EP0370326B1 - Verfahren zur Behandlung von faserigen Materialien mit modifizierten Organopolysiloxanen und die so behandelten Materialien - Google Patents
Verfahren zur Behandlung von faserigen Materialien mit modifizierten Organopolysiloxanen und die so behandelten Materialien Download PDFInfo
- Publication number
- EP0370326B1 EP0370326B1 EP89120826A EP89120826A EP0370326B1 EP 0370326 B1 EP0370326 B1 EP 0370326B1 EP 89120826 A EP89120826 A EP 89120826A EP 89120826 A EP89120826 A EP 89120826A EP 0370326 B1 EP0370326 B1 EP 0370326B1
- Authority
- EP
- European Patent Office
- Prior art keywords
- process according
- stage
- weight
- organopolysiloxane copolymer
- compound
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
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Classifications
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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
- D06M15/21—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
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- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06N—WALL, FLOOR, OR LIKE COVERING MATERIALS, e.g. LINOLEUM, OILCLOTH, ARTIFICIAL LEATHER, ROOFING FELT, CONSISTING OF A FIBROUS WEB COATED WITH A LAYER OF MACROMOLECULAR MATERIAL; FLEXIBLE SHEET MATERIAL NOT OTHERWISE PROVIDED FOR
- D06N3/00—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof
- D06N3/12—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof with macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds, e.g. gelatine proteins
- D06N3/128—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof with macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds, e.g. gelatine proteins with silicon polymers
Definitions
- the present invention relates to a method for treating fibrous materials with modified organopolysiloxanes and the fibrous materials treated in this way.
- the object of the present invention was to find a system which eliminates the disadvantages of the prior art and gives the treated textiles a particularly soft feel, good to very good waterproofness with good whiteness retention, the effects also with regard to washing - and resistance to cleaning should meet increased requirements.
- the present patent application thus relates to a method for treating fibrous materials with modified organopolysiloxanes, as described in more detail in claim 1.
- a method for treating fibrous materials with modified organopolysiloxanes as described in more detail in claim 1.
- claims 2 to 13 certain embodiments of this method are protected and in claim 14 the fibrous materials treated with the modified organopolysiloxanes are claimed.
- the modified organopolysiloxane copolymers are prepared in two stages. In the first stage, organopolysiloxane copolymers are prepared from conventional cyclic siloxanes (A) and (meth) acrylate silanes, vinylsilanes and / or cyclic vinylsiloxanes (B).
- the cyclic siloxanes (A) are known. Suitable Compounds are hexamethyltricyclosiloxane, octamethyltetracyclosiloxane, decamethylpentacyclosiloxane, dodekamethylhexacyclosiloxane and trimethyltriphenyltricyclosiloxane.
- cyclic vinylsiloxanes can be considered as starting components (B).
- the tetramethyltetravinylcyclosiloxane is mentioned as an example, but other known cyclic vinylsiloxanes can also be used according to the invention without any problems.
- Octamethyltetracyclosiloxane and compounds of the formula (1) or. Have proven to be particularly suitable for the preparation of the first stage organopolysiloxane copolymers.
- the compounds (A) and (B) are used to prepare the organopolysiloxane copolymers in amounts of from 85 to 99.99, in particular 90 to 99.8,% by weight to 15 to 0.01, in particular 10 to 0.2,% by weight implemented.
- this 1st stage is known in principle from DE-A-3 617 267.
- this preparation is carried out in the presence of a crosslinking agent.
- Tetraalkoxysilanes and / or also can be used as crosslinkers the compounds (B), if n 3, are used.
- trifunctional crosslinkers such as methyltrimethoxisilane or ethyltriethoxisilane are also suitable. These compounds are used in amounts of 0.1 to 15% by weight; in particular 0.5 to 10% by weight, based on the sum of (A) and (B).
- alkylbenzenesulfonic acids such as dodecyclobenzenesulfonic acid
- dodecyclobenzenesulfonic acid are used in amounts of 0.05 to 10% by weight, in particular in amounts of 0.5 to 6% by weight, based on the sum of compounds (A) and (B).
- a mixture of alkylbenzenesulfonic acids and a dispersing aid is used as emulsifier (1).
- Straight and / or branched chain alcohols with 8 to 20, in particular 12 to 18, carbon atoms have proven to be such assistants.
- the amount of dispersing aid in the emulsifier (1) can outweigh this.
