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WO1996032529A1 - Substrat polymerique avec produits d'addition et procede de fabrication par diffusion causee par un phenomene thermique - Google Patents

Substrat polymerique avec produits d'addition et procede de fabrication par diffusion causee par un phenomene thermique Download PDF

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Publication number
WO1996032529A1
WO1996032529A1 PCT/US1996/005094 US9605094W WO9632529A1 WO 1996032529 A1 WO1996032529 A1 WO 1996032529A1 US 9605094 W US9605094 W US 9605094W WO 9632529 A1 WO9632529 A1 WO 9632529A1
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WO
WIPO (PCT)
Prior art keywords
substrate
particles
powder
polymer
additive
Prior art date
Application number
PCT/US1996/005094
Other languages
English (en)
Inventor
Frederick Robert Hopf
Keith Alan Horn
Richard Bidwell Heath
Original Assignee
Alliedsignal Inc.
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Alliedsignal Inc. filed Critical Alliedsignal Inc.
Publication of WO1996032529A1 publication Critical patent/WO1996032529A1/fr

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Classifications

    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M10/00—Physical treatment of fibres, threads, yarns, fabrics, or fibrous goods made from such materials, e.g. ultrasonic, corona discharge, irradiation, electric currents, or magnetic fields; Physical treatment combined with treatment with chemical compounds or elements
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D1/00—Processes for applying liquids or other fluent materials
    • B05D1/02—Processes for applying liquids or other fluent materials performed by spraying
    • B05D1/04—Processes for applying liquids or other fluent materials performed by spraying involving the use of an electrostatic field
    • B05D1/06—Applying particulate materials
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D7/00—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials
    • B05D7/02—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials to macromolecular substances, e.g. rubber
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B60—VEHICLES IN GENERAL
    • B60C—VEHICLE TYRES; TYRE INFLATION; TYRE CHANGING; CONNECTING VALVES TO INFLATABLE ELASTIC BODIES IN GENERAL; DEVICES OR ARRANGEMENTS RELATED TO TYRES
    • B60C9/00—Reinforcements or ply arrangement of pneumatic tyres
    • B60C9/0042—Reinforcements made of synthetic materials
    • 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
    • D06M10/00—Physical treatment of fibres, threads, yarns, fabrics, or fibrous goods made from such materials, e.g. ultrasonic, corona discharge, irradiation, electric currents, or magnetic fields; Physical treatment combined with treatment with chemical compounds or elements
    • D06M10/04—Physical treatment combined with treatment with chemical compounds or elements
    • 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
    • D06M23/00—Treatment of fibres, threads, yarns, fabrics or fibrous goods made from such materials, characterised by the process
    • D06M23/08—Processes in which the treating agent is applied in powder or granular form

