3 steht, oder wenigstens ein Reaktionsprodukt aus einem Dialdehyd obiger Formel mit einem linearen aliphatischen Polyol der Formel (I):
R₁-CH(OH) - (CH₂)m-CH(OH)-R₂ I
worin
R₁ und R₂, die gleich oder verschieden sein können, für ein Wasserstoffatom oder eine Methyl-, Ethyl-, n-Propyl- oder Isopropylgruppe stehen und m für 0 bis 4 steht, oder
mit einem verzweigten aliphatischen Polyol der Formel (II): worin
R₂ für OH, (CH₂)y-CH₃, (CH₂)z-CH₂OH, NO₂ steht;
R₄ Für H, (CH₂)y-CH₃, (CH₂)z-CH₂OH steht;
x für 0 bis 2 steht;
y für 0 bis 5 steht und
z für 0 bis 2 steht,
oder eine Mischung von Dialdehyd und Reaktionsprodukt, - b) ein Polymerisat mit einem Glasübergangspunkt von -40 °C bis +10 °C, das ausgewählt ist unter entsprechenden Polyacrylaten, Polyurethanen, Polyamiden, Polyaminoamiden, Polyvinylacetaten und Polysiloxanen und Copolymerisaten davon, und
- c) wenigstens ein saures Metallsalz als Katalysator enthält.
- a) at least one dialdehyde of the formula:
OHC- (CH₂) n -CHO
wherein
n represents 0 to 10, preferably 0 to 3, or at least one reaction product of a dialdehyde of the above formula with a linear aliphatic polyol of the formula (I):
R₁-CH (OH) - (CH₂) m -CH (OH) -R₂ I
wherein
R₁ and R₂, which may be the same or different, represent a hydrogen atom or a methyl, ethyl, n-propyl or isopropyl group and m represents 0 to 4, or
with a branched aliphatic polyol of the formula (II): wherein
R₂ is OH, (CH₂) y -CH₃, (CH₂) z -CH₂OH, NO₂;
R₄ represents H, (CH₂) y -CH₃, (CH₂) z -CH₂OH;
x represents 0 to 2;
y represents 0 to 5 and
z represents 0 to 2,
or a mixture of dialdehyde and reaction product, - b) a polymer with a glass transition point from -40 ° C to +10 ° C, which is selected from corresponding polyacrylates, polyurethanes, polyamides, polyaminoamides, polyvinyl acetates and polysiloxanes and copolymers thereof, and
- c) contains at least one acidic metal salt as a catalyst.
Als Dialdehyd kommt bevorzugt 1,2-Ethandial oder 1,5-Pentandial zur Anwendung, das üblicherweise in wäßriger Lösung eingesetzt wird.The dialdehyde used is preferably 1,2-ethanedial or 1,5-pentanedial, which is usually used in aqueous solution.
Das Reaktionsprodukt aus den Dialdehyden mit Polyolen wird hergestellt, indem man die Komponenten, ggf. in einem reaktionsinerten Lösungsmittel, vorzugsweise Wasser, zusammengibt. Der pH-Wert der Mischung wird auf 3 - 4 eingestellt, z.B. durch Zugabe von Säuren (HCl, H₂SO₄, H₃PO₄ und dgl.) oder bei Verwendung von stark sauer eingestellten Dialdehyden durch Zugabe von anorganischen oder organischen Basen (z.B. NaOH, KOH, Mono-, Di- oder Triethanolamin). Dialdehyd und Polyol kann man in unterschiedlichen Mengen einsetzen. Das Gewichtsverhältnis von Dialdehyd zu Polyol beträgt vorzugsweise 70 : 30 bis 30 : 70. Vorzugsweise kommt das Polyol jedoch im Unterschuß zur Anwendung, so daß man ein Gemisch aus Dialdehyd und Reaktionsprodukt erhält.The reaction product from the dialdehydes with polyols is prepared by combining the components, if appropriate in an inert solvent, preferably water. The pH of the mixture is adjusted to 3-4, e.g. by adding acids (HCl, H₂SO₄, H₃PO₄ and the like) or, when using strongly acidic dialdehydes, by adding inorganic or organic bases (e.g. NaOH, KOH, mono-, di- or triethanolamine). Dialdehyde and polyol can be used in different amounts. The weight ratio of dialdehyde to polyol is preferably 70:30 to 30:70. However, the polyol is preferably used in a deficit so that a mixture of dialdehyde and reaction product is obtained.