- Stage 1 is now carried out as follows: Water, advantageously distilled or double-distilled water and the emulsifier or the emulsifier mixture are weighed in first and a homogeneous solution is prepared by stirring, if appropriate with heating. Then the compounds (A) and (B) and the crosslinker are slowly added to the previously prepared aqueous solution and a homogeneous mixture is prepared with stirring at a slightly elevated temperature. The pre-emulsion thus produced is homogenized using a high-pressure emulsifying device. A stable dispersion of the organopolysiloxane copolymer is obtained (concentration about 10 to 45%).
- copolymerization is carried out with at least one vinyl monomer.
- the known base monomers such as vinyl esters, e.g. Vinyl acetate, but especially methacrylic or acrylic acid esters, e.g. Methacrylic or acrylic acid esters of alcohols with 1 to 6 carbon atoms, are used.
- the alkyl acrylates with 2 to 6 carbon atoms in the alkyl radical are particularly suitable as base monomers. These monomers are used in the second stage, based on the total monomer, in amounts of at least 50% by weight, in particular 55-9O% by weight.
- the monomers are acrylic and methacrylic acid nitrile, acrylamide, styrene, vinyl ether, methacrylic and acrylic acid esters of alcohols with 8 to 12 carbon atoms, conjugated diolefins, such as e.g. Butadiene or isoprene, vinyl chloride, vinylidene chloride, allyl methacrylate and ethylene dimethacrylate.
- Particularly suitable vinyl monomers are alkyl acrylates with 2 to 6 carbon atoms in the alkyl radical, acrylonitrile and styrene.
- crosslinkable vinyl monomers are incorporated into the modified organopolysiloxane copolymers.
- Suitable vinyl monomers here are monomers which contain N-methylol groups, in particular carboxamide methylol groups.
- Etherified N-methylol groups where alcohols having 1 to 4 carbon atoms, in particular methanol, are used for the etherification, are also suitable as reactive groups.
- Monomers by which these groups are introduced into the modified product include, in particular, N-addition products of formaldehyde with methacrylamide or acrylamide, and also allyl or methallyl carbamate, with the monomethylol compounds in question preferably being copolymerized.
- N-methylolacrylamide etherified with methanol can be used.
- the crosslinkable monomers are polymerized in amounts, based on the total vinyl monomer, of at least 0.5% by weight, preferably 1.0% to 10% by weight.
- hydrophilic vinyl monomers examples include 2-acrylamido-2-methylpropane sodium sulfonate and / or sodium vinyl sulfonate, but also allyl alcohol.
- the reaction in the second stage is carried out such that the weight ratio of organopolysiloxane copolymer to vinyl monomer is 1: 0.5 to 1: 4, in particular 1: 1 to 1: 2.5.
- the second stage reaction also takes place in the presence of emulsifiers. It is generally sufficient to continue working with the emulsifier (1). However, it is particularly advantageous to add further emulsifiers during the second stage.
- the known nonionic emulsifiers namely the customary ethoxylation products of higher fatty alcohols, fatty acids, fatty amines and fatty acid amides or their salts with volatile acids, can be used for this purpose.
- nonionic compounds examples include: ethoxylated isotridecyl alcohol with an average of 10 to 50 ethylene oxide, 2,6,8-trimethylnonyloxipolyethylene glycol with 10 to 30 ethylene oxide, ethoxylated N- (stearyl) - or (N-hexadecyl) trimethylene diamine with 10 ethylene oxide .
- emulsifier (2) emulsifiers
- emulsifier (2) emulsifiers
- emulsifier (2) emulsifiers
- sulfonated or sulfated ethoxylated fatty alcohols or alkylphenols for example nonylphenol 5 to 15 ethylene oxide ether sulfate and sulfated cetyl, stearyl and / or isotridecyl alcohol ethoxylated with 10 to 15 ethylene oxide.
- protective colloids that can be used are known to the person skilled in the art.
- the compounds known for emulsion polymerization in particular polyvinyl alcohol, polyacrylic derivatives and particularly preferably polyvinylpyrrolidone, are used, in quantities of 0.1 to 5% by weight, based on the finished dispersion.
- the copolymerization is carried out essentially in a known manner.
- the procedure is such that the component prepared in process step (1), together with any additional emulsifiers and protective colloids and water, is placed in a reaction vessel and adjusted to a weakly acidic to neutral pH.
- the monomers or the monomer mixture are placed in a feed vessel and slowly stirred into the reaction vessel.
- the polymerization takes place with slow stirring at temperatures of about 50 to 75 ° C.
