Classifications

• • D—TEXTILES; PAPER
  • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
  • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
  • D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
  • D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
  • D06M15/21—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
  • D06M15/263—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of unsaturated carboxylic acids; Salts or esters thereof
• • D—TEXTILES; PAPER
  • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
  • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
  • D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
  • D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
  • D06M15/21—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
  • D06M15/244—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of halogenated hydrocarbons
• • 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
  • D06N3/04—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 by reactions only involving carbon-to-carbon unsaturated bonds
  • D06N3/047—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 by reactions only involving carbon-to-carbon unsaturated bonds with fluoropolymers
• • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
  • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
  • Y10T428/00—Stock material or miscellaneous articles
  • Y10T428/31504—Composite [nonstructural laminate]
  • Y10T428/3154—Of fluorinated addition polymer from unsaturated monomers

Definitions

• the invention relates to an aqueous dispersion for producing corrosion and weather-resistant coatings on materials such as fiber fabrics, in particular synthetic fiber fabrics, glass, glass fabrics, metal, ceramics and the like, which contains a-polyvinylidene fluoride, an acrylic copolymer and a pigment, and a process for Creation of corrosion and weather resistant coatings using this dispersion.
• the polyvinyl chloride used for this purpose is set to be soft with the help of additives, and usually contains a "plasticizer content of 40 to 60 wt .-%.
• the polyvinyl chloride surface is subject to degradation and destruction under the influence of light when used outdoors, for example as a truck tarpaulin or as a material for air-filled halls. As a result of this degradation, the polyvinyl chloride becomes brittle, becomes rough and cracked, with the result that the surfaces coated with it become very dirty and attacked.
• membrane building materials for example glass fabrics coated with polytetrafluoroethylene. These membrane building materials show excellent weather resistance outdoors, very good dirt repellency de properties and are practically non-flammable. Their disadvantage is the complex production method, which leads to a very expensive end product. Furthermore, only special glass filament fabrics can be used as fabrics, the yarns of which are made of fine threads and which are consequently also cost-intensive. These substrate fabrics also have a much lower elongation than polyester fabrics, for example. The tear strength of coated glass fabrics is therefore lower than that of corresponding polyester fabrics.
• Air-drying aqueous polyvinylidene fluoride dispersions are known from DE-OS 23 25 304, which contain vinylidene fluoride, an acrylate polymer and optionally pigments, flow control agents, solvents, surface-active agents, thickeners and the like. These dispersions result in hard and tough coatings. If they are applied to synthetic fiber fabrics in layer thicknesses, as are customary for coatings made of soft polyvinyl chloride, rigid products are obtained which are not suitable for truck tarpaulins, air-filled halls, conveyor belts and the like. In addition, the wetting agents to be used according to this prior art increase the susceptibility of the fiber fabrics to dirt.
• DE-OS 28 18 385 describes polyvinylidene fluoride moldings with a textile fabric which are obtained by pressing extruded polyvinylidene fluoride sheets at elevated temperature with a thermoplastic polyester fleece.
• the rigid composite panels obtained in this way serve as semi-finished products for container construction. Due to their rigidity, they are also unsuitable for the membrane construction materials application mentioned above.
• the object of the present invention is to provide an aqueous dispersion and a method with who succeeds in forming corrosion-resistant and weather-resistant coatings on materials, in particular on synthetic fiber fabrics, so that membrane building materials are obtained which are suitable as truck tarpaulins, for air-filled halls, tents, cover mats, conveyor belts and the like, while at the same time minimizing the environmental impact is achieved by organic solvents.