Als Polyole verwendet man vorzugsweise lineare C₁-C₆-Diole, insbesondere diejenigen der obigen Formel (I), in der R₁ und R₂ für ein Wasserstoffatom stehen sowie die Polyole der obigen allgemeinen Formel (II), worin x, y und z für 0 oder 1 stehen.The polyols used are preferably linear C₁-C₆ diols, in particular those of the formula (I) above, in which R₁ and R₂ represent a hydrogen atom and the polyols of the general formula (II) above, wherein x, y and z are 0 or 1 stand.
Besonders bevorzugte Polyole sind Glykol, Propylenglykol, 1,4-Butandiol, 1,6-Hexandiol, Neopentylglykol, Glycerin, Pentraerythrit und 2-Ethyl-2-nitro-1,3-propandiol.Particularly preferred polyols are glycol, propylene glycol, 1,4-butanediol, 1,6-hexanediol, neopentyl glycol, glycerin, pentraerythritol and 2-ethyl-2-nitro-1,3-propanediol.
Als Polymer kommen erfindungsgemäß zwei Typen in Frage, nämlich auf dem hier in Rede stehenden Gebiet übliche filmbildende Polymere und selbstvernetzende Polymere, sowie Copolymerisate davon, welche einen Glasübergangspunkt von -40 °C bis +10 °C aufweisen.According to the invention, two types of polymer are possible, namely film-forming polymers and self-crosslinking polymers which are customary in the field in question here, and copolymers thereof which have a glass transition point of from -40 ° C. to +10 ° C.
Die Polymere (Copolymere) können ausgewählt sein unter Polyacrylaten, Polyurethanen, Polyamiden, Polyaminoamiden, Polyvinylacetaten und Polysiloxanen.The polymers (copolymers) can be selected from polyacrylates, polyurethanes, polyamides, polyaminoamides, polyvinyl acetates and polysiloxanes.
Die filmbildenden Polymerisate ziehen in üblicher Weise auf die Faser auf, ohne daß sie eine chemische Bindung mit der Faser eingehen.The film-forming polymers are drawn onto the fiber in a conventional manner without forming a chemical bond with the fiber.
Bei den selbstvernetzenden Polymerisaten handelt es sich um solche, welche in der Lage sind, unter den Ausrüstungsbedingungen (ca. 120 bis 160oC) eine Reaktion mit der Textilfaser unter Ausbildung einer chemischen Bindung einzugehen. Derartige selbstvernetzende Polymerisate enthalten daher im allgemeinen funktionelle Gruppen, wie freie Estergruppen, Hydroxygruppen, Aminogruppen, Isocyanatgruppen und dergleichen, welche mit funktionellen Gruppen der Textilfaser reagieren können.The self-crosslinking polymers are those which are capable of reacting with the textile fiber to form a chemical bond under the finishing conditions (approx. 120 to 160 o C). Such self-crosslinking polymers therefore generally contain functional groups, such as free ester groups, hydroxyl groups, amino groups, isocyanate groups and the like, which can react with functional groups of the textile fiber.
Bevorzugte Polymerisate sind:
- Polyacrylate und Copolymerisate davon, zum Beispiel Butylacrylat/Vinylacetat-, Ethylacrylat/Vinylacetat-, 2-Ethylhexylacryl/Vinylacetat-, Butylacrylat/Vinylacetat/Maleinsäure-, Butylacrylat/Vinylacetat/Maleinsäureester- oder Butylacrylat/Acrylsäure-Polymerisate.
- Polyvinylacetate und Copolymerisate davon, z.B. die bereits genannten Polymerisate sowie ein Vinylacetat/Ethylen-Polymerisat.
- Polyurethane und Copolymerisate von, z.B. Polyesterurethane auf Basis aliphatischer Diisocyanate und Polyurethan-Polyester-Prepolymerisate mit 2 bis 3 % blockierten aromatischen Isocyanatgruppen.
- Polysiloxane (Siliconelastomere), d.h. Organosiloxane mit funktionellen Gruppen wie -0H oder -NH₂, beispielsweise primäres hydroxylfunktionelles Polydimethylsiloxan; primäres aminofunktionelles Polydimethylsiloxan; primäre hydroxylfunktionelle Polydimethylsiloxan-Polyoxyethylen-Copolymerisate und primäre aminofunktionelle Polydimethylsiloxan-Polyoxyethylen-Copolymerisate.Preferred polymers are:
- Polyacrylates and copolymers thereof, for example butyl acrylate / vinyl acetate, ethyl acrylate / vinyl acetate, 2-ethylhexyl acrylic / vinyl acetate, butyl acrylate / vinyl acetate / maleic acid, butyl acrylate / vinyl acetate / maleic acid ester or butyl acrylate / acrylic acid polymers.