- the reaction is started by adding the usual polymerization initiators, especially hydrogen peroxide, sodium hydroxymethanesulfinate and tertiary butyl hydroperoxide, which are used in a customary manner.
- process steps 1 and 2 can also be carried out in immediate succession (one-pot process).
- dispersions of the modified organopolysiloxane copolymers are obtained in the manner described.
- These dispersions can be used directly for the treatment of fiber materials, in particular by coating, i.e. the coating pastes can generally be prepared in a simple manner, especially without catalysts and stabilizers.
- the dispersions obtained are thus used directly in the coating, it being only necessary to use customary thickening and defoaming agents.
- Preparations known from textile printing e.g. Starch and modified starch, vegetable gums and mucilages, such as tragacanth, alginates and locust bean gum, cellulose derivatives such as carboxymethyl cellulose, hydroxyethyl cellulose and synthetic thickeners such as polyacrylic acid.
- the desired viscosity is set using these thickeners, for which purpose generally only small amounts, namely 0.4 to 6% by weight, based on the coating composition, are required.
- the defoaming agents used are also known. For this purpose, those based on silicones or ethoxylated compounds are preferably used.
- the coating composition is then applied to the textile material to be treated in a known manner by doctoring (for example using rollers or, above all, air and rubber-coated doctor blades), brushing, printing and the like.
- doctoring for example using rollers or, above all, air and rubber-coated doctor blades
- work is generally carried out continuously, while the coating composition, for example, is spread on discontinuously in the laboratory.
- the goods run at a speed of 5 to 25 m / minute and are passed through a heating channel immediately after application and dried at temperatures of 100 to 190 ° C and condensed if necessary, with an average residence time of between half and 6 Minutes.
- the circulation is between 5 to 100 g / m2.
- Lighter materials which are processed for leisure and rainwear or umbrella fabrics, have a circulation of 5 to 20 g / m2.
- Medium-weight materials such as tarpaulin, canvas, tent and awning fabrics or terry articles are provided with 20 to 70 g / m2 and heavier materials, such as particularly technical fabrics, have a print run of up to 100 g / m2 (details based on solid substance) , it being expedient or even necessary to apply the desired number of runs in two or more passes, particularly in the case of larger runs, in order to achieve a uniform, coherent film, which is easily possible by the process according to the invention.
- Most articles are only coated on one side, but the other side can also be coated in the same way.
- the materials coated on both sides, but especially the one-sided, are impregnated.
- This re-impregnation optimizes the effects and, in the case of the coating on one side only, also provides the other side with a particular water-repellent finish.
- the post-impregnation is carried out in a known manner using the known finishing agents, such as metal salt-containing paraffin emulsions and silicone emulsions, and can also be provided with an oleophobic, rot-proof and / or crease-free finish can be combined, the known equipment also being used.
- the post-impregnation process engineering is generally known. As a rule, padding is carried out and then completed by drying and condensing. The additional impregnation can also be carried out before coating.
- the coating compositions can also contain other substances suitable for textile treatment, such as, in particular, finishing agents.
- substances suitable for textile treatment such as, in particular, finishing agents. Examples include aminoplast condensates. Soft-grip agents and flame retardants, as well as the corresponding catalysts if necessary, should also be mentioned.
- finishing liquors can also contain other substances suitable for textile treatment, such as finishing agents.
- finishing agents include aminoplast condensates.
- the method according to the invention is for the coating and finishing of fibrous materials of all kinds, Particularly suitable for textile fibrous materials in the form of woven, knitted or non-woven fabrics. These can be made both from natural fibers, such as cellulose or keratin fibers, and from synthetic fibers, such as polyacrylonitrile, polyamide or polyester. Of course, textile materials that consist of mixtures of natural and synthetic fibers are also suitable. It should be emphasized that, according to the method according to the invention, even slightly adjusted fabrics. how taffeta and / or slightly adjusted poplin fabrics can be treated. This is particularly important, for example, for rain protection clothing such as anoraks or the like.
- the modified organopolysiloxane copolymers used according to the invention have the advantage that they can be easily formulated into liquors and pastes and, above all, the pastes can be processed well with only minimal stickiness and good durability (pot life approx. 1 week).
- the compatibility with other polymers is almost unlimited due to the lack of catalysts.