• the subclaims relate to particularly preferred embodiments of this object of the application and to a method for producing corrosion-resistant and weather-resistant coatings on materials, in particular synthetic fiber fabrics, using this aqueous dispersion according to the invention.
• the aqueous dispersion according to the invention results in homogeneous, firmly adhering and very flexible coatings, which are also smooth, glossy and waterproof, even in larger application amounts on synthetic fiber fabrics.
• the invention thus relates to an aqueous dispersion of the type defined at the outset, which is characterized by a content of
• the aqueous dispersion preferably contains the polyvinylidene fluoride in an amount of 30 to 45% by weight.
• the polyvinylidene fluoride is preferably used with an average primary particle size of less than 0.5 ⁇ m, produced by the process according to DE-PS 1 939 852.
• the aqueous dispersion contains 35 to 45% by weight of water.
• the acrylic copolymer contained in the aqueous dispersion is preferably a water-soluble copolymer of acrylic acid and / or methacrylic acid and one or more monomers copolymerizable therewith, such as acrylamide, methacrylamide, acrylonitrile, methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, butyl acrylate, butyl methacrylate, styrene, butadiene and butadiene or vinyl acetate.
• the acrylic copolymer is preferably used in the form of the ammonium salt.
• the aqueous acrylic copolymer solutions which can be obtained under the name "Glascol HA 4" from Allied Colloids, Ltd., Great Britain are particularly preferably used. These are clear, white or pale yellow solutions of the ammonium salt of acrylic copolymer having a viscosity of 30 to 70 poise at 20 ° C, a solids content of 30 + or - 1%, a pH value of 7.5 to 8.5, a specific gravity of 1.07 p / cm J exhibit. These acrylic copolymer solutions form water-resistant, soft and flexible films.
• the acrylic copolymers used in the aqueous dispersion according to the invention result in an increase in the adhesive strength of the coating composition on the substrate and in an increase in the flexibility and the softness of the grip of the entire composite material.
• the aqueous dispersion according to the invention preferably additionally contains 2.5 to 10% by weight, preferably 2.5 to 5% by weight, based on polyvinylidene fluoride, of a plasticizer, such as Polypropylene adipate, polybutylene adipate, polypropylene sebacate, polybutylene sebacate and / or an ethylene / vinyl acetate copolymer.
• a plasticizer such as Polypropylene adipate, polybutylene adipate, polypropylene sebacate, polybutylene sebacate and / or an ethylene / vinyl acetate copolymer.
• an adhesion promoter such as a silane adhesion promoter, such as, for example, j-methacryloxypropyltrimethoxysilane, is also recommended here.
• auxiliary solvent to the aqueous dispersion which also serves as an auxiliary solvent for the light stabilizer, such as, for example, methyl ethyl ketone, ethyl acetate and / or xylene.
• the aqueous dispersion according to the invention contains 4 to 20% by weight, preferably 5 to 15% by weight, of a low-boiling alcohol, which preferably has a boiling point of not more than 120 ° C. at normal pressure.
• a low-boiling alcohol which preferably has a boiling point of not more than 120 ° C. at normal pressure.
• Low molecular weight alcohols of this type which are preferred according to the invention are primary, secondary or tertiary aliphatic alcohols having 1 to 5 carbon atoms, such as methanol, Ethanol, propyl alcohol, one of the butanols and especially isopropyl alcohol.
• This low-molecular alcohol is that the claimed dispersion has a good wetting of the substrate without introducing disruptive wetting agent residues into the finished coating.
• this low-molecular alcohol makes it easier to disperse in the polyvinylidene fluoride. If the claimed dispersion dries too quickly, it is advisable to use the low-boiling alcohol in combination with a solvent that delays drying. Solvents with boiling points / ranges between 120 and 180 ° C., such as diethylene glycol dimethyl ether, xylene, butyl glycol or mixtures thereof, are preferably used for this purpose. The amount of these higher-boiling solvents can replace up to 50% by weight of the low-boiling amount of alcohol.