- Polyvinyl acetates and copolymers thereof, for example the polymers already mentioned and a vinyl acetate / ethylene polymer.
- Polyurethanes and copolymers of, for example polyester urethanes based on aliphatic diisocyanates and polyurethane-polyester prepolymers with 2 to 3% blocked aromatic isocyanate groups.
- Polysiloxanes (silicone elastomers), ie organosiloxanes with functional groups such as -0H or -NH₂, for example primary hydroxyl-functional polydimethylsiloxane; primary amino functional polydimethylsiloxane; primary hydroxyl-functional polydimethylsiloxane-polyoxyethylene copolymers and primary amino-functional polydimethylsiloxane-polyoxyethylene copolymers.
Die Polymerisate dienen dazu, die bei der Hochveredelung von Textilfasern auftretenden Vergilbungsprobleme zu verringern und den Fasern Schutz zu verleihen, d.h. den mit der Veredelung einhergehenden Verlust an Reißfestigkeit zu verringern.The polymers serve to reduce the yellowing problems which arise in the finishing of textile fibers and to give the fibers protection, i.e. to reduce the loss of tear strength associated with the finishing.
Weiter enthält das erfindungsgemäße Mittel einen Katalysator, der dazu dient, eine Reaktion (Vernetzung) der Cellulosefasern unter Beteiligung des Dialdehydes bzw. dessen Reaktionsproduktes herbeizuführen. Geeignete Katalysatoren sind saure Metallsalze, insbesondere Magnesium- und Aluminiumhalogenide oder Mischungen davon. Wenn die Katalysatoren in Mischung zur Anwendung kommen, kann das Mischungsverhältnis (in Gewichtsteilen) in einem weiten Bereich variieren. Für die besonders bevorzugte Katalysatorenmischung aus Magnesiumchlorid und Aluminiumchlorid (einschließlich aller basischen Aluminiumchloride) liegt es beispielsweise im Bereich von 100:0,5 bis 100:30.The agent according to the invention further contains a catalyst which serves to bring about a reaction (crosslinking) of the cellulose fibers with the participation of the dialdehyde or its reaction product. Suitable catalysts are acidic metal salts, especially magnesium and aluminum halides or mixtures thereof. If the catalysts are used in a mixture, the mixing ratio (in parts by weight) can vary within a wide range. For the particularly preferred catalyst mixture of magnesium chloride and aluminum chloride (including all basic aluminum chlorides), it is, for example, in the range from 100: 0.5 to 100: 30.
Das erfindungsgemäße Mittel kann auch in zwei oder drei Teilen vorliegen, die erst bei Gebrauch zusammengegeben werden. Vorzugsweise liegt das Mittel in zwei Teilen vor, wobei der erste Teil die erwähnten Komponenten a) und b) und der zweite Teil die Komponente c) enthält.The agent according to the invention can also be present in two or three parts which are only put together when in use. The agent is preferably in two parts, the first part containing the components a) and b) mentioned and the second part containing the component c).
Der Katalysator wird vorzugsweise unmittelbar vor Anwendung des erfindungsgemäßen Mittels mit den Komponenten a) und b) direkt oder in der Flotte vereinigt.The catalyst is preferably combined with components a) and b) directly or in the liquor immediately before use of the agent according to the invention.
Die erfindungsgemäßen Komponenten a) bis c) kommen vorzugsweise in folgendem Gewichtsverhältnis zur Anwendung:
Die erfindungsgemäßen Zusammensetzungen können auch Stabilisatoren enthalten, die dazu dienen, die Zusammensetzung lagerstabil und homogen zu machen, wenn selbstvernetzende Polymerisate bzw. Copolymerisate darin enthalten sind. Geeignete Stabilisatoren sind beispielsweise Polyole der obigen Formeln (I) und (II) sowie Polyglykole der Formel
HO(CH₂-CH₂-O-)K-CH₂-CH₂-OH,
wobei
k für 100 bis 6000 steht.The compositions according to the invention can also contain stabilizers which serve to make the composition stable in storage and homogeneous if self-crosslinking polymers or copolymers are contained therein. Suitable stabilizers are, for example, polyols of the above formulas (I) and (II) and polyglycols of the formula
HO (CH₂-CH₂-O-) K -CH₂-CH₂-OH,
in which
k stands for 100 to 6000.