- fibrous materials in particular textiles, are obtained from the coating, which have excellent waterproof properties and at the same time have a pleasant, soft feel, without the whiteness being significantly impaired. It is particularly noteworthy that the watertightness and above all its resistance to cleaning is given to a remarkably high degree. Otherwise, the further properties of the treated remain in the method according to the invention as well as in the known methods Materials such as especially the filling effect and the improved crease resistance are preserved. It cannot be inferred from the prior art in any way that the modified organopolysiloxane copolymers used here would provide the desired synergism with regard to the level of effects and the persistence of the effects. But excellent overall effects can also be achieved in a simple manner within the scope of the usual equipment.
- the whiteness is determined using a formula developed by GANZ (see RG Griesser, Textilveredlung 18 (1983), No. 5, pages 157 to 162).
- the "ELREPHO 2000 spectral photometer for remission measurements” from DATACOLOR has proven itself for these investigations.
- the water resistance is determined according to DIN 53886 and the irrigation according to DIN 53888 (duration 10 minutes).
- the mixture obtained is then homogenized on a high-pressure homogenizing machine at 250 bar and 55 ° C. for homogenization.
- the emulsion obtained is then placed in a 1 liter four-necked flask equipped with a contact thermometer, reflux condenser, stirrer and nitrogen inlet tube and the polymerization is completed under nitrogen at 95 ° C. for 3 hours.
- the organopolysiloxane copolymer dispersion obtained has a dry matter content of approximately 22%.
- the mixture in the feed vessel is pumped into the polymerization vessel over 15 minutes (stirrer speed 200 revolutions per minute), the temperature is set to 64 ° C. and the polymerization is carried out as follows: First 4 ml of 30% hydrogen peroxide are added, the mixture is stirred for 2 minutes and the addition of 8680 microliters of a 10% solution of sodium hydroxymethanesulfinate is started (metering rate 104 microliters per minute) and the temperature is kept constant between 63 and 67.degree . After 60 minutes, 0.5 ml of 10% sodium carbonate solution are poured in and after 135 minutes the main reaction has ended.
- the dispersion obtained has a dry matter content of 42.3% and a pH of 4 to 5.
- a white polyamide taffeta (approx. 70 g / m2) is treated as follows: 1000 g of the dispersion of the modified organopolysiloxane copolymer prepared as described above mixed with 30 g of a commercially available thickener based on polyacrylic acid (diluted 1: 1 with distilled water) and 3 ml of a commercially available nonionic defoamer and slowly added 1 ml of 25% ammonia while stirring.
- the coating composition is adjusted to a viscosity of 13000 mPa.s (product A according to the invention).
- a product B is prepared as follows: 1000 g of the copolymer dispersion given in Example 1 of DE-PS 2 616 797 are mixed with 10 g of a compound having the formula H2N (CH2) 2NH (CH2) 3Si (OC2H5) 3, 20 g of dibutyltin dilaurate and 20 g of 60% acetic acid a coating compound mixed.
- a product C is prepared as follows: 600 g of the copolymerization dispersion given in Example 1 of DE-PS 2 616 797 and 400 g of a commercially available approximately 60% dispersion of an ⁇ , ⁇ -dihydroxidimethylpolysiloxane (viscosity of the silicone approximately 80,000 mPa.s at 20 ° C.) are mixed with the components mentioned under product B are mixed to form a coating material.
- the polyamide taffeta is coated in one coat with 8 g / m 2 (based on solid substance), finally dried, with an aqueous liquor composed of 60 g / l® Scotchgard FC 270 (3M Company) and 10 g / l of a commercially available approx. 60% extender based on fat-modified synthetic resin, impregnated again, briefly dried and condensed at approx. 150 ° C for 2-3 minutes.
- the results of the equipment obtained are summarized in the following table after being displayed in a normal climate:
- Example 1 is repeated in the manner described, with the exception that 7.45 g of vinyl tributoxisilane are used instead of the methacryloyloxypropyltriethoxisilane given there and the same amount of lauryl alcohol is used in the 1st stage for the reaction instead of the cetyl alcohol.
- Example 1 the following monomers are copolymerized based on the organopolysiloxane copolymer of stage 1 of Example 1 in the manner described in Example 1, stage 2: 147 g butyl acrylate, 98 g vinyl acetate, 17 g styrene and 12 g of N-methoxymethylacrylamide.
- a polyester / cotton poplin (67:33, approx. 110 g / m2) or a pure cotton poplin (120 g / m2) is coated in one coat with the dispersion prepared in this way, which is adjusted to approx. 45% by weight dry matter (edition 10 or 12 g / m2) and, as indicated in Example 1, impregnated and finished, a good degree of whiteness, good washable and cleaning-resistant water resistance and, above all, a pleasantly soft soft hand grip are obtained.