Definitions

  • the present invention relates to a polymer substrate with additives diffused therein and to the thermally induced diffusion process for making the same. More particularly, this invention relates to an organic polymer fiber or article manufactured therefrom with an additive or additives diffused therein to stabilize, modify or enhance properties thereof.
  • This invention specifically relates to woven polyester or polyamide fabric which has a light stabilizer diffused therein by a thermally induced diffusion process to render the fabric resistant to fading and degradation by light without substantially impairing physical properties.
  • This invention also specifically relates to polyester fiber and polyester or polyamide fabric which has an adhesion promoter substantially diffused therein by a thermally induced diffusion process to improve adhesion to various coatings.
  • Automotive applications require lightfastness for dyed materials, such as seat belts, to minimize color changes and strength loss on exposure to UV light.
  • Many of the dyes currently used in seat belts are not Lightfast, and it is unlikely that significantly more light stable dyes will become available in the foreseeable future.
  • the established polymers presently used to produce fiber for narrow web are also not likely to be replaced by significantly more light stable polymers in the near future since the more light stable polymers have comparatively unacceptable strength properties.
  • One approach toward reducing the photodegradation of polymers and/or dyes within them is to add a very light stable, strongly absorbing material which will effectively screen the incoming radiation by competing with the dye and polymer components for absorption of the damaging wavelengths of light. If the screen absorbs and effectively converts the damaging wavelengths of light to harmless thermal energy, the dyed polymer substrate will have improved lightfastness and be able to pass more stringent lightfastness requirements.
  • Light stabilizers are known for use with polymer substrates such as films, fibers and articles manufactured therefrom.
  • the two most common methods of incorporating the light stabilizers are via mixing with the base polymer and by coating, dipping or overspraying the film, fiber or woven fabric. Since damage to dyes as well as the polymer structure itself occurs primarily near the surfaces where Light is absorbed, mixing with the base polymer, where the stabilizer is uniformly distributed throughout the article, is wasteful, inefficient, and expensive.
  • a light stabilizer in regions of a filament or yarn bundle that are not exposed to light, e.g., in fill fibers, or the portions of fibers covered at crossover points.
  • the solvents and/or other liquids used as carriers for the stabilizer can pose environmental and workplace hazards.
  • Most solvent based application methods also have the drawback that the solvent carrier penetrates the interstitial spaces of fiber yarns, woven fabrics and polymer structures with surface texture to carry with it the light stabilizer or other additive. The result is that the additive is placed deep within the object where it is ineffective at stabilization or surface property modification. It would therefore be advantageous to have a solvent-free and thus environmentally friendly process to apply UV light stabilizers and/or other property modifiers or additives to polymeric substrates such as molded objects, fiber and fabric, and in particular to seat belt webbing. Such a process should strategically concentrate the stabilizer in the substrate near its surface where it is most beneficial and economical.
  • the present invention is a solvent-free, environmentally friendly, cost- effective process of incorporating additives within a polymer substrate to stabilize and/or modify the same.
  • the process eliminates the use of solvents, levelling agents, pH modifiers, and dispersing aids while making efficient use of the additives, which are placed only at selected surfaces rather than being uniformly distributed throughout the substrate. It also permits the incorporation of a wider range of additives since many of those that are thermally unstable or cause undesirable color or cut molecular weight or are volatilized at the higher polymer processing temperatures are thermally stable at the treating temperatures used in the process of this invention.
  • This process comprises the steps of a.
  • the powder comprising a plurality of dry, heat fusible particles selected from the group consisting of heat stabilizers, preservatives, antistatic agents, adhesion promoting agents, light stabilizers, flame retardants, antisoiling agents, antistain agents, mixtures thereof and mixtures thereof with dyeing agents; and b. heating the particles to a temperature above the T g of the substrate and above the melting point of the particles but below the melting point of the substrate for a time sufficient to melt the particles and cause the melt to diffuse into the substrate.
  • This invention also includes a product made in accordance with this process.
  • the present invention is a solvent-free process for inco ⁇ orating an additive within a polymer substrate, comprising the steps of a. electrostatically depositing an effective amount of a dye-free powder onto a surface of a polymer substrate, the powder comprising a plurality of dry, heat fusible additive particles; and b. heating the particles to a temperature above the T, of the substrate and above the melting point of the particles but below the melting point of the substrate for a time sufficient to melt the particles and cause the melt to substantially diffuse into the substrate.
  • the product made by this process is also part of the present invention.
  • the present invention is also a solvent-free process for rendering a surface of a polymer substrate stable to light, with the attendant advantages stated previously.
  • the process comprises the steps of: a. electrostatically depositing an effective amount of a powder onto a surface of a polymer substrate, the powder comprising a plurality of dry, heat fusible, light stabilizing particles; and b. heating the particles to a temperature above the T g of the substrate and above the melting point of the particles but below the melting point of the substrate for a time sufficient to melt the particles and cause the melt to diffuse into the substrate.
  • This embodiment preferably is a continuous process wherein the substrate is a length of woven fabric, preferably polyester, which is maintained under tension during the depositing and heating steps.