Bevorzugt sind die Polyole der Formel (II) sowie die erwähnten Polyglykole. Der Stabilisator ist im allgemeinen in Anteilen von 1 bis 10 Gew.-Teilen in der Zusammensetzung vorhanden.The polyols of the formula (II) and the polyglycols mentioned are preferred. The stabilizer is generally present in the composition in proportions of 1 to 10 parts by weight.
Weiter kann das erfindungsgemäße Mittel ein Hydrophobisierungsmittel enthalten, um das Textilgut hydrophob auszurüsten. Das Hydrophobisierungsmittel wird vorzugsweise zu dem ersten Teil des erfindungsgemäßen Mittels gegeben.Furthermore, the agent according to the invention can contain a hydrophobizing agent in order to make the textile material hydrophobic. The hydrophobizing agent is preferably added to the first part of the agent according to the invention.
Als Hydrophobisierungsmittel kommen die auf dem hier in Rede stehenden Gebiet üblichen Mittel zur Anwendung, beispielsweise kann es sich um Paraffine in Form einer Emulsion, insbesondere Metallsalze höherer Fettsäuren, wie Aluminium- oder Zirkoniumstearate oder um Aminoplaste handeln. Das Hydrophobisierungsmittel ist im allgemeinen in Anteilen von 1 bis 15 Gew.-Teilen in der Zusammensetzung enthalten.The agents which are customary in the field in question are used as hydrophobizing agents, for example paraffins in the form of an emulsion, in particular metal salts of higher fatty acids, such as aluminum or zirconium stearates, or aminoplasts. The hydrophobizing agent is generally contained in the composition in proportions of 1 to 15 parts by weight.
Die erfindungsgemäßen Mittel können auch übliche Zusätze enthalten, z.B. Tenside oder andere Zusätze, die in der Flotte verwendet werden.The agents according to the invention can also contain conventional additives, e.g. Surfactants or other additives used in the fleet.
Mit den erfindungsgemäßen Mitteln ist eine formaldehydfreie Ausrüstung von (insbesondere cellulosehaltigem) Textilgut möglich. Es hat sich gezeigt, daß die Scheuerfestigkeit, Trocken- und Naßreibechtheit, Waschkrumpf und Selbstglättungsverhalten gegenüber der nicht behandelten Ware deutlich verbesser wird.With the agents according to the invention, formaldehyde-free finishing of (in particular cellulose-containing) textile goods is possible. It has been shown that the abrasion resistance, fastness to dry and wet rubbing, washing shrinkage and self-smoothing behavior are markedly improved compared to the untreated goods.
Die Vernetzerkomponente a) der erfindungsgemäßen Mittel besitzt eine höhere Reaktivität gegenüber der Cellulosefaser als die bisher bekannten formaldehydfreien Vernetzer, wie N,N′-Dimethyldihydroxyethylenharnstoff, und eine mit den Dimethylolharnstoffverbindungen vergleichbare Reaktivität. Dadurch werden auch vergleichbare Effekte in bezug auf die Trocken- und Naßknittererholung, Zug- und Weiterreißfestigkeit wie bei der konventionellen Pflegeleichtausrüstung erreicht.The crosslinker component a) of the agents according to the invention has a higher reactivity to the cellulose fiber than the previously known formaldehyde-free crosslinkers, such as N, N'-dimethyldihydroxyethyleneurea, and a reactivity comparable to the dimethylolurea compounds. This also achieves comparable effects in terms of dry and wet crease recovery, tensile and tear strength as with conventional low-maintenance equipment.
Darüber hinaus ist die Vergilbungstendenz bei Anwendung der erfindungsgemäßen Mittel deutlich reduziert.In addition, the tendency to yellowing when using the agents according to the invention is significantly reduced.
Weiter läßt sich durch die Anwesenheit eines Stabilisators die erfindungsgemäße Vernetzerkomponente a) auch zusammen mit selbstvernetzenden Polymerisaten zur Anwendung bringen, ohne daß eine Instabilität und Inhomogenität des Mittels bzw. der Flotte, in der das Mittel gelöst ist, zu befürchten ist.Furthermore, the crosslinker component a) according to the invention can also be combined by the presence of a stabilizer use with self-crosslinking polymers without fear of instability and inhomogeneity of the agent or of the liquor in which the agent is dissolved.
