EP0084772A2 - Grafted siloxane dispersions for the finishing of textile materials - Google Patents

Grafted siloxane dispersions for the finishing of textile materials Download PDF

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Publication number
EP0084772A2
EP0084772A2 EP83100041A EP83100041A EP0084772A2 EP 0084772 A2 EP0084772 A2 EP 0084772A2 EP 83100041 A EP83100041 A EP 83100041A EP 83100041 A EP83100041 A EP 83100041A EP 0084772 A2 EP0084772 A2 EP 0084772A2
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Prior art keywords
weight
vinyl
organopolysiloxane
groups
textile
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German (de)
French (fr)
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EP0084772B1 (en
EP0084772A3 (en
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Heinrich Dr. Alberts
Helmut Dr. Steinberger
Wilfried Dipl.-Ing. Kortmann
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Bayer AG
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Bayer AG
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    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
    • D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
    • D06M15/37—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • D06M15/643—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds containing silicon in the main chain
    • 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
    • D06M15/356—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of other unsaturated compounds containing nitrogen, sulfur, silicon or phosphorus atoms
    • D06M15/3568—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of other unsaturated compounds containing nitrogen, sulfur, silicon or phosphorus atoms containing silicon

Definitions

  • the present invention relates to textile finishing agents based on aqueous silicone graft polymer dispersions which are obtained in water by emulsifying graft polymers which contain mixtures of vinyl group-containing polysiloxanes and polymethylhydrogensiloxanes and polymerized units of vinyl monomers as grafted polymer components.
  • Silicones are used in the textile industry as water repellents. Compared to other strongly hydrophobic substances, e.g. Paraffin and waxes, silicones have the advantage that they have no fat character, which has a favorable effect on the "handle" of the treated tissue; that they can be fixed on the fiber in such a way that they withstand a comparatively high degree of washing or solvent treatment of the textile; that they are largely resistant to chemicals and weathering and ultimately have a quite remarkable softening and smoothing effect on the textile.
  • strongly hydrophobic substances e.g. Paraffin and waxes
  • the softening effect of the silicones has such a strong effect on some textiles (cotton, polyester, polyamide) that the treated textile finally becomes soft and lobbed, which can be undesirable for some applications.
  • acrylates or polyacrylates and methacrylates can be used to increase the stiffness of fabrics.
  • these products do not give the textiles the desired elasticity and resilience, even when used in combination with silicones.
  • the object of the invention is achieved in that aqueous finishes of special graft copolymers which are obtained by polymerizing vinyl monomers in the presence of mixtures of polymethylhydrogensiloxanes and vinyl group-containing polysiloxanes are used to finish textile material.
  • the present invention thus relates to textiles Finishing agent containing a graft polymer dispersion consisting of vinyl group-containing diorganopolysiloxane, methylhydrogenpolysiloxane and polymerized units of optionally halogen-containing vinyl and / or (meth) acrylic compounds.
  • Olefins such as ethylene, propylene, isobutylene, vinyl esters of aliphatic or aromatic carboxylic acids, preferably vinyl acetate, vinyl propionate, ⁇ , ⁇ -unsaturated mono- or dicarboxylic acids and their derivatives, mention may be made of (meth) acrylic acid, methyl (meth) acrylate, ethyl (meth) - acrylate, propyl or isopropyl (meth) acrylate, n-butyl, iso- or tert-butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, (meth) acrylamide derivatives, quaternized (meth) acrylamide derivatives, (Meth) acrylonitrile, maleic anhydride, maleic amide, N-alkyl-maleinamides and imides, maleic acid semiester or diesters, vinyl aromatics such as styrene, cC-
  • polyunsaturated vinyl compounds or allyl compounds can be used.
  • Divinylbenzene, (meth) acrylic acid esters of polyhydric alcohols such as e.g. Ethylene glycol dimethacrylate, diethylene glycol diacrylate and divinyl ether, furthermore triallyl cyanurate, triallyl citrate.
  • the mixtures of polymethylhydrogensiloxanes, vinyl group-containing polysiloxanes and vinyl monomers are subjected to radical polymerization with the addition of radical formers and, if appropriate, molecular weight regulators subjected.
  • Stable dispersions are obtained which consist of an organopolysiloxane component and polymerized units of one or more vinyl monomers and which are characterized in that they contain cross-bridged graft polymers of organopolysiloxanes via polymerized units of the vinyl monomers used and some of the Si-H groups of the polymethylhydrogensiloxanes by monoaddition of the used vinyl compounds are modified.
  • graft polymers produced in this way are soluble or dispersible in water; Even with a high silicone content, these polymers can be easily emulsified in water with relatively little emulsifier additives.
  • the radical polymerization of the vinyl monomers can be started in a manner known per se with the aid of radical formers, UV rays, ⁇ -, ⁇ - or ⁇ -rays or thermally without further additives.
  • the radiation-initiated polymerization is preferably carried out in the presence of sensitizers, cf. e.g. A.D. Jenkins, A. Ledwith, Reactivity, Mechanism and Structure in Polymer Chemistry, John Wiley + Son, London, New York, 1974, p. 465.
  • radical formers are used in amounts between 0.001 to 2, preferably 0.02 to 0.8% by weight, based on the total mixture of organopolysiloxane, polyester and vinyl monomers.
  • Azo initiators such as azo-bis-iso-butyronitrile (AIBN), azo esters, azo-imino esters or azo-N-alkyl amides, peroxides such as di-tert-butyl peroxide, di-cumyl peroxide, di-benzoyl peroxide and peresters are examples of radical formers such as amyl perpivalate, tert-butyl perpivalate, tert-butyl peroctoate, tert-butyl perbenzoate, tert-butyl. perneodecanoate, percarbonates such as cyclohexyl percarbonate or bisisopropyl percarbonate or hydroperoxides such as cumyl
  • Suitable initiators are also benzpinacol, benzpinacol derivatives or other thermally labile, highly substituted ethane derivatives.
  • the polymerization can also be started with the help of redox systems at temperatures lower than the purely thermal decomposition temperatures of the radical formers.
  • peroxides and amines such as e.g. Benzoyl peroxide and triethylamine, trialkylboron compounds and oxygen, hydroperoxides and sulfinic acids, formaldehyde or aldoses or combinations with low-quality transition metal salts and sulfur dioxide / peroxide redox systems.
  • the polymerization reaction can be continuous or dis continuously, without pressure or at reaction pressures of up to 300 bar, preferably up to 15 bar, at reaction temperatures between -20 ° C. and + 250 ° C., preferably 70 to 190 ° C.
  • the polymerization can also be carried out in the presence of solvents or diluents, such as water, alcohols such as methanol, ethanol, tert-butanol, aliphatic or aromatic hydrocarbons, halogenated hydrocarbons such as chlorobenzene or fluorinated compounds, ethers such as dioxane or Tetrahydrofuran, esters such as ethyl acetate.
  • solvents or diluents such as water, alcohols such as methanol, ethanol, tert-butanol, aliphatic or aromatic hydrocarbons, halogenated hydrocarbons such as chlorobenzene or fluorinated compounds, ethers such as dioxane or Tetrahydrofuran
  • the polymerization reaction can be carried out in the presence of molecular weight regulators.
  • Mercaptans such as n- or tert-dodecyl mercaptan, thioglycol, thioglycerol or thioacetic acid esters may be mentioned as regulators.
  • sulfur-free molecular weight regulators such as hydrocarbons
  • examples include paraffin fractions such as petroleum ether, light or light petroleum, d / -olefins such as propylene, isobutylene, butene-1, furthermore ketones such as acetone, methyl ethyl ketone or cyclohexanone, furthermore aldehydes such as formaldehyde, acetaldehyde , Propionaldehyde, isobutyraldehyde or allyl compounds such as allyl alcohol, allyl acetate, isobutene diacetate or allyl carbonates.
  • paraffin fractions such as petroleum ether, light or light petroleum
  • d / -olefins such as propylene, isobutylene, butene-1
  • ketones such as acetone, methyl ethyl ketone or cyclohexanone
  • aldehydes such as formaldehyde, ace
  • enol ethers which are derived, on the one hand, from aliphatic or cycloaliphatic aldehydes or ketones and, on the other hand, from alkyl, cycloalkyl or derive aralkyl alcohols.
  • the cycloaliphatic aldehydes or ketones can be substituted or bridged in the ring and / or contain a double bond. Examples include butyraldehyde, valeraldehyde, cyclohexylaldehyde, cyclohexenylaldehyde, bicyclo [2,2,1] hexenylaldehyde and cyclohexanone.
  • Preferred are the cycloaliphatic aldehydes or ketones, which are optionally substituted by one or two C 1 -C 5 alkyl groups, in particular by methyl groups in the ring.
  • Suitable alcohols are C 1 -C 20 -alkanols, which may optionally be branched or unsaturated, and also C 5 -C 10 -cycloalkanols and C 7 -C 20 -aralkyl alcohols, the cycloalkyl or aryl group of which may optionally be substituted by lower alkyl radicals.
  • Examples include methanol, ethanol, n-propanol, isobutanol, 2-ethylhexanol, cyclohexanol and benzyl alcohol.
  • the enol ethers used as molecular weight regulators are used in amounts of 0.01-10% by weight, preferably 0.05-1% by weight, based on the sum of the monomers.
  • the enol ethers can be added at any time during the polymerization, the enol ether used as regulator is preferably added at the start of the polymerization.
  • Also suitable as telogens are halogenated hydrocarbons such as methylene chloride, tetrachloroethane, dibromoethane, etc. As expected, the viscosities of the dispersions can be controlled with the aid of such regulators.
  • the graft polymer dispersions are prepared in such a way that mixtures of a terminally vinyl-functional organopolysiloxane, a methylhydrogenpolysiloxane and one or more vinyl monomers are brought to a reaction temperature which triggers the polymerization in the presence of a radical generator. If desired, mixtures of terminally vinyl-functional and non-functional organopolysiloxanes can also be introduced into the reaction mixture.
  • the polymerization can be carried out by a continuous or batch process. In principle, the order of addition of the components to be reacted is arbitrary, but the best results are achieved if mixtures of vinylsiloxane and hydrogen siloxane and vinyl monomers are used simultaneously in the course of the polymerization reaction.
  • the conversion of the monomers used is determined by the chosen polymerization process and the reaction conditions. In the discontinuous mode of polymerization, the highest possible sales are achieved strives so that at least 80% of the monomers used, but preferably more than 90% are converted.
  • the residual monomers are removed by known methods by distillation at normal pressure or under reduced pressure. The residual monomer contents which were effectively found in the dispersions after working up are negligibly low, they are generally below 1,000 ppm, preferably below 100 ppm.
  • This monoaddition changes the polarity and hydrophobicity of the polysiloxane chain and improves the interaction with the textile substrate.
  • the silicone-vinyl polymer dispersions obtained in accordance with the invention are particularly suitable for the coating and finishing of natural or synthetic fibers, threads or textile fabrics. They give textile objects the voluminous, soft feel that is characteristic of silicone, as well as permanent elasticity and resilience.
  • the silicone-vinyl polymer dispersions obtained according to the invention have an emulsifying behavior which is comparatively more favorable than that of pure silicones of corresponding viscosity.
  • the emulsifiers used advantageously consist of a mixture of a hydrophilic and a hydrophobic component.
  • Suitable compounds are e.g. Fatty acid esters of polyhydric alcohols, e.g. Stearic acid esters of glycols, glycerol or sorbitol, as well as higher fatty alcohols or the adducts of ethylene oxide with these fatty alcohols, fatty acids or similar compounds with an active hydrogen atom.
  • anion-active emulsifiers such as sodium lauryl sulfate or sodium dodecylbenzenesulfonate or cation-active emulsifiers such as quaternary ammonium compounds are also suitable.
  • silicone-vinyl copolymers according to the invention are applied to the substrate to be treated by the known methods, for example by padding, drying and condensing, by spraying or slapping.
  • the silicone graft polymer component can be thermally or catalytically crosslinked, if appropriate with the addition of further reactive silicone derivatives such as e.g. Polymethylhydrogensiloxanen done.
  • the purely thermal crosslinking takes place at temperatures from around 120 ° C.
  • the catalytically activated crosslinking can take place at room temperature.
  • Known systems such as platinum or platinum compounds, organotin compounds but also peroxides or other radical initiators are suitable as catalysts.
  • UV-activated crosslinking can also be carried out successfully. Crosslinking improves the solvent and wash resistance of the equipment. In the case of catalytic crosslinking, it is advisable to use appropriate inhibitors, such as Use acetylene alcohols, especially methylenedinol.
  • the polydiorganosiloxanes are prepared in a manner known per se (cf. W. Noll, "Chemistry and Technology of Silicones", Verlag Chemie, Weinheim / Bergstrasse, 2nd ed., 1968, K ap. 5, p. 162 ff.) .
  • siloxanes listed in the examples are identified as follows:
  • the mixture is stirred for 1 hour and then the volatile constituents are removed by distillation.
  • the mixture is stirred at 150 ° C. for 1 hour, then evacuated and virtually completely freed of unreacted monomers.
  • the graft polymer obtained has a viscosity of 1500 mPas at 25 ° C. and has a composition which corresponds to an 88% monomer conversion.
  • the mixture is stirred at 125 ° C. for 1 hour, carefully released and evacuated. The volatile components are deducted.
  • the graft polymer contains 45% by weight polymerized units made of vinylidene fluoride 22% by weight units made of polysiloxane B 33% by weight units made of polysiloxane C.
  • samples of the cotton shirt poplin are equipped with the graft polymer dispersion according to the invention as follows:
  • the application takes place in the manner described above.
  • DMDHEU dimethyldihydroxyethylene urea
  • acrylate dispersions and plasticizers based on fatty acid amides and / or silicones are added to the finishing liquor.
  • the application is carried out by dipping (picking up liquor 70-100% of the weight of the goods), squeezing and then drying. This is followed by a calendering and condensation step at 140-160 ° C for 4 to 6 minutes.
  • Example 12 In comparison to Example 11, in Example 12 according to the invention the advantageous grip, tear resistance and crease angle remain virtually unchanged even after 5 washes at 60 ° C., while Example 11 after 5 washes under the same conditions shows marked deteriorations in the handle (rough, empty) and marked deterioration of tear resistance and crease angle.
  • a 100% co-circular knitted fabric (100 kg) structured in the longitudinal direction is dyed with reaction dyes on a nozzle dyeing machine, rinsed hot and cold several times and soaped at cooking temperature; so that all unfixed dye components are removed.
  • the last rinsing bath remains in the machine.
  • 2 kg of a head graft polymer dispersion according to the invention from Example 4 (corresponds to 2% of WG.) are passed through a batch vessel.
  • the pH of the rinsing liquor was previously adjusted to 6.0 with acetic acid.
  • the treatment bath is at 1 ° C / min. heated to 35 ° C. After reaching the final temperature, the goods remain for 15 minutes. in the equipment fleet.
  • the liquor is then drained off, the goods are removed from the dyeing apparatus and dried continuously at 125 ° C.
  • the handle of the treated goods is full, soft and smooth.