• the aqueous dispersion contains 0.5 to 5.% by weight of a thickener, for example a water-soluble ammonium polyacrylate.
• a thickener for example a water-soluble ammonium polyacrylate.
• the "Latekoll AS" aqueous solution of ammonium polyacrylate available from BASF is particularly preferred.
• the aqueous dispersion according to the invention contains conventional UV light stabilizers, such as benzotriazole derivatives and / or sterically hindered amino groups containing light stabilizers, as light stabilizers.
• the light stabilizer mixture consisting of "Tinuvin P" and “Tinuvin 770" is particularly preferred. This light stabilizer is preferably used as a solution in particular ethyl acetate.
• Suitable pigments or fillers according to the invention are light-resistant and weather-resistant substrates, such as, for example, titanium dioxide of the rutile type, inorganic pigments or metal bronzes.
• antimony trioxide in order to make the coatings obtainable according to the invention flame-retardant, it is suitable to add antimony trioxide to the aqueous dispersion of the invention, the application rates expediently being between 3 and 7% by weight, based on the overall formulation.
• a particularly clear effect with regard to flame resistance is achieved by a synergistic combination of antimony trioxide and melamine cyanurate.
• Such particularly effective mixtures preferably consist of 1 to 5% by weight of antimony trioxide and 0.5 to 2% by weight of melamine cyanurate, based on the overall formulation. Most preferred is a combination of about 2% by weight of antimony trioxide with about 1% by weight of melamine cyanurate.
• the aqueous dispersion according to the invention has the advantage that it can be produced not only using dried polyvinylidene fluoride but also using material that is moist with centrifuges.
• This relatively large amount of water-binding material (40% by weight of water) is mixed with the constituents already described (acrylic copolymer, pigments, fillers, etc.) to produce the claimed dispersion and gently ground on a ball mill, sand mill or the like.
• the light stabilizer and the plasticizer are each used pre-dissolved in suitable solvents. Only for the production of dispersions with a particularly high polyvinylidene fluoride content should part of the water or the entire residual moisture be removed from the centrifuge-moist material.
• the claimed aqueous dispersion is suitable for producing corrosion-resistant and weather-resistant coatings on any materials, such as woven, non-woven or knitted fiber sheet structures, in particular synthetic fibers, on glass, glass fabrics, metal, ceramics and the like.
• the claimed aqueous dispersion is particularly suitable for coating P olyesterfasergeweben or polyamide fiber fabrics. These fiber fabrics preferably have basis weights of 80 to 350 g / m 2 .
• the invention further relates to a method for producing corrosion-resistant and weather-resistant coatings on materials, in particular synthetic fiber fabrics, which is characterized in that the aqueous dispersion described above is applied to the material and burned in after any predrying.
• the aqueous dispersion is applied to the surface to be coated by customary application methods, such as brushing, rolling, dipping, spraying and the like, and is dried at temperatures from 100 to 140 ° C., preferably from 120 to 130 ° C.
• the drying time is preferably 3 to 6 minutes. Then the applied coating is baked at temperatures of 170 to 210 ° C, and in particular from 190 to 200 ° C for 1 to 3 minutes.
• the material is pre-impregnated with a polyvinylidene fluoride latex.
• a polyvinylidene fluoride latex for this purpose, the polyvinylidene fluoride latices described in DE-PS 19 39 852 are preferably used.
• the pre-impregnation produced in this way is dried and baked at the temperatures given above with regard to the coatings to be produced.
• the pre-impregnation of the material with the polyvinylidene fluoride latex can be repeated up to 3 times, whereby each application must be dried and baked, although this can also be done after the entire pre-impregnation has been completed. It is preferably dried at 100 to 140 ° C. for 3 to 6 minutes and baked at 170 to 190 ° C. for 1 to 3 minutes. Then the application of the Deck cover in the manner described above.
• the material to be coated can also be pretreated with adhesion agent as methacryloxypropyltrimethoxysilane before the pre-impregnation is applied.
• application amounts of 80 to 200 g / m 2 are obtained per application of the dispersion, depending on its concentration and the type of material.