Die Erfindung betrifft auch ein Verfahren zur Ausrüstung von cellulosehaltigem Textilgut, das dadurch gekennzeichnet ist, daß man eine Flotte herstellt, indem man die beiden Teile eines erfindungsgemäßen Textilveredelungsmittels, gegebenenfalls zusammen mit üblichen Zusätzen, in Wasser löst, das Textilgut mit der Flotte imprägniert, trocknet und zur Kondensation einer Hitzebehandlung unterzieht.The invention also relates to a process for finishing cellulose-containing textile goods, which is characterized in that a liquor is prepared by dissolving the two parts of a textile finishing agent according to the invention, if appropriate together with conventional additives, in water, impregnating the textile goods with the liquor and drying them and subjected to heat treatment for condensation.
Im allgemeinen sind die erfindungsgemäßen Mittel in der Flotte in einer Menge von etwa 0,2 bis 1,5 Gew.-%, bezogen auf das Gesamtgewicht der Flotte, vorhanden. Der pH-Wert der Flotte beträgt im allgemeinen 2,0 bis 6,0, insbesondere 2,5 - 4,0.In general, the agents according to the invention are present in the liquor in an amount of about 0.2 to 1.5% by weight, based on the total weight of the liquor. The pH of the liquor is generally 2.0 to 6.0, in particular 2.5 to 4.0.
Die Flotte kann weitere für die Ausrüstung von cellulosehaltigem Textilgut übliche Zusätze enthalten, wie Weichmachungsmittel, Tenside, Antistatika, zusätzliche Hydrophobisierungsmittel, Schiebefestmittel und dgl.The liquor can contain other additives customary for the finishing of cellulose-containing textile goods, such as plasticizers, surfactants, antistatic agents, additional hydrophobizing agents, anti-slip agents and the like.
Das Imprägnieren des Textilgutes erfolgt dann in üblicher Weise, beispielsweise durch Foulardisieren und Abquetschen des Textilgutes auf eine Flottenaufnahme von etwa 60 bis 100 %.The textile goods are then impregnated in a customary manner, for example by padding and squeezing the textile goods to a liquor absorption of about 60 to 100%.
Anschließend erfolgt eine Trocknung und ein Kondensationsschritt, bei dem die Vernetzung der Textilfasern bzw. der Polymerisate erfolgt. Die Trocknung erfolgt zweckmäßig 0,5 bis 3 Minuten bei 110 bis 130 °C. Die Kondensation führt man im allgemeinen einige Minuten bei 150 bis 180 °C durch. Kondensation und Trocknung können auch in einer Stufe erfolgen, beispielsweise durch eine Schockkondensation (STK-Verfahren) bei etwa 130 bis 180 °C (1 bis 5 Minuten).This is followed by drying and a condensation step in which the textile fibers or the polymers are crosslinked. Drying is conveniently carried out at 110 to 130 ° C for 0.5 to 3 minutes. The condensation is generally carried out at 150 to 180 ° C. for a few minutes. Condensation and drying can also take place in one step, for example by shock condensation (STK method) at about 130 to 180 ° C (1 to 5 minutes).
Die nachfolgenden Beispiele erläutern die Erfindung.The following examples illustrate the invention.
In den nachfolgenden Tabellen 1 und 2 ist die Zusammensetzung der zur Anwendung kommenden Mittel sowie der Flotte angegeben. Die Flotte wurde hergestellt, indem die beiden Teile des erfindungsgemäßen Mittels und gegebenenfalls der Stabilisator in die Flotte gegeben wurden.Tables 1 and 2 below show the composition of the agents used and the fleet. The liquor was produced by adding the two parts of the agent according to the invention and optionally the stabilizer to the liquor.
Die auszurüstende Ware wurde in der Flotte foulardiert, auf 80 % Flottenaufnahme abgequetscht und bei der angegebenen Temperatur schockkondensiert.The goods to be equipped were padded in the liquor, squeezed to 80% liquor absorption and shock-condensed at the temperature specified.
Die Eigenschaften der auf diese Weise ausgerüsteten Gewebe wurden anschließend bestimmt. Hierzu wurden die Gewebe 24 Stunden bei Normklima (20 °C/ 65 % relative Luftfeuchtigkeit) gelagert und anschließend den jeweiligen Tests unterzogen. Die Ergebnisse sind in Tabelle 3 zusammengestellt.