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Textile Engineering (AREA)
  • Graft Or Block Polymers (AREA)
  • Silicon Polymers (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
  • Silicon Compounds (AREA)
  • Pens And Brushes (AREA)
  • Curing Cements, Concrete, And Artificial Stone (AREA)

Abstract

Die vorliegende Erfindung betrifft ein Textilausrüstungsmittel, enthaltend eine Pfropfpolymerisatdispersion, die aus A. einem vinylgruppenhaltigen Organopolysiloxan, B. einem Organopolysiloxan mit Si-H-Gruppen und C. polymerisierten Einheiten aus Vinylmonomeren besteht. Dabei ist ein Teil der Organopolysiloxankomponenten über polymerisierte Einheiten der eingesetzten Vinylmonomeren verknüpft und ein Teil der Si-H-Gruppen des Si-H-Organopolysiloxans durch Monoaddition der eingesetzten Vinylverbindungen modifiziert.The present invention relates to a textile finishing agent containing a graft polymer dispersion which consists of A. an organopolysiloxane containing vinyl groups, B. an organopolysiloxane with Si-H groups and C. polymerized units of vinyl monomers. Some of the organopolysiloxane components are linked via polymerized units of the vinyl monomers used and some of the Si-H groups of the Si-H organopolysiloxane are modified by monoaddition of the vinyl compounds used.

Description

Die vorliegende Erfindung betrifft Textilausrüstungsmittel auf Basis wäßriger Siliconpfropfpolymerisatdispersionen, die durch Emulgierung von Pfropfpolymerisaten, die als Pfropfsubstrat Gemische aus vinylgruppenhaltigen Polysiloxanen und Polymethylhydrogensiloxanen und als aufgepfropfte Polymerkomponente polymerisierte Einheiten aus Vinylmonomeren enthalten, in Wasser erhalten werden.The present invention relates to textile finishing agents based on aqueous silicone graft polymer dispersions which are obtained in water by emulsifying graft polymers which contain mixtures of vinyl group-containing polysiloxanes and polymethylhydrogensiloxanes and polymerized units of vinyl monomers as grafted polymer components.

Silicone werden in der Textilindustrie als Hydrophobiermittel verwendet. Gegenüber anderen stark hydrophoben Substanzen, z.B. Paraffin und Wachsen, besitzen Silicone den Vorteil, daß sie keinen Fettcharakter haben, was sich günstig auf den "Griff" des behandelten Gewebes auswirkt; daß sie auf der Faser derart fixierbar sind, daß sie in vergleichsweise hohem Maße einer Wäsche oder Lösungsmittelbehandlung des Textils standhalten; daß sie weitgehend chemikalien- und witterungsbeständig sind und schließlich auf das Textil eine recht beachtliche weichmachende und glättende Wirkung ausüben.Silicones are used in the textile industry as water repellents. Compared to other strongly hydrophobic substances, e.g. Paraffin and waxes, silicones have the advantage that they have no fat character, which has a favorable effect on the "handle" of the treated tissue; that they can be fixed on the fiber in such a way that they withstand a comparatively high degree of washing or solvent treatment of the textile; that they are largely resistant to chemicals and weathering and ultimately have a quite remarkable softening and smoothing effect on the textile.

Der weichmachende Effekt der Silicone wirkt sich auf einigen Textilien (Baumwolle, Polyester, Polyamid) jedoch so stark aus, daß sich das behandelte Textil schließlich weich und lappig angreift, was für manche Anwendungen unerwünscht sein kann.However, the softening effect of the silicones has such a strong effect on some textiles (cotton, polyester, polyamide) that the treated textile finally becomes soft and lobbed, which can be undesirable for some applications.

Vielmehr werden Rückstellvermögen und eine gewisse Elastizität des behandelten Gewebes gefordert.Rather, resilience and a certain elasticity of the treated tissue are required.

Nach dem Stande der Technik kann man zur Erhöhung der Steifigkeit von Geweben Acrylate bzw. Polyacrylate und -Methacrylate einsetzen. Diese Produkte verleihen den Textilien aber nicht die erwünschte Elastizität und das Rückstellvermögen, auch dann nicht, wenn man sie in Kombination mit Siliconen anwendet.In the prior art, acrylates or polyacrylates and methacrylates can be used to increase the stiffness of fabrics. However, these products do not give the textiles the desired elasticity and resilience, even when used in combination with silicones.

Es war daher Aufgabe der vorliegenden Erfindung, Ausrüstungsmittel zu entwickeln, die textilen flächigen oder faserigen Gebilden sowohl Sprungelastizität als auch ein gewisses Rückstellvermögen bei gleichzeitiger weicher und volumiger Griffgebung verleihen.It was therefore an object of the present invention to develop finishing agents which give textile sheet-like or fibrous structures both resilience and a certain resilience with a soft and voluminous feel at the same time.