- stage 2 is carried out as follows, based on the organopolysiloxane copolymer of stage 1 of example 1: Be in the polymerization vessel 645 g of the dispersion prepared in stage 1, 11.2 g of the ethoxylated nonylphenol sodium sulfate mentioned there, 2.55 g of the 10% solution of polyvinylpyrrolidone, 169 g of double distilled water, 0.55 g of 2-acrylamido-2-methylpropane sodium sulfonate and 5.9 g of a 10% sodium carbonate solution filled at intervals of about 3 minutes and stirred together at a speed of 250 revolutions / minute for 1 hour.
- the polymerization is carried out as described in Example 1. A stable dispersion of 30% by weight is obtained.
- a cotton poplin (approx. 120 g / m2) is equipped with the dispersion prepared in this way as follows: It's going to be a fleet 30 g / l of a 70% aqueous solution of a cellulose crosslinking agent (mixture of dimethyloldihydroxyethylene urea and 6: 1 pentamethylolmelamine etherified with methanol with about 4% neutral salt), 9 g / l of an approx.
- a cellulose crosslinking agent mixture of dimethyloldihydroxyethylene urea and 6: 1 pentamethylolmelamine etherified with methanol with about 4% neutral salt
- the fabric finished in this way has a very good, permanent water repellency and a pleasantly soft, full silicone grip without significantly affecting the degree of whiteness.
- Example 1 the following monomers are copolymerized based on the organopolysiloxane copolymer of stage 1 of this example in the manner described there under stage 2: 182 g butyl acrylate 99.3 g of ethyl acrylate 5.1 g acrylamide 1.6 g of 2-acrylamido-2-methylpropane sodium sulfonate and 24.3 g of N-butoxymethyl methacrylamide.
- a commercially available release paper is coated with the following composition: 200 g of product A according to the invention mentioned in Example 1, 2 g of a commercially available thickener based on polyacrylic acid (diluted 1: 1 with distilled water), 0.5 g of a commercially available defoamer (®RESPUMIT SI from Bayer) and 5 ml / l of a 10% ammonia.
- 200 g of product A according to the invention mentioned in Example 1 2 g of a commercially available thickener based on polyacrylic acid (diluted 1: 1 with distilled water), 0.5 g of a commercially available defoamer (®RESPUMIT SI from Bayer) and 5 ml / l of a 10% ammonia.
- the circulation is 5 g / m2 (based on dry matter).
- the coated paper is then dried at 90 ° C. for 10 minutes and condensed at 120 ° C. for 15 minutes.
- the paper which is provided with a soft, water-repellent and waterproof film in this way, is outstandingly suitable as release paper.
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Textile Engineering (AREA)
- Dispersion Chemistry (AREA)
- Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
- Silicon Polymers (AREA)
- Graft Or Block Polymers (AREA)
- Processing And Handling Of Plastics And Other Materials For Molding In General (AREA)
- Processes Of Treating Macromolecular Substances (AREA)
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
AT89120826T ATE92551T1 (de) | 1988-11-19 | 1989-11-10 | Verfahren zur behandlung von faserigen materialien mit modifizierten organopolysiloxanen und die so behandelten materialien. |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DE3839136 | 1988-11-19 | ||
DE3839136A DE3839136A1 (de) | 1988-11-19 | 1988-11-19 | Verfahren zur behandlung von faserigen materialien mit modifizierten organopolysiloxanen und die so behandelten materialien |
Publications (3)
Publication Number | Publication Date |
---|---|
EP0370326A2 EP0370326A2 (de) | 1990-05-30 |
EP0370326A3 EP0370326A3 (de) | 1992-04-08 |
EP0370326B1 true EP0370326B1 (de) | 1993-08-04 |
Family
ID=6367482
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
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EP89120826A Expired - Lifetime EP0370326B1 (de) | 1988-11-19 | 1989-11-10 | Verfahren zur Behandlung von faserigen Materialien mit modifizierten Organopolysiloxanen und die so behandelten Materialien |