Claims (12)
dadurch gekennzeichnet, daß es
OHC-(CH₂)n-CHO
worin
n für 0 bis 10 steht, oder wenigstens ein Reaktionsprodukt aus einem Dialdehyd obiger Formel mit einem linearen aliphatischen Polyol der Formel (I):
R₁-CH (0H) - (CH₂)m-CH(0H)-R₂ I
worin
R₁ und R₂, die gleich oder verschieden sein können, für ein Wasserstoffatom oder eine Methyl-, Ethyl-, n-Propyl- oder Isopropylgruppe stehen und m für 0 bis 4 steht, oder
mit einem verzweigten aliphatischen Polyol der Formel (II):
R₂ für OH, (CH₂)y-CH₃, (CH₂)z-CH₂OH, NO₂steht;
R₄ für H, (CH₂)y-CH₃, (CH₂)z-CH₂OH steht;
x für 0 bis 2 steht;
y für 0 bis 5 steht und
z für 0 bis 2 steht,
oder eine Mischung von Dialdehyd und Reaktionsprodukt,
characterized in that it
OHC- (CH₂) n -CHO
wherein
n represents 0 to 10, or at least one reaction product of a dialdehyde of the above formula with a linear aliphatic polyol of the formula (I):
R₁-CH (0H) - (CH₂) m -CH (0H) -R₂ I
wherein
R₁ and R₂, which may be the same or different, represent a hydrogen atom or a methyl, ethyl, n-propyl or isopropyl group and m represents 0 to 4, or
with a branched aliphatic polyol of the formula (II):
R₂ is OH, (CH₂) y -CH₃, (CH₂) z -CH₂OH, NO₂;
R₄ is H, (CH₂) y -CH₃, (CH₂) z -CH₂OH;
x represents 0 to 2;
y represents 0 to 5 and
z represents 0 to 2,
or a mixture of dialdehyde and reaction product,
HO-(CH₂CH₂O-)k-CH₂CH₂OH,
wobei k für 100 bis 6000 steht.16. Textile finishing agent according to one of the preceding claims, characterized in that it additionally contains a stabilizer which is selected from at least one polyol of the formula (I) or (II) and a polyglycol of the formula
HO- (CH₂CH₂O-) k -CH₂CH₂OH,
where k stands for 100 to 6000.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE19883832089 DE3832089A1 (en) | 1988-09-21 | 1988-09-21 | TEXTILE FINISHING AGENT AND METHOD FOR FINISHING CELLULOSE-CONTAINING TEXTILE GOODS |
| DE3832089 | 1988-09-21 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| EP0360248A2 true EP0360248A2 (en) | 1990-03-28 |
| EP0360248A3 EP0360248A3 (en) | 1992-01-02 |
Family
ID=6363428
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| EP19890117400 Withdrawn EP0360248A3 (en) | 1988-09-21 | 1989-09-20 | Composition for finishing textiles, and process for the treatment of cellulosic textiles |
Country Status (2)
| Country | Link |
|---|---|
| EP (1) | EP0360248A3 (en) |
| DE (1) | DE3832089A1 (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0470613A1 (en) * | 1990-08-10 | 1992-02-12 | OSi Specialties, Inc. | Silicone textile finishes |
| US6043328A (en) * | 1995-05-19 | 2000-03-28 | Novartis Ag | Polysiloxane-polyol macromers, their preparation and their use |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2785996A (en) * | 1955-01-24 | 1957-03-19 | Quaker Chemical Products Corp | Compositions and method of treating textile materials |
| US4472167A (en) * | 1983-08-26 | 1984-09-18 | The United States Of America As Represented By The Secretary Of Agriculture | Mild-cure formaldehyde-free durable-press finishing of cotton textiles with glyoxal and glycols |
-
1988
- 1988-09-21 DE DE19883832089 patent/DE3832089A1/en not_active Withdrawn
-
1989
- 1989-09-20 EP EP19890117400 patent/EP0360248A3/en not_active Withdrawn
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0470613A1 (en) * | 1990-08-10 | 1992-02-12 | OSi Specialties, Inc. | Silicone textile finishes |
| US6043328A (en) * | 1995-05-19 | 2000-03-28 | Novartis Ag | Polysiloxane-polyol macromers, their preparation and their use |
Also Published As
| Publication number | Publication date |
|---|---|
| DE3832089A1 (en) | 1990-03-29 |
| EP0360248A3 (en) | 1992-01-02 |
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