Die erfindungsgemäße Aufgabe wird dadurch gelöst, daß man zur Ausrüstung von textilem Material wäßrige Dispersionen von speziellen Pfropfcopolymeren einsetzt, die durch Polymerisation von Vinylmonomeren in Gegenwart von Mischungen aus Polymethylhydrogensiloxanen und vinylgruppenhaltigen Polysiloxanen erhalten werden.The object of the invention is achieved in that aqueous finishes of special graft copolymers which are obtained by polymerizing vinyl monomers in the presence of mixtures of polymethylhydrogensiloxanes and vinyl group-containing polysiloxanes are used to finish textile material.

Gegenstand der vorliegenden Erfindung sind somit Textilausrüstungsmittel, enthaltend eine Pfropfpolymerisatdispersion die aus vinylgruppenhaltigen Diorganopolysiloxan, Methylhydrogenpolysiloxan und polymerisierten Einheiten aus gegebenenfalls-Halogen enthaltenden Vinyl-und/oder (Meth)Acrylverbindungen bestehen.The present invention thus relates to textiles Finishing agent containing a graft polymer dispersion consisting of vinyl group-containing diorganopolysiloxane, methylhydrogenpolysiloxane and polymerized units of optionally halogen-containing vinyl and / or (meth) acrylic compounds.

Die Pfropfmodifizierung von Organopolysiloxanen mit Vinylmonomeren wird beispielsweise in den Patentschriften GB 766 528, GB 806 582, GB 869 482 und DAS 1 694 973 beschrieben. Ferner ist aus US 4 166 078 bekannt, Si-H-Siloxane durch Pfropfung mit Vinylmonomeren zu modifizieren. Weiterhin wird in US 4 172 101 die Pfropfmodifizierung von vinylsubstituierten Polysiloxanen beschrieben.The graft modification of organopolysiloxanes with vinyl monomers is described for example in the patents GB 766 528, GB 806 582, GB 869 482 and DAS 1 694 973. It is also known from US Pat. No. 4,166,078 to modify Si-H-siloxanes by grafting with vinyl monomers. US Pat. No. 4,172,101 also describes the graft modification of vinyl-substituted polysiloxanes.

Ferner wird in W. Noll "Chemie und Technologie der Silicone"; Verlag Chemie, Weinheim, Bergstr. 2. Auflage (1968), S. 391 beschrieben, daß durch Kombination von Si-H-Siloxanen mit Si-Vinylsiloxanen. in Gegenwart von Radikalbildnern vernetzte Produkte erhalten werden.Furthermore, W. Noll "Chemistry and Technology of Silicones"; Verlag Chemie, Weinheim, Bergstr. 2nd edition (1968), p. 391 describes that by combining Si-H-siloxanes with Si-vinylsiloxanes. crosslinked products are obtained in the presence of radical formers.

überraschenderweise wurde gefunden, daß bei der radikalischen Polymerisation von Vinylmonomeren in Gegenwart von Mischungen aus Si-H-Siloxanen und Si-Vinylsiloxanen unvernetzte, zum Teil niedrigviskose Pfropfpolymerisate erhalten werden.Surprisingly, it was found that in the free-radical polymerization of vinyl monomers in the presence of mixtures of Si-H-siloxanes and Si-vinylsiloxanes, uncrosslinked, partly low-viscosity graft polymers are obtained.

Die Pfropfpolymerisate enthalten A) Polymethylhydrogensiloxane der allgemeinen Formel

Figure imgb0001
worin

  • a eine ganze Zahl zwischen 1 und 120,
  • b eine ganze Zahl zwischen 0 und 140 und
  • X eine Methylgruppe oder Wasserstoff bedeutet.
  • B) vinylgruppenhaltige Polysiloxane der Formel
    Figure imgb0002
    worin
  • R' ausgewählt ist aus Alkylresten mit 1 bis 32 Kohlenstoffatomen, Arylreste, Vinylresten und Fluoralkylresten mit 3 bis 18 Kohlenstoffatomen, so daß das Polymer 0.0002 bis 3 Gew.-% Vinyl enthält und c einen Wert hat, daß die Viskosität des Polymers von 100 bis 1 000 000 mPa.s bei 25°C variiert.
  • C) Vinylmonomere, für die beispielhaft aufgeführt seien:'
The graft polymers contain A) polymethylhydrogensiloxanes of the general formula
Figure imgb0001
 wherein
  • a is an integer between 1 and 120,
  • b is an integer between 0 and 140 and
  • X represents a methyl group or hydrogen.
  • B) vinyl group-containing polysiloxanes of the formula
    Figure imgb0002
     wherein
  • R 'is selected from alkyl groups with 1 to 32 carbon atoms, aryl groups, vinyl groups and fluoroalkyl groups with 3 to 18 carbon atoms, so that the polymer contains 0.0002 to 3% by weight of vinyl and c has a value such that the viscosity of the polymer is from 100 to 1,000,000 mPa.s at 25 ° C varies.
  • C) vinyl monomers, for example: '

Olefine wie Ethylen, Propylen, Isobutylen, Vinylester aliphatischer oder aromatischer Carbonsäuren, vorzugsweise Vinylacetat, Vinylpropionat, α,β-ungesättigte Mono-oder Dicarbonsäuren und ihre Derivate, erwähnt seien (Meth)acrylsäure, Methyl(meth)acrylat, Ethyl(meth)-acrylat, Propyl- bzw. isopropyl(meth)acrylat, n-Butyl-, iso- oder tert.-Butyl(meth)acrylat, 2-Ethylhexyl(meth)-acrylat, (Meth)acrylamidderivate, quaternisierte (Meth)-acrylamidderivate, (Meth)Acrylnitril, Maleinsäureanhydrid, Maleinsäureamid, N-Alkyl-Maleinamide und -imide, Maleinsäure-halb- oder -diester, Vinylaromaten wie Styrol, cC-Methylstyrol, 4-Chlorstyrol, Vinylchlorid, Vinylidenchlorid, Vinylidenfluorid, Tetrafluorethylen, Vinylether wie Ethylvinylether oder n-Butylvinylether; aus der Reihe der Allylverbindungen seien angeführt Allylalkohol, Allylacetat, Isobutendiacetat, 2-Methylenpropandiol-1,3, Allylethylcarbonat, Allylphenylcarbonat. Falls die Vernetzung oder Erhöhung der Molekulargewichte der Vinylharzphase gewünscht wird, können mehrfach ungesättigte Vinylverbindungen oder Allylverbindungen eingesetzt werden. Erwähnt seien Divinylbenzol, (Meth)Acrylsäureester mehrwertiger Alkohole wie z.B. Ethylenglykoldimethacrylat, Diethylenglykoldiacrylat und Divinylether, ferner Triallylcyanurat, Triallylcitrat.Olefins such as ethylene, propylene, isobutylene, vinyl esters of aliphatic or aromatic carboxylic acids, preferably vinyl acetate, vinyl propionate, α, β-unsaturated mono- or dicarboxylic acids and their derivatives, mention may be made of (meth) acrylic acid, methyl (meth) acrylate, ethyl (meth) - acrylate, propyl or isopropyl (meth) acrylate, n-butyl, iso- or tert-butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, (meth) acrylamide derivatives, quaternized (meth) acrylamide derivatives, (Meth) acrylonitrile, maleic anhydride, maleic amide, N-alkyl-maleinamides and imides, maleic acid semiester or diesters, vinyl aromatics such as styrene, cC-methylstyrene, 4-chlorostyrene, vinyl chloride, vinylidene chloride, vinylidene fluoride, tetrafluoroethylene, vinyl ethers such as ethyl vinyl ether or n-butyl vinyl ether; Allyl alcohol, allyl acetate, isobutene diacetate, 2-methylene-propanediol-1,3, allyl ethyl carbonate, allyl phenyl carbonate are mentioned from the series of allyl compounds. If it is desired to crosslink or increase the molecular weights of the vinyl resin phase, polyunsaturated vinyl compounds or allyl compounds can be used. Divinylbenzene, (meth) acrylic acid esters of polyhydric alcohols such as e.g. Ethylene glycol dimethacrylate, diethylene glycol diacrylate and divinyl ether, furthermore triallyl cyanurate, triallyl citrate.

Die Mischungen aus Polymethylhydrogensiloxanen, vinylgruppenhaltigen Polysiloxanen und Vinylmonomeren werden unter Zusatz von Radikalbildnern und gegebenenfalls Molekulargewichtsreglern einer radikalischen Polymerisation unterzogen. Man erhält stabile Dispersionen, die aus einer Organopolysiloxankomponente und polymerisierten Einheiten eines oder mehrerer Vinylmonomerer bestehen und die dadurch gekennzeichnet sind, daß sie über polymerisierte Einheiten der eingesetzten Vinylmonomeren querverbrückte Pfropfpolymere aus Organopolysiloxanen enthalten und ein Teil der Si-H-Gruppen der Polymethylhydrogensiloxane durch Monoaddition der eingesetzten Vinylverbindungen modifiziert sind. Solchermaßen hergestellte Pfropfpolymere sind, je nach Zusammensetzung, in Wasser löslich oder dispergierbar; auch bei hohem Silicongehalt lassen sich diese Polymeren durch relativ wenig Emulgatorzusätze leicht in Wasser emulgieren.The mixtures of polymethylhydrogensiloxanes, vinyl group-containing polysiloxanes and vinyl monomers are subjected to radical polymerization with the addition of radical formers and, if appropriate, molecular weight regulators subjected. Stable dispersions are obtained which consist of an organopolysiloxane component and polymerized units of one or more vinyl monomers and which are characterized in that they contain cross-bridged graft polymers of organopolysiloxanes via polymerized units of the vinyl monomers used and some of the Si-H groups of the polymethylhydrogensiloxanes by monoaddition of the used vinyl compounds are modified. Depending on the composition, graft polymers produced in this way are soluble or dispersible in water; Even with a high silicone content, these polymers can be easily emulsified in water with relatively little emulsifier additives.