• both sides of the material can also be coated simultaneously in the dipping process.
• Additional surface smoothing for example with the help of so-called smoothing rollers or structuring of the surface with the help of structure rollers, is also possible at temperatures of 180 to 220 ° C.
• the aqueous dispersion according to the invention which consists predominantly of polyvinylidene fluoride, enables the permanent coating of synthetic fiber fabrics in particular, since it does not suffer any degradation reactions due to weather influences and thus maintains the decorative appearance of the coated surface unchanged.
• the claimed aqueous dispersion also has the advantage that it is easy to apply even in thicker layers and, thanks to the low application temperatures, enables the use of high-strength polyester fiber fabrics.
• the tensile strength and the large number of these fabrics allow an exact adaptation to the later use.
• the claimed dispersion and the method according to the invention provide weather-resistant, flexible, smooth, closed and dirt-repellent coatings of high quality.
• the fabrics coated in this way are particularly suitable for use in air-inflated halls, tent roofs, conveyor belts and special tarpaulins all kinds.
• Two coatings are applied, then dried at 130 to 135 ° C. for 5 to 6 minutes and baked at 200 to 210 ° C. for 2 to 3 minutes.
• a polymer coating with a basis weight of 180 to 210 g / m 2 with a smooth, white and closed surface is obtained.
• a polyester fabric with a weight per unit area of 275 g / m 2 is used and the fabric is pre-impregnated in accordance with the procedure described in Example 1.
• the mixture is dried at 120 to 125 ° C. for 6 minutes and baked at 190 to 200 ° C. for 3 minutes.
• a polymer coating with a basis weight of 250 to 270 g / m 2 is obtained and a metallic shiny, flexible and watertight membrane building material is obtained.
• M an uses a polyester fabric with a basis weight of 200 g / m 2 as the material.
• a polyester fabric with a basis weight of 200 g / m 2 is used as the material.
• the polyester fabric is impregnated with a polyvinylidene fluoride latex which contains 0.1% ⁇ -methacryloxypropyltrimethoxysilane.
• the material is applied by dipping and brushing, pre-drying at 130 ° C. for 6 minutes and baking at 210 ° C. for 3 minutes.
• the mixture is dried at 125 ° C. for 5 minutes and baked at 205 ° C. for 3 minutes. After coating three times, a polymer application amount of about 380 g / m 2 is obtained and a very flexible, smooth membrane building material is obtained.
• a polymer application of 550 to 600 g / m 2 is achieved .
• a polymer application of 250 to 350 g / m 2 is effected.
• polyester fabric described in Example 3 is used, but no pre-impregnation is carried out.
• a polymer application of 360 to 420 g / m 2 is achieved .
• polyester fabric described in Example 2 is used without pre-impregnation and coated three times with an aqueous dispersion of
• a polymer application of 250 to 330 g / m 2 is achieved and flexible, waterproof coatings are obtained.
• a polymer application of 410 to 430 g / m 2 is achieved in this way .
• Example 9 To demonstrate the flame retardancy of the coating, the same polyester fabric as in Example 9 is used and this is coated three times with the dispersion also mentioned in Example 9, in which 3.0% by weight of water by 2.0% by weight of antimony trioxide (Stibiox) and 1.0% by weight of melamine cyanurate were replaced.
• Stibiox antimony trioxide

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• Chemical & Material Sciences (AREA)
• Chemical Kinetics & Catalysis (AREA)
• Engineering & Computer Science (AREA)
• Textile Engineering (AREA)
• Paints Or Removers (AREA)
• Compositions Of Macromolecular Compounds (AREA)
• Laminated Bodies (AREA)
• Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)

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Publications (3)

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• 1981
  • 1981-01-23 DE DE19813102169 patent/DE3102169A1/de not_active Withdrawn
• 1982
  • 1982-01-08 DE DE8282100126T patent/DE3261636D1/de not_active Expired
  • 1982-01-08 AT AT82100126T patent/ATE10958T1/de not_active IP Right Cessation
  • 1982-01-08 EP EP82100126A patent/EP0057813B1/fr not_active Expired
  • 1982-01-25 GB GB8202059A patent/GB2095265B/en not_active Expired
• 1983
  • 1983-05-10 US US06/491,345 patent/US4510282A/en not_active Expired - Fee Related

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