Country Status (5)
Country | Link |
---|---|
EP (1) | EP0370326B1 (es) |
JP (1) | JPH02175973A (es) |
AT (1) | ATE92551T1 (es) |
DE (2) | DE3839136A1 (es) |
ES (1) | ES2058445T3 (es) |
Families Citing this family (8)
Publication number | Priority date | Publication date | Assignee | Title |
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DE4101884C2 (de) * | 1991-01-23 | 2001-05-03 | Sonderhoff Ernst Fa | Verfahren zur Herstellung von Schaumstoffbeschichtungen oder zur Flächenverklebung von Materialien und dessen Anwendung |
DE4330967A1 (de) * | 1993-09-13 | 1995-03-16 | Pfersee Chem Fab | Organische Siliciumverbindungen enthaltende Zusammensetzungen für die Behandlung von Fasermaterialien |
DE59600007D1 (de) * | 1995-03-09 | 1997-08-07 | Wacker Chemie Gmbh | Bindemittel für textile Flächengebilde |
FR2796272B1 (fr) * | 1999-07-15 | 2003-09-19 | Oreal | Composition sans cire structuree sous forme rigide par un polymere |
GB0029198D0 (en) * | 2000-11-30 | 2001-01-17 | Ciba Sc Holding Ag | Liquid dispersion polymer compositions their preparation and their use |
US8080257B2 (en) | 2000-12-12 | 2011-12-20 | L'oreal S.A. | Cosmetic compositions containing at least one hetero polymer and at least one film-forming silicone resin and methods of using |
US6716420B2 (en) | 2001-10-05 | 2004-04-06 | L′Oreal | Methods of use and of making a mascara comprising at least one coloring agent and at least one heteropolymer |
US20050008598A1 (en) | 2003-07-11 | 2005-01-13 | Shaoxiang Lu | Cosmetic compositions comprising a structuring agent, silicone powder and swelling agent |
Family Cites Families (11)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3398017A (en) * | 1964-09-14 | 1968-08-20 | Dow Corning | Water repellent treatment |
GB1389873A (en) * | 1972-07-19 | 1975-04-09 | Vnii Pererabotke Nefti | Method for preparing branched copolymers of ethylene with unsaturated silicon-containing monomers |
DE2404432A1 (de) * | 1974-01-30 | 1975-08-07 | Pfersee Chem Fab | Verfahren zum veredeln von textilmaterial, das polyacrylnitrilfasern enthaelt |
GB1604519A (en) * | 1977-07-25 | 1981-12-09 | Bausch & Lomb | Polysiloxane polymers and contact lens and other biomedical articles formed therefrom |
DE3105148A1 (de) * | 1981-02-12 | 1982-09-09 | Wacker-Chemie GmbH, 8000 München | "verfahren zur beschichtung von unterlagen" |
DE3108595A1 (de) * | 1981-03-06 | 1982-09-16 | Wacker-Chemie GmbH, 8000 München | Verfahren zur beschichtung von unterlagen |
DE3151924A1 (de) * | 1981-12-30 | 1983-07-07 | Bayer Ag, 5090 Leverkusen | Waessrige polysiloxanzubereitungen |
DE3201194A1 (de) * | 1982-01-16 | 1983-07-28 | Bayer Ag, 5090 Leverkusen | Vernetzbare pfropfpolymerisat-dispersionen aus hydrogensiloxan-gruppen und si-vinyl-gruppen enthaltenden organopolysiloxanen |
GB8319300D0 (en) * | 1983-07-16 | 1983-08-17 | Ciba Geigy Ag | Treating textiles |
DE3535136A1 (de) * | 1985-10-02 | 1987-04-09 | Bayer Ag | Diorganosiloxanpolymerisatpulver |
DE3617267A1 (de) * | 1986-05-23 | 1987-11-26 | Bayer Ag | Kerbschlagzaehe pfropfpolymerisate |
-
1988
- 1988-11-19 DE DE3839136A patent/DE3839136A1/de not_active Withdrawn
-
1989
- 1989-11-10 AT AT89120826T patent/ATE92551T1/de not_active IP Right Cessation
- 1989-11-10 DE DE8989120826T patent/DE58905149D1/de not_active Expired - Fee Related
- 1989-11-10 EP EP89120826A patent/EP0370326B1/de not_active Expired - Lifetime
- 1989-11-10 ES ES89120826T patent/ES2058445T3/es not_active Expired - Lifetime
- 1989-11-16 JP JP1296304A patent/JPH02175973A/ja active Pending
Also Published As
Publication number | Publication date |
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ES2058445T3 (es) | 1994-11-01 |
ATE92551T1 (de) | 1993-08-15 |
EP0370326A3 (de) | 1992-04-08 |
DE58905149D1 (de) | 1993-09-09 |
JPH02175973A (ja) | 1990-07-09 |
DE3839136A1 (de) | 1990-05-23 |
EP0370326A2 (de) | 1990-05-30 |
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