Die erfindungsgemäß verwendeten wasserlöslichen oder wasserdispergierbaren Organopolysiloxan-Pfropfpolymeren bestehen aus:

  • 1. 15 bis 95 Gew.-% eines Pfropfsubstrates, bestehend aus
    • A. 5 bis 95 Gew.-% Vinylgruppen enthaltenden Diorganopolysiloxan und
    • B. 5 bis 95 Gew.-% Methylhydrogenpolysiloxan und
  • 2. 85 bis 5 Gew.-% polymerisierten Einheiten aus Vinylverbindungen,

wobei die Summe der Komponenten 1. und 2. stets 100 % beträgt.The water-soluble or water-dispersible organopolysiloxane graft polymers used according to the invention consist of:
  • 1. 15 to 95 wt .-% of a graft substrate consisting of
    • A. 5 to 95 wt .-% vinyl groups containing diorganopolysiloxane and
    • B. 5 to 95 wt .-% methylhydrogenpolysiloxane and
  • 2. 85 to 5% by weight of polymerized units of vinyl compounds,

the sum of components 1. and 2. is always 100%.

Vorzugsweise enthalten die erfindungsgemäßen wäßrigen Polysiloxanzubereitungen Pfropfpolymerisatdispersionen

  • 1. 40-90 Gew.-% eines Pfropfsubstrates bestehend aus
    • a) 20-80 Gew.-% Vinylgruppen enthaltenden Diorganopolysiloxan
    • b) 80-20 Gew.-% Polymethylhydrogensiloxan und
  • 2. als zumindest teilweise aufgepfropfte Polymerphase 60 bis 10 Gew.-% polymerisierten Einheiten aus n-Butylacrylat

wobei die Summe der Komponenten stets 100 Gew.-% beträgt.The aqueous polysiloxane preparations according to the invention preferably contain graft polymer dispersions
  • 1. 40-90 wt .-% of a graft substrate consisting of
    • a) 20-80% by weight of vinyl groups-containing diorganopolysiloxane
    • b) 80-20% by weight of polymethylhydrogensiloxane and
  • 2. 60 to 10% by weight of polymerized units of n-butyl acrylate as the at least partially grafted polymer phase

the sum of the components always being 100% by weight.

Die radikalische Polymerisation der Vinylmonomeren kann in an und für sich bekannter Weise mit Hilfe von Radikalbildnern, UV-Strahlen, α-, ß- oder γ-Strahlen oder thermisch ohne weitere Zusätze gestartet werden. Die strahlungsinitiierte Polymerisation wird vorzugsweise in Gegenwart von Sensibilisatoren durchgeführt, vgl. z.B. A.D. Jenkins, A. Ledwith, Reactivity, Mechanism and Structure in Polymer Chemistry, John Wiley + Son, London, New York, 1974, S. 465.The radical polymerization of the vinyl monomers can be started in a manner known per se with the aid of radical formers, UV rays, α-, β- or γ-rays or thermally without further additives. The radiation-initiated polymerization is preferably carried out in the presence of sensitizers, cf. e.g. A.D. Jenkins, A. Ledwith, Reactivity, Mechanism and Structure in Polymer Chemistry, John Wiley + Son, London, New York, 1974, p. 465.

Um die radikalische Polymerisation der Vinylmonomeren zu starten, werden Radikalbildner in Mengen zwischen 0,001 bis 2, vorzugsweise 0,02 bis 0,8 Gew.-% bezogen auf die Gesamtmischung aus Organopolysiloxan, Polyester und Vinylmonomeren eingesetzt. Als Radikalbildner seien beispielhaft aufgeführt Azo-Initiatoren wie Azo-bis-iso-buttersäurenitril (AIBN), Azoester, Azo-Iminoester oder Azo-N-Alkylamide, Peroxide wie di- tert.-Butylperoxid, di-Cumylperoxid, di-Benzoylperoxid, Perester wie Amylperpivalat, tert.-Butylperpivalat, tert.-Butylperoctoat, tert.-Butylperbenzoat, tert.-Butyl-. perneodecanoat, Percarbonate wie Cyclohexylpercarbonat oder Bisisopropylpercarbonat oder Hydroperoxide wie z.B. Cumylhydroperoxid, tert.-Butylhydroperoxid.In order to start the radical polymerization of the vinyl monomers, radical formers are used in amounts between 0.001 to 2, preferably 0.02 to 0.8% by weight, based on the total mixture of organopolysiloxane, polyester and vinyl monomers. Azo initiators such as azo-bis-iso-butyronitrile (AIBN), azo esters, azo-imino esters or azo-N-alkyl amides, peroxides such as di-tert-butyl peroxide, di-cumyl peroxide, di-benzoyl peroxide and peresters are examples of radical formers such as amyl perpivalate, tert-butyl perpivalate, tert-butyl peroctoate, tert-butyl perbenzoate, tert-butyl. perneodecanoate, percarbonates such as cyclohexyl percarbonate or bisisopropyl percarbonate or hydroperoxides such as cumyl hydroperoxide, tert-butyl hydroperoxide.

Geeignete Initiatoren sind ferner Benzpinakol, Benzpinakolderivate oder andere thermisch labile hochsubstituierte Ethanderivate.Suitable initiators are also benzpinacol, benzpinacol derivatives or other thermally labile, highly substituted ethane derivatives.

Die Polymerisation kann ferner mit Hilfe von Redoxsystemen bei tieferen Temperaturen als den rein thermischen Zerfalltemperaturen der Radikalbildner entspricht, gestartet werden.The polymerization can also be started with the help of redox systems at temperatures lower than the purely thermal decomposition temperatures of the radical formers.

Als Redox-Initiatoren seien beispielhaft erwähnt Kombinationen aus Peroxiden und Aminen, wie z.B. Benzoylperoxid und Triethylamin, Trialkylborverbindungen und Sauerstoff, Hydroperoxide und Sulfinsäuren, Formaldehyd oder Aldosen oder Kombinationen mit niederwertigen übergangsmetallsalzen und Schwefeldioxid/Peroxid-Redoxsysteme.Combinations of peroxides and amines, such as e.g. Benzoyl peroxide and triethylamine, trialkylboron compounds and oxygen, hydroperoxides and sulfinic acids, formaldehyde or aldoses or combinations with low-quality transition metal salts and sulfur dioxide / peroxide redox systems.

Die Polymerisationsreaktion kann kontinuierlich oder diskontinuierlich, drucklos oder bei Reaktionsdrucken bis z.B. 300 bar, vorzugsweise bis 15 bar, bei Reaktionstemperaturen zwischen -20°C und +250°C, vorzugsweise 70 bis 190°C, durchgeführt werden. Falls erwünscht, kann die Polymerisation auch in Gegenwart von Lösungsmitteln oder Verdünnungsmitteln durchgeführt werden, genannt seien Wasser, Alkohole, wie Methanol, Ethanol, tert.-Butanol, aliphatische oder aromatische Kohlenwasserstoffe, Halogen-Kohlenwasserstoffe wie Chlorbenzol oder fluorierte Verbindungen, Ether wie Dioxan oder Tetrahydrofuran, Ester wie z.B. Essigsäureethylester. Vorzugsweise wird die Polymerisation aber lösungsmittelfrei durchgeführt.The polymerization reaction can be continuous or dis continuously, without pressure or at reaction pressures of up to 300 bar, preferably up to 15 bar, at reaction temperatures between -20 ° C. and + 250 ° C., preferably 70 to 190 ° C. If desired, the polymerization can also be carried out in the presence of solvents or diluents, such as water, alcohols such as methanol, ethanol, tert-butanol, aliphatic or aromatic hydrocarbons, halogenated hydrocarbons such as chlorobenzene or fluorinated compounds, ethers such as dioxane or Tetrahydrofuran, esters such as ethyl acetate. However, the polymerization is preferably carried out without solvents.

Falls gewünscht, kann die Polymerisationsreaktion in Gegenwart von Molekulargewichtsreglern durchgeführt werden. Als Regler seien aufgeführt Mercaptane, wie n- oder tert.-Dodecylmercaptan, Thioglykol, Thioglycerin oder Thioessigsäureester. Ferner schwefelfreie Molekulargewichtsregler wie Kohlenwasserstoffe, beispielhaft seien genannt Paraffinfraktionen wie z.B. Petrolether, Leicht- oder Waschbenzin, d/-Olefine wie z.B. Propylen, Isobutylen, Buten-1, ferner Ketone wie z.B. Aceton, Methylethylketon oder Cyclohexanon, ferner Aldehyde wie z.B. Formaldehyd, Acetaldehyd, Propionaldehyd, Isobutyraldehyd oder Allylverbindungen wie z.B. Allylalkohol, Allylacetat, Isobutendiacetat oder Allylcarbonate. Für das erfindungsgemäße Verfahren sind Enolether geeignet, die sich einerseits von aliphatischen oder cycloaliphatischen Aldehyden oder Ketonen und andererseits von Alkyl-, Cycloalkyl-oder Aralkylalkohole ableiten. Die cycloaliphatischen Aldehyde oder Ketone können im Ring substituiert oder überbrückt sein und/oder eine Doppelbindung enthalten. Beispielhaft seien Butyraldehyd, Valeraldehyd, Cyclohexylaldehyd, Cyclohexenylaldehyd, Bicyclo-[2,2,1]-hexenylaldehyd und Cyclohexanon genannt. Bevorzugt sind die cycloaliphatischen Aldehyde oder Ketone, die gegebenenfalls durch eine oder zwei C1-C5-Alkylgruppen, insbesondere durch Methylgruppem im Ring substituiert sind.If desired, the polymerization reaction can be carried out in the presence of molecular weight regulators. Mercaptans such as n- or tert-dodecyl mercaptan, thioglycol, thioglycerol or thioacetic acid esters may be mentioned as regulators. Furthermore, sulfur-free molecular weight regulators such as hydrocarbons, examples include paraffin fractions such as petroleum ether, light or light petroleum, d / -olefins such as propylene, isobutylene, butene-1, furthermore ketones such as acetone, methyl ethyl ketone or cyclohexanone, furthermore aldehydes such as formaldehyde, acetaldehyde , Propionaldehyde, isobutyraldehyde or allyl compounds such as allyl alcohol, allyl acetate, isobutene diacetate or allyl carbonates. Suitable for the process according to the invention are enol ethers which are derived, on the one hand, from aliphatic or cycloaliphatic aldehydes or ketones and, on the other hand, from alkyl, cycloalkyl or derive aralkyl alcohols. The cycloaliphatic aldehydes or ketones can be substituted or bridged in the ring and / or contain a double bond. Examples include butyraldehyde, valeraldehyde, cyclohexylaldehyde, cyclohexenylaldehyde, bicyclo [2,2,1] hexenylaldehyde and cyclohexanone. Preferred are the cycloaliphatic aldehydes or ketones, which are optionally substituted by one or two C 1 -C 5 alkyl groups, in particular by methyl groups in the ring.

Geeignete Alkohole sind C1-C20-Alkanole, die gegebenenfalls verzweigt oder ungesättigt sein können, sowie c5-C10-Cycloalkanole und C7-C20-Aralkylalkohole, deren Cycloalkyl- bzw. Arylgruppe gegebenenfalls durch niedere Alkylreste substituiert sein können. Als Beispiele seien Methanol, Ethanol, n-Propanol, Isobutanol, 2-Ethylhexanol, Cyclohexanol und Benzylalkohol genannt.Suitable alcohols are C 1 -C 20 -alkanols, which may optionally be branched or unsaturated, and also C 5 -C 10 -cycloalkanols and C 7 -C 20 -aralkyl alcohols, the cycloalkyl or aryl group of which may optionally be substituted by lower alkyl radicals. Examples include methanol, ethanol, n-propanol, isobutanol, 2-ethylhexanol, cyclohexanol and benzyl alcohol.

Die Herstellung von Enolethern ist ausführlich in der Literatur beschrieben, zum Beispiel in Houben-Weyl, Methoden der Organischen Chemie, Band VI/3. Seite 90, Georg Thieme Verlag, Stuttgart, 1965.The preparation of enol ethers is described in detail in the literature, for example in Houben-Weyl, Methods of Organic Chemistry, Volume VI / 3. Page 90, Georg Thieme Verlag, Stuttgart, 1965.

Die als Molekulargewichtsregler verwendeten Enolether werden in Mengen von 0,01-10 Gew.-%, vorzugsweise von 0,05-1 Gew.-%, bezogen auf die Summe der Monomeren, eingesetzt. Die Zugabe der Enolether während der Polymerisation kann zu jedem beliebigen Zeitpunkt erfolgen, vorzugsweise wird der als Regler verwendete Enolether zu Beginn der Polymerisation zugesetzt. Als Telogene kommen ferner in Frage Halogenkohlenwasserstoffe wie Methylenchlorid, Tetrachlorethan, Dibromethan usw. Wie zu erwarten, lassen sich mit Hilfe derartiger Regler die Viskositäten der Dispersionen steuern.The enol ethers used as molecular weight regulators are used in amounts of 0.01-10% by weight, preferably 0.05-1% by weight, based on the sum of the monomers. The enol ethers can be added at any time during the polymerization, the enol ether used as regulator is preferably added at the start of the polymerization. Also suitable as telogens are halogenated hydrocarbons such as methylene chloride, tetrachloroethane, dibromoethane, etc. As expected, the viscosities of the dispersions can be controlled with the aid of such regulators.

Die Herstellung der Pfropfpolymerisatdispersionen geschieht in der Weise, daß Mischungen aus einem endständig Vinyl-funktionellen Organopolysiloxan, einem Methylhydrogenpolysiloxan und einem oder mehrerer Vinylmonomerer in Gegenwart eines Radikalbildners auf eine, die Polymerisation auslösende, Reaktionstemperatur gebracht werden. Falls gewünscht, können auch Mischungen aus endständig vinylfunktionellen und nichtfunktionellen Organopolysiloxanen in die Reaktionsmischung eingetragen werden. Die Polymerisation kann nach kontinuierlichem oder diskontinuierlichem Verfahren durchgeführt werden. Im Prinzip ist die Reihenfolge der Zugabe der zur Reaktion zu bringenden Komponenten beliebig, die besten Resultate werden aber erzielt, wenn Mischungen aus Vinylsiloxan- und Hydrogensiloxan und Vinylmonomeren gleichzeitig bei der Durchführung der Polymerisationsreaktion eingesetzt werden.The graft polymer dispersions are prepared in such a way that mixtures of a terminally vinyl-functional organopolysiloxane, a methylhydrogenpolysiloxane and one or more vinyl monomers are brought to a reaction temperature which triggers the polymerization in the presence of a radical generator. If desired, mixtures of terminally vinyl-functional and non-functional organopolysiloxanes can also be introduced into the reaction mixture. The polymerization can be carried out by a continuous or batch process. In principle, the order of addition of the components to be reacted is arbitrary, but the best results are achieved if mixtures of vinylsiloxane and hydrogen siloxane and vinyl monomers are used simultaneously in the course of the polymerization reaction.

Die Umsetzung der eingesetzten Monomeren wird vom gewählten Polymerisationsverfahren und den Reaktionsbedingungen bestimmt. Bei der diskontinuierlichen Polymerisationsweise werden möglichst hohe Umsätze angestrebt, so daß mindestens 80 % der eingesetzten Monomeren, vorzugsweise aber mehr als 90 % umgesetzt werden. Die Entfernung der Restmonomeren erfolgt nach bekannten Verfahren destillativ bei Normaldruck oder unter vermindertem Druck. Die nach der Aufarbeitung in den Dispersionen noch effektiv gefundenen Restmonomergehalte sind vernachlässigbar gering, sie liegen im allgemeinen unter 1 000 ppm, vorzugsweise unter 100 ppm.The conversion of the monomers used is determined by the chosen polymerization process and the reaction conditions. In the discontinuous mode of polymerization, the highest possible sales are achieved strives so that at least 80% of the monomers used, but preferably more than 90% are converted. The residual monomers are removed by known methods by distillation at normal pressure or under reduced pressure. The residual monomer contents which were effectively found in the dispersions after working up are negligibly low, they are generally below 1,000 ppm, preferably below 100 ppm.

Im Verlaufe der radikalischen Pfropfreaktion findet neben der Polymerisation und Pfropfpolymerisation der Vinylmonomeren auch eine Monoaddition der Vinylmonomeren an die Si-H-Funktion der Methyl-H-Siloxane statt, etwa nach folgendem Reaktionsschema:

Figure imgb0003
In the course of the radical graft reaction, in addition to the polymerization and graft polymerization of the vinyl monomers, there is also a monoaddition of the vinyl monomers to the Si-H function of the methyl-H-siloxanes, for example according to the following reaction scheme:
Figure imgb0003

Durch diese Monoaddition wird die Polarität und Hydrophobie der Polysiloxankette verändert und die Wechselwirkung mit dem textilen Substrat verbessert.This monoaddition changes the polarity and hydrophobicity of the polysiloxane chain and improves the interaction with the textile substrate.

Die erfindungsgemäß erhaltenen Silicon-Vinylpolymer-Dispersionen sind besonders geeignet für die Beschichtung und die Ausrüstung von natürlichen oder synthetischen Fasern, Fäden oder textilen Flächengebilden. Sie verleihen textilen Gegenständen sowohl den für Silicon charakteristischen voluminösen weichen Griff als auch eine permanente Elastizität und Rückstellvermögen.The silicone-vinyl polymer dispersions obtained in accordance with the invention are particularly suitable for the coating and finishing of natural or synthetic fibers, threads or textile fabrics. They give textile objects the voluminous, soft feel that is characteristic of silicone, as well as permanent elasticity and resilience.

Die erfindungsgemäß erhaltenen Silicon-Vinyl-Polymer-Dispersionen besitzen ein gegenüber reinen Siliconen entsprechender Viskosität vergleichsweise günstigeres Emulgierverhalten.The silicone-vinyl polymer dispersions obtained according to the invention have an emulsifying behavior which is comparatively more favorable than that of pure silicones of corresponding viscosity.

Sie lassen sich relativ leicht mit Hilfe der bekannten Emulgatoren und Emulgiertechniken in stabile Emulsionen überführen.They can be converted relatively easily into stable emulsions with the aid of the known emulsifiers and emulsification techniques.

Die verwendeten Emulgatoren bestehen zweckmäßigerweise aus einer Mischung einer hydrophilen und einer hydrophoben Komponente. Geeignete Verbindungen sind z.B. Fettsäureester mehrwertiger Alkohole, wie z.B. Stearinsäureester von Glykolen, Glycerin oder Sorbit, sowie höhere Fettalkohole oder die Anlagerungsprodukte von Ethylenoxid an diese Fettalkohole, Fettsäuren oder ähnliche Verbindungen mit aktivem Wasserstoffatom. Geeignet sind aber auch anionaktive Emulgatoren wie Natriumlaurylsulfat oder Natriumdodecylbenzolsulfonat oder auch kationaktive Emulgatoren wie quaternäre Ammoniumverbindungen.The emulsifiers used advantageously consist of a mixture of a hydrophilic and a hydrophobic component. Suitable compounds are e.g. Fatty acid esters of polyhydric alcohols, e.g. Stearic acid esters of glycols, glycerol or sorbitol, as well as higher fatty alcohols or the adducts of ethylene oxide with these fatty alcohols, fatty acids or similar compounds with an active hydrogen atom. However, anion-active emulsifiers such as sodium lauryl sulfate or sodium dodecylbenzenesulfonate or cation-active emulsifiers such as quaternary ammonium compounds are also suitable.

Die Aufbringung der erfindungsgemäßen Silicon-Vinyl-Copolymere auf das zu behandelnde Substrat erfolgt nach den bekannten Methoden beispielsweise durch Foulardieren, Trocknen und Kondensieren, durch Sprühen oder Pflatschen.The silicone-vinyl copolymers according to the invention are applied to the substrate to be treated by the known methods, for example by padding, drying and condensing, by spraying or slapping.

Nach dem Auftragen der erfindungsgemäßen wäßrigen Siliconpfropfpolymerdispersion auf das textile Substrat, kann thermisch oder katalytisch eine Vernetzung der Siliconpfropfpolymerkomponente, gegebenenfalls unter Zusatz weiterer reaktiver Silikonderivate wie z.B. Polymethylhydrogensiloxanen erfolgen. Die rein thermische Vernetzung erfolgt bei Temperaturen ab etwa 120°C. Die katalytisch aktivierte Vernetzung kann bereits bei Raumtemperatur erfolgen. Als Katalysatoren kommen die bekannten Systeme wie Platin oder Platinverbindungen, Organozinnverbindungen aber auch Peroxide oder andere Radikalstarter in Frage. Mit Erfolg kann auch eine UV-Strahlen aktivierte Vernetzung durchgeführt werden. Durch die Vernetzung wird die Lösungsmittel- und Waschbeständigkeit der Ausrüstung verbessert. Bei der katalytischen Vernetzung empfiehlt es sich, entsprechende Inhibitoren, wie z.B. Acetylenalkohole, insbesondere Methylentinol, einzusetzen.After the aqueous silicone graft polymer dispersion according to the invention has been applied to the textile substrate, the silicone graft polymer component can be thermally or catalytically crosslinked, if appropriate with the addition of further reactive silicone derivatives such as e.g. Polymethylhydrogensiloxanen done. The purely thermal crosslinking takes place at temperatures from around 120 ° C. The catalytically activated crosslinking can take place at room temperature. Known systems such as platinum or platinum compounds, organotin compounds but also peroxides or other radical initiators are suitable as catalysts. UV-activated crosslinking can also be carried out successfully. Crosslinking improves the solvent and wash resistance of the equipment. In the case of catalytic crosslinking, it is advisable to use appropriate inhibitors, such as Use acetylene alcohols, especially methylenedinol.

Die folgenden Beispiele sollen die Erfindung näher erläutern, ohne sie in ihrem Umfang einzuschränken.The following examples are intended to explain the invention in more detail without restricting its scope.

Wenn nicht anderes vermerkt, sind Mengenangaben als Gewichtsteile bzw. Gewichtsprozente zu verstehen.Unless otherwise noted, quantities are to be understood as parts by weight or percentages by weight.

Herstellung der Ausgangssubstanzen:Production of the starting substances:

Die Herstellung der Polydiorganosiloxane erfolgt in an sich bekannter Weise (vgl. W. Noll, "Chemie und Technologie der Silicone", Verlag Chemie, Weinheim/Bergstraße, 2. Aufl., 1968, Kap. 5, S. 162 ff.).The polydiorganosiloxanes are prepared in a manner known per se (cf. W. Noll, "Chemistry and Technology of Silicones", Verlag Chemie, Weinheim / Bergstrasse, 2nd ed., 1968, K ap. 5, p. 162 ff.) .

Die in den Beispielen aufgeführten Siloxane sind wie folgt gekennzeichnet:

Figure imgb0004
The siloxanes listed in the examples are identified as follows:
Figure imgb0004

Beispiel 1example 1

In einem 40 1-Autoklaven mit Rückflußkühler werden 10,5 kg eines Polysiloxans B, 9 kg eines Polysiloxans C vorgelegt und unter Stickstoffüberleitung auf 110°C erwärmt. Dann werden gleichzeitig 2 Lösungen innerhalb von 5 Stunden hinzugegeben:

  • Lös. 1: 7,5 kg n-Butylacrylat
  • Lös. 2: 1,5 kg Polysiloxan C 45 g t-Butylperpivalat
10.5 kg of a polysiloxane B, 9 kg of a polysiloxane C are placed in a 40 1 autoclave with a reflux condenser and heated to 110 ° C. with nitrogen transfer. Then 2 solutions are added simultaneously within 5 hours:
  • Solution 1: 7.5 kg of n-butyl acrylate
  • Sol. 2: 1.5 kg polysiloxane C 45 g t-butyl perpivalate

Der Ansatz wird 1 Stunde nachgerührt und dann werden die flüchtigen Anteile destillativ entfernt.The mixture is stirred for 1 hour and then the volatile constituents are removed by distillation.

Viskosität bei 25°C: 12 000 m.Pas.Viscosity at 25 ° C: 12,000 m.Pas.

Zusammensetzung:

  • 37 % Einheiten aus Polysiloxan B
  • 37 % Einheiten aus Polysiloxan C
  • 26 % polymerisierte Einheiten aus n-Butylacrylat
Composition:
  • 37% polysiloxane B units
  • 37% polysiloxane C units
  • 26% polymerized units from n-butyl acrylate

Beispiel 2Example 2

In einem 6 1-Rührkessel werden unter Schutzgas 3 kg Polysiloxan B, 150 g Polysiloxan C auf 100°C erwärmt. Dann wird eine Lösung aus

  • 1,75 kg n-Butylacrylat
  • 15 g Tetrahydrobenzaldehydbenzylenolether
  • 7,5 g t-Butylperpivalat in 5 Stunden hinzugepumpt. Man rührt 1 Stunde nach und zeiht die flüchtigen Anteile im Vakuum ab. Das Endprodukt hat bei 25°C eine Viskosität von 40 mPa.s und folgenden Zusammensetzung:
    • 28 % polymerisierte Einheiten aus Butylacrylat 3 % Anteile aus Polysiloxan C
    • 69 % Anteile aus Polysiloxan B
In a 6 1 stirred kettle, 3 kg of polysiloxane B and 150 g of polysiloxane C are heated to 100 ° C. under protective gas. Then a solution will come out
  • 1.75 kg of n-butyl acrylate
  • 15 g of tetrahydrobenzaldehyde benzyl enol ether
  • 7.5 g t-butyl perpivalate pumped in 5 hours. The mixture is stirred for 1 hour and the volatile constituents are stripped off in vacuo. The end product has a viscosity of 40 mPa.s at 25 ° C and the following composition:
    • 28% polymerized units from butyl acrylate 3% parts from polysiloxane C
    • 69% shares from polysiloxane B

Beispiel 3Example 3

In einem 6 1 Rührkessel werden unter Stickstoff 1500 g Polysiloxan B, 750 g Polysiloxan D, 750 g Polysiloxan C, 1 g Tetrahydrobenzaldehydenolether auf 150°C aufgeheizt. Dann werden zwei Lösungen gleichzeitig innerhalb von 4 Stunden hinzugegeben:

  • Lösung 1 1000 g n-Butylacrylat
  • Lösung 2 500 g Polysiloxan C 10 g tert.-Butylperoctoat 4 g Tetrahydrobenzaldehydbenzylenolether.
In a 6 l stirred kettle, 1500 g of polysiloxane B, 750 g of polysiloxane D, 750 g of polysiloxane C, 1 g of tetrahydrobenzaldehyde-ether ether are heated to 150 ° C. under nitrogen. Then two solutions are added simultaneously within 4 hours:
  • Solution 1 1000 g of n-butyl acrylate
  • Solution 2 500 g polysiloxane C 10 g tert-butyl peroctoate 4 g tetrahydrobenzaldehyde benzene ol ether.

Der Ansatz wird 1 Stunde bei 150°C nachgerührt, sodann evakuiert und praktisch vollständig von nicht umgesetzten Monomeren befreit. Das erhaltene Pfropfpolymerisat weist eine Viskosität von 1500 mPas bei 25°C auf und weist eine Zusammensetzung auf, die einem 88 %igen Monomerumsatz entspricht.The mixture is stirred at 150 ° C. for 1 hour, then evacuated and virtually completely freed of unreacted monomers. The graft polymer obtained has a viscosity of 1500 mPas at 25 ° C. and has a composition which corresponds to an 88% monomer conversion.

Beispiel 4,5Example 4.5

In einen 6 1-Rührkessel werden unter Stickstoff die unter Vorlage angegebenen Komponenten eingefüllt und auf 110°C erwärmt. Innerhalb von 3 Stunden wird die Monomer-Initiatorlösung hinzugegeben und dann 1 Stunde nachgerührt. Nach Abziehen der flüchtigen Anteile im Vakuum wird abgekühlt.

Figure imgb0005
In a 6 1 stirred kettle, the components specified under template are introduced under nitrogen and heated to 110.degree. The monomer initiator solution is added within 3 hours and then stirred for 1 hour. After the volatile constituents have been stripped off in vacuo, the mixture is cooled.
Figure imgb0005

Beispiel 6Example 6

In einem 6 1-Stahlautoklaven werden 900 g Polysiloxan C und 600 g Polysiloxan B, 2,5 g di-tert.-Butylperoxid und 450 g Vinylidenfluorid vorgelegt. Der Ansatz wird auf 125°C erwärmt und 30 Minuten bei 125°C gerührt. Dann werden Lösung 1 und 2 innerhalb von 3 Stunden hinzugegeben.In a 6 1 steel autoclave 900 g of polysiloxane C and 600 g of polysiloxane B, 2.5 g of di-tert-butyl peroxide and 450 g of vinylidene fluoride. The mixture is heated to 125 ° C. and stirred at 125 ° C. for 30 minutes. Then solutions 1 and 2 are added within 3 hours.

Lösung 1 250 g Polysiloxan C 12,5 g di-tert.-ButylperoxidSolution 1 250 g polysiloxane C 12.5 g di-tert-butyl peroxide

Lösung 2 1300 g Vinylidenfluorid.Solution 2 1300 g vinylidene fluoride.

Der Ansatz wird 1 Stunde bei 125°C nachgerührt, vorsichtig entspannt und evakuiert. Die flüchtigen Anteile werden abgezogen. Das Pfropfpolymerisat enthält 45 Gew.-% polymerisierte Einheiten aus Vinylidenfluorid 22 Gew.-% Einheiten aus Polysiloxan B 33 Gew.-% Einheiten aus Polysiloxan CThe mixture is stirred at 125 ° C. for 1 hour, carefully released and evacuated. The volatile components are deducted. The graft polymer contains 45% by weight polymerized units made of vinylidene fluoride 22% by weight units made of polysiloxane B 33% by weight units made of polysiloxane C.

Beispiel 7Example 7

Zu 40,0 kg einer Pfropfcopolymerdispersion des Beispiels 1 werden unter Rühren 1,4 kg eines mit 50 Mol Ethylenoxid umgesetzten Oleylalkohols und 1,2 kg eines mit 6 Mol Ethylenoxid umgesetzten Tridecylalkohols gegeben. Die Mischung wird auf 60°C erwärmt und unter Rühren werden 57,4 kg entionisiertes Wasser eingearbeitet. Man erhält eine homogene und stabile Emulsion des Pfropfcopolymers. Gegebenenfalls kann zur feineren Verteilung mittels einer Hochdruckhomogenisiermaschine (z.B. Alfa-Laval, Typ SH 20) in einem oder mehreren Gängen bei 200 bar homogenisiert werden.1.4 kg of an oleyl alcohol reacted with 50 mol of ethylene oxide and 1.2 kg of a tridecyl alcohol reacted with 6 mol of ethylene oxide are added to 40.0 kg of a graft copolymer dispersion of Example 1 with stirring. The mixture is heated to 60 ° C. and 57.4 kg of deionized water are incorporated with stirring. A homogeneous and stable emulsion of the graft copolymer is obtained. If necessary, homogenization can be carried out in one or more gears at 200 bar for fine distribution using a high-pressure homogenizing machine (e.g. Alfa-Laval, type SH 20).

Beispiele 8 bis 9Examples 8 to 9

In gleicher Verfahrensweise, wie in Beispiel 4 erläutert, erhält man Emulsionen aus den Copolymerisaten in folgenden Zusammensetzungen:

Figure imgb0006
In the same procedure as explained in Example 4, emulsions are obtained from the copolymers in the following compositions:
Figure imgb0006

Zum Vergleich werden Muster der Baumwoll-Hemdenpopeline mit der erfindungsgemäßen Pfropfpolymerdispersion wie folgt ausgerüstet:

Figure imgb0007
For comparison, samples of the cotton shirt poplin are equipped with the graft polymer dispersion according to the invention as follows:
Figure imgb0007

Die Applikation erfolgt in der wie vorher beschriebenen Weise.The application takes place in the manner described above.

Beispiel 10-15 (Ausrüstung von Baumwoll-Hemdenpopeline)Example 10-15 (Finishing Cotton Shirt Poplin)

Zur Verbesserung des "wash and wear"-Verhaltens von Baumwoll-Hemdenpopeline werden die Materialien mit Kunstharzen ausgerüstet, z.B. mit Dimethyldihydroxyethylenharnstoff (= DMDHEU). Hierdurch wird einerseits das Entknitterungsverhalten, trocken und naß, deutlich verbessert, zum anderen der Griff, die Reißfestigkeit, die Einreißfestigkeit, die Scheuerfestigkeit und die Vernähbarkeit verschlechtert. Um diese Nachteile zu kompensieren, werden Acrylatdispersionen und Weichmachungsmittel auf Basis von Fettsäureamiden und/oder Siliconen der Ausrüstungsflotte zugesetzt.To improve the "wash and wear" behavior of cotton shirt poplin, the materials are made with synthetic resins equipped, for example with dimethyldihydroxyethylene urea (= DMDHEU). On the one hand, this significantly improves the wrinkling behavior, dry and wet, on the other hand the grip, tear resistance, tear resistance, abrasion resistance and sewability deteriorate. In order to compensate for these disadvantages, acrylate dispersions and plasticizers based on fatty acid amides and / or silicones are added to the finishing liquor.

Beispiel: 120-180 g/1 Acrylatdispersion 15-30 g/1 Weichmachungsmittel 12-18 g/1 MgCl2. 6 H20Example: 120-180 g / 1 acrylic dispersion 15-30 g / 1 plasticizer 12-18 g / 1 MgCl 2 . 6 H 2 0

Die Applikation erfolgt durch Tauchen (Flottenaufnahme 70-100 % vom Warengewicht), Abquetschen und anschließendes Trocknen. Hieran schließt sich ein Kalandrier- und Kondensationsschritt bei 140-160°C während 4 bis 6 Minuten an.The application is carried out by dipping (picking up liquor 70-100% of the weight of the goods), squeezing and then drying. This is followed by a calendering and condensation step at 140-160 ° C for 4 to 6 minutes.

Figure imgb0008
Figure imgb0008

Im Vergleich zum Beispiel 11 bleibt beim erfindungsgemäßen Beispiel 12 auch nach 5 Wäschen bei 60°C der vorteilhafte Griff, Reißfestigkeit und Knitterwinkel praktisch unverändert erhalten, während Beispiel 11 nach 5 Wäschen unter gleichen Bedingungen deutliche Verschlechterungen im Griff (rauh, leer) und deutliche Verschlechterung von Reißfestigkeit und Knitterwinkel aufweist.In comparison to Example 11, in Example 12 according to the invention the advantageous grip, tear resistance and crease angle remain virtually unchanged even after 5 washes at 60 ° C., while Example 11 after 5 washes under the same conditions shows marked deteriorations in the handle (rough, empty) and marked deterioration of tear resistance and crease angle.

Beispiel 16Example 16

Auswirkung von Co-Rundwirkware.Impact of co-circular knitted fabrics.

Eine in Längsrichtung strukturierte 100 %ige Co-Rundwirkware (100 kg) wird auf einer Düsenfärbemaschine mit Reaktionfarbstoffen gefärbt, mehrmals heiß und kalt gespült und bei Kochtemperatur geseift; so daß alle unfixierten Farbstoffanteile entfernt sind.A 100% co-circular knitted fabric (100 kg) structured in the longitudinal direction is dyed with reaction dyes on a nozzle dyeing machine, rinsed hot and cold several times and soaped at cooking temperature; so that all unfixed dye components are removed.

Das letzte Spülbad verbleibt in der Maschine. Hierzu werden 2 kg einer erfindungsgemäßen Copfropfpolymerdispersion des Beispiels 4 (entspricht 2 % v. WG.) über ein Ansatzgefäß gegeben. Der pH-Wert der Spülflotte wurde vorher mit Essigsäure auf 6.0 eingestellt.The last rinsing bath remains in the machine. For this purpose, 2 kg of a head graft polymer dispersion according to the invention from Example 4 (corresponds to 2% of WG.) Are passed through a batch vessel. The pH of the rinsing liquor was previously adjusted to 6.0 with acetic acid.

Das Behandlungsbad wird bei laufender Ware mit je 1°C/ min. auf 35°C aufgeheizt. Nach Erreichen der Endtemperatur verbleibt die Ware 15 min. in der Ausrüstungsflotte.The treatment bath is at 1 ° C / min. heated to 35 ° C. After reaching the final temperature, the goods remain for 15 minutes. in the equipment fleet.

Danach wird die Flotte abgelassen, die Ware dem Färbeapparat entnommen und bei 125°C kontinuierlich getrocknet. Der Griff der behandelten Ware ist voll, weich und oberflächenglatt.The liquor is then drained off, the goods are removed from the dyeing apparatus and dried continuously at 125 ° C. The handle of the treated goods is full, soft and smooth.

Messung der Elastizität:

  • Aus dem Gewirke werden an verschiedenen Stellen je 3 Prüflinge berührungsfrei aufgehängt. Am unteren Ende wird eine Klammer angebracht, die mit einem Gewicht von 25 N (2.5 Kp.) belastet wird. Nach 30 Minuten wird die Längung des Prüflings gemessen.
  • Meßwert: % statistische Dehnung.
  • Nach Abnahme des Gewichtes wird nach 30 Min. die bleibende Längung gemessen.
  • Meßwert: % bleibende Dehnung..
Figure imgb0009
 Measurement of elasticity:
  • 3 test specimens are hung from the knitted fabric at various points without contact. At the lower end a clip is attached, which is loaded with a weight of 25 N (2.5 Kp.). The elongation of the test specimen is measured after 30 minutes.
  • Measured value:% statistical elongation.
  • After the weight has been removed, the permanent elongation is measured after 30 minutes.
  • Measured value:% permanent elongation ..
Figure imgb0009

Claims (5)

1. Textilausrüstungsmittel, enthaltend eine Pfropfpolymerisatdispersion bestehend aus A. einem vinylgruppenhaltigen Organopolysiloxan B. einem Organopolysiloxan mit Si-H-Gruppen und C. polymerisierte Einheiten aus Vinylmonomeren,
wobei ein Teil der Organopolysiloxankomponenten über polymerisierte Einheiten der eingesetzten Vinylmonomeren verknüpft ist und ein Teil der Si-H-Gruppen des Si-H-Organopolysiloxans durch Monoaddition der eingesetzten Vinylverbindungen modifiziert ist.1. Textile finishing agent containing a graft polymer dispersion consisting of A. an organopolysiloxane containing vinyl groups B. an organopolysiloxane with Si-H groups and C. polymerized units from vinyl monomers,
where part of the organopolysiloxane components is linked via polymerized units of the vinyl monomers used and part of the Si-H groups of the Si-H organopolysiloxane is modified by monoaddition of the vinyl compounds used. 2. Textilausrüstungsmittel gemäß Anspruch 1, enthaltend eine Pfropfpolymerisatdispersion bestehend aus 1. 15-95 Gew.-% eines Pfropfsubstrates, enthaltend A) 5-95 Gew.-% Vinylgruppen enthaltenden Diorganipolysiloxanen und B) 5-95 Gew.-% Methyl-hydrogen-polysiloxan, wobei die Summe der Komponenten A und B 100 % beträgt und 2. 85-5 Gew.-% polymerisierten Einheiten aus Vinylverbindungen, wobei die Summe der Komponenten 1 und 2 stets 100 % beträgt. 2. Textile finishing agent according to claim 1, comprising a graft polymer dispersion consisting of 1. 15-95 wt .-% of a graft substrate containing A) 5-95% by weight of vinyl groups containing diorganipolysiloxanes and B) 5-95% by weight of methyl hydrogen polysiloxane, the sum of components A and B being 100% and 2. 85-5% by weight of polymerized units of vinyl compounds, the sum of components 1 and 2 always being 100%. 3. Textilausrüstungsmittel gemäß einem der Ansprüche 1 oder 2, enthaltend eine Pfropfpolymerisatdispersion bestehend aus 1. 40-90 Gew.-% eines Pfropfsubstrates, enthaltend A) 20-80 Gew.-% Vinylgruppen enthaltenden Diorganopolysiloxanen B) 80-20 Gew.-% Methyl-hydrogen-polysiloxan und 2. 60-10 Gew.-% polymerisierten Einheiten aus n-Butylacrylat,
wobei die Summe der Komponenten 1. A + B und 1. + 2. stets 100 Gew.-% beträgt.3. Textile finishing agent according to one of claims 1 or 2, comprising a graft polymer dispersion consisting of 1. 40-90 wt .-% of a graft substrate containing A) 20-80% by weight of vinyl groups containing diorganopolysiloxanes B) 80-20% by weight of methyl hydrogen polysiloxane and 2. 60-10% by weight of polymerized units of n-butyl acrylate,
the sum of components 1. A + B and 1. + 2. is always 100% by weight. 4. Textilausrüstungsmittel, gemäß einem der Ansprüche 1 bis 3, enthaltend A. 40-90 Gew.-% Wasser B. 5-59,9 Gew.-% Siliconpfropypolymerisatdispersion und C. 0,1-5 Gew.-% Emulgier- bzw. Dispergierhilfsmittel, sowie gegebenenfalls Vernetzungskatalysatoren und Inhibitoren. 4. Textile finishing agent, according to one of claims 1 to 3, containing A. 40-90 wt% water B. 5-59.9% by weight silicone graft polymer dispersion and C. 0.1-5% by weight of emulsifying or dispersing agents, and, if appropriate, crosslinking catalysts and inhibitors. 5. Verfahren zur Ausrüstung von textilen Materialien, dadurch gekennzeichnet, daß man auf das textile Material ein Ausrüstungsmittel gemäß einem der Ansprüche 1 - 4 aufbringt.5. A method of finishing textile materials, characterized in that an finishing agent according to one of claims 1-4 is applied to the textile material.
EP83100041A 1982-01-16 1983-01-05 Grafted siloxane dispersions for the finishing of textile materials Expired EP0084772B1 (en)

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DE19823201205 DE3201205A1 (en) 1982-01-16 1982-01-16 GRAFT MODIFIED SILOXANE DISPERSIONS FOR EQUIPMENT OF TEXTILE MATERIALS

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Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0469613A2 (en) * 1990-08-02 1992-02-05 Dow Corning Toray Silicone Company, Limited Organopolysiloxane/acrylate ester copolymer emulsion
EP0552983A2 (en) * 1992-01-23 1993-07-28 Shin-Etsu Chemical Co., Ltd. Coating compositions and air bags coated with them
EP0632157A1 (en) * 1993-06-30 1995-01-04 Shin-Etsu Chemical Co., Ltd. Agent for water-repellent treatment of fibers
EP0661399A1 (en) * 1993-12-30 1995-07-05 Dow Corning Corporation Catalyst compositions and methods for the preparation thereof
EP0661400A1 (en) * 1993-12-30 1995-07-05 Dow Corning Corporation Fiber treatment compositions and methods for the preparation thereof
EP0731207A1 (en) * 1995-03-09 1996-09-11 Wacker-Chemie GmbH Binder for textile material
US6506220B2 (en) 1998-09-30 2003-01-14 Unilever Home & Personal Care Usa Division Of Conopco Treatment for fabrics

Families Citing this family (14)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4684670A (en) * 1983-08-26 1987-08-04 General Electric Company Ultraviolet radiation-curable silicone release compositions
JPH01168971A (en) * 1987-12-23 1989-07-04 Nisshin Kagaku Kogyo Kk Elastic processing agent for fiber and feeling-improving agent
JPH01168972A (en) * 1987-12-25 1989-07-04 Nisshin Kagaku Kogyo Kk Elastic processing agent for fiber providing hydrophilic properties
JP2703603B2 (en) * 1989-02-09 1998-01-26 日信化学工業株式会社 Fiber treatment agent
DE19629585C2 (en) * 1995-09-06 1998-12-10 Heidenhain Gmbh Dr Johannes Angle measuring device
US6375685B2 (en) * 1997-05-13 2002-04-23 The Procter & Gamble Company Textile finishing process
DE69823051T2 (en) * 1997-10-24 2005-03-17 Daikin Industries, Ltd. AQUEOUS RESIN DISPERSION COMPOSITION
DE60105845T2 (en) * 2000-12-15 2005-02-10 Unilever N.V. TEXTILE WASH
US6616980B2 (en) 2001-04-24 2003-09-09 Crompton Corporation Emulsion polymerized acrylated silicone copolymer for wrinkle reduction
EP1660947A1 (en) * 2003-07-25 2006-05-31 Dow Corning Corporation Silicone rubber composition
US7452957B2 (en) * 2005-08-31 2008-11-18 Kimberly-Clark Worldwide, Inc. Hydrophilic silicone elastomers
US20100145001A1 (en) * 2006-12-12 2010-06-10 Unilever Plc branched organic-inorganic polymers
WO2018180615A1 (en) 2017-03-31 2018-10-04 信越化学工業株式会社 Fiber treatment agent for electron beam fixing
JP7008432B2 (en) * 2017-03-31 2022-01-25 信越化学工業株式会社 Fiber to which silicone is fixed and its manufacturing method

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3249581A (en) * 1963-11-29 1966-05-03 Dow Corning Olefin-substituted silicone potting compounds
FR2343010A1 (en) * 1976-03-04 1977-09-30 Pfersee Chem Fab PROCESS FOR POLYMERIZATION OF ACRYLIC ESTERS IN THE PRESENCE OF HYDROGENOPOLYSILOXANES AND APPLICATION OF THE PRODUCTS TO FIBER TREATMENT
FR2352032A1 (en) * 1976-05-20 1977-12-16 Dow Corning RADIATION VULCANIZABLE COMPOSITIONS COMPRISING A POLYDIORGANOSILOXANE MERCAPTOALKYL AND A VINYL MONOMETER
EP0002744A1 (en) * 1977-12-16 1979-07-11 SWS Silicones Corporation Harderable masses based on modified organic polysiloxane mixtures with in situ generated particles and method for preparation of the modified organic polysiloxanes
EP0004947A1 (en) * 1978-04-14 1979-10-31 SWS Silicones Corporation Organopolysiloxanes modified by graft polymerization of vinyl monomers as well as their use in curable compositions

Family Cites Families (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3555109A (en) * 1967-09-08 1971-01-12 Stauffer Wacker Silicone Corp In situ generation of unique particulate matter in organopolysiloxanes
US3627836A (en) * 1968-11-15 1971-12-14 Stauffer Wacker Silicone Corp Modified organopolysiloxanes with mono and polyolefinic cross-linked particles generated in situ
BE754668A (en) * 1969-08-13 1971-02-10 Stauffer Wacker Silicone Corp MODIFIED ORGANOPOLYSILOXANES AND THEIR PREPARATION
US4014851A (en) * 1973-12-26 1977-03-29 General Electric Company Polyolefin-filled vinyloranopolysiloxane composition and method of preparation
US4123472A (en) * 1975-09-05 1978-10-31 Sws Silicones Corporation Oil resistant modified silicone composition
DE2641201A1 (en) * 1976-09-14 1978-03-16 Consortium Elektrochem Ind MIXTURES CONTAINING DIORGANOPOLYSILOXANES AND PROCESS FOR THEIR PREPARATION

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3249581A (en) * 1963-11-29 1966-05-03 Dow Corning Olefin-substituted silicone potting compounds
FR2343010A1 (en) * 1976-03-04 1977-09-30 Pfersee Chem Fab PROCESS FOR POLYMERIZATION OF ACRYLIC ESTERS IN THE PRESENCE OF HYDROGENOPOLYSILOXANES AND APPLICATION OF THE PRODUCTS TO FIBER TREATMENT
FR2352032A1 (en) * 1976-05-20 1977-12-16 Dow Corning RADIATION VULCANIZABLE COMPOSITIONS COMPRISING A POLYDIORGANOSILOXANE MERCAPTOALKYL AND A VINYL MONOMETER
EP0002744A1 (en) * 1977-12-16 1979-07-11 SWS Silicones Corporation Harderable masses based on modified organic polysiloxane mixtures with in situ generated particles and method for preparation of the modified organic polysiloxanes
EP0004947A1 (en) * 1978-04-14 1979-10-31 SWS Silicones Corporation Organopolysiloxanes modified by graft polymerization of vinyl monomers as well as their use in curable compositions

Cited By (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0469613A2 (en) * 1990-08-02 1992-02-05 Dow Corning Toray Silicone Company, Limited Organopolysiloxane/acrylate ester copolymer emulsion
EP0469613A3 (en) * 1990-08-02 1992-03-25 Dow Corning Toray Silicone Company, Limited Organopolysiloxane/acrylate ester copolymer emulsion
EP0552983A2 (en) * 1992-01-23 1993-07-28 Shin-Etsu Chemical Co., Ltd. Coating compositions and air bags coated with them
EP0552983A3 (en) * 1992-01-23 1993-10-13 Shin-Etsu Chemical Co., Ltd. Coating compositions and air bags coated with them
US5399402A (en) * 1992-01-23 1995-03-21 Shin-Etsu Chemical Co., Ltd. Air bag coating composition and air bag
EP0632157A1 (en) * 1993-06-30 1995-01-04 Shin-Etsu Chemical Co., Ltd. Agent for water-repellent treatment of fibers
EP0661399A1 (en) * 1993-12-30 1995-07-05 Dow Corning Corporation Catalyst compositions and methods for the preparation thereof
EP0661400A1 (en) * 1993-12-30 1995-07-05 Dow Corning Corporation Fiber treatment compositions and methods for the preparation thereof
EP0731207A1 (en) * 1995-03-09 1996-09-11 Wacker-Chemie GmbH Binder for textile material
US6506220B2 (en) 1998-09-30 2003-01-14 Unilever Home & Personal Care Usa Division Of Conopco Treatment for fabrics

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