  • the preferred tension ranges from about 445 to about 6670 N, more preferably from about 1110 to about 5560 N, and most preferably from about 2200 to about 4450 N
  • the preferred heat treatment is at a temperature of about 200 to about 250°C, more preferably about 210 to about 240° C, for about 1 to about 6 minutes, more preferably about 1.5 to about 3.5 minutes.
  • the heating step also serves to set the dye particles on the surface.
  • this embodiment permits the simultaneous solvent-free dyeing of the substrate when the powder further comprises a plurality of dry, heat fusible dye particles.
  • This invention also includes the product made in accordance with this process, which preferably is a seat belt webbing.
  • the products made in accordance with the above-described processes of the present invention preferably are characterized by having the additive particles diffused therein at a loading of from about 0.01 to about 10 weight percent, more preferably from about 0.1 to about 5.0 weight percent, and most preferably from about 0.1 to about 2.0 weight percent.
  • the additive is distributed in surface regions of the substrate to modify surface properties.
  • a particularly preferred product of the present invention is a dyed, woven polyester fabric, preferably a narrow web for seat belts, comprising a plurality of multi-filament wa ⁇ and multi-filament weft yarn bundles wherein the powder diffused into the woven fabric at the loadings set forth above comprises a plurality of light stabilizer particles, preferably of a hydroxybenzophenone, and most preferably of 2,4-dihydroxybenzophenone, further characterized by a n inimum weight ratio of the stabilizer within the multi-filament wa ⁇ to that within the multi- filament weft yam bundles of about 1 to 1, with higher weight ratios being preferred.
  • the stabilizer is diffused at intermittent regions into the filaments of the multi-filament wa ⁇ yarn bundle. Those regions that do not contain any stabilizer correspond to cross-over points in the webbing, i.e., where the wa ⁇ yarn bundle crosses over the weft yarn bundle.
  • the product comprises at least one multi- filament yarn bundle characterized by asymmetric stabilizer diffusion therein, with respect to a cross-section thereof.
  • this invention is a solvent-free process for rendering a surface of a polyester or polyamide substrate adherent to another material, such as polyurethane, polyvinyl chloride, or rubber, comprising the steps of: a. electrostatically depositing an effective amount of a powder onto the surface of the polymer substrate, the powder comprising a plurality of dry, heat fusible, adhesion promoting particles; and b. heating the particles to a temperature above the T g of the substrate and above the melting point of the particles but below the melting point of the substrate for a time sufficient to melt the particles and cause the melt to diffuse into the substrate.
  • This invention includes a polyester tire cord made in accordance with this process and having improved adhesion to rubber, as well as the resulting tire. It also includes a woven polyester or polyamide fabric made in accordance with this process and having improved adhesion to a coating of polyurethane, polyvinyl chloride, or rubber, such as neoprene, as well as the resulting coated fabric.
  • FIGURE 1 is a perspective view of a partial length of a filament taken from a multi-filament wa ⁇ yarn bundle having a medium loading of powder diffused therein, showing the intermittent regions of powder diffused therein;
  • FIGURES 2A, 2B, 2C and 2D are views in cross-section of multi-filament wa ⁇ yarns having, respectively, no powder diffused therein, a high loading of powder diffused therein, a medium loading of powder diffused therein, and a low loading of powder diffused therein.
  • DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention permits the inco ⁇ oration of a wide range of additives at selective surfaces/sites of a polymer substrate to stabilize and/or modify the same.
  • the process essentially comprises the steps of: (a) electrostatically depositing an effective amount of a powder onto a surface of a polymer substrate, the powder comprising a plurality of dry, heat fusible, additive particles; and (b) heating the particles to a temperature above the T ( of the substrate and above the melting point of the particles but below the melting point of the substrate for a time sufficient to melt the particles and cause the melt to substantially diffuse into the substrate.
  • polymer fibers and articles manufactured from such fibers e.g., mono- or multi-filament fiber, cordage, broad and narrow fabrics (woven, nonwoven, and knitted).
  • the polymer substrate can additionally include film, molded objects, and the like, so long as the chosen substrate is capable of having the additive particles substantially diffused thereinto according to the processes to be described.
  • Preferred polychlorotrifluoroethylene films include homopolymers and copolymers of chlorotrifluoroethylene.
  • the more preferred polychlorotrifluoroethylene films are commercially available from AlliedSignal Inc., Morristown, New Jersey as ACLAR ⁇ film or HALAR®film as indicated in the following Table I:
  • the preferred substrates are fabrics, particularly narrow woven fabrics, and cordage.
  • Organic polymer substrates are preferred, such as substrates composed of homopolymers, copolymers, blends, and grafts of the following materials: polyamides; polyesters; polyolefins; polyvinyls; fluoropolymers; acrylics; aramids; acetates; and polycarbonates.
  • Inorganic polymer substrates composed of, e.g., polyphosphazenes, polythiazyls, may also be used, although they are less preferred.
  • the substrates may be formed from a combination of different polymers, e.g., fabrics may be formed which utilize different fiber types in a hybrid construction (a fabric blend) taking advantage of the different fiber properties, or a substrate may be formed from fabric layers of different fiber types.
  • the preferred substrates are formed with organic polymers, although blends of organic and inorganic polymeric substrates, e.g., fabric blends of organic and inorganic fibers, are considered to be part of the present invention.
  • polyamide denotes those synthetic long chain polyamides having recurring amide groups as an integral part of the polymer chain.
  • Exemplary of such polyamides are nylon 6; nylon 6,6; nylon 4,6; nylon 7; nylon 10. nylon 11; nylon 12; etc.
  • the preferred polyamide substrates are the broad woven coated fabrics wherein the coatings can be polyurethanes, polyvinyl chlorides, and various rubbers, such as neoprene.
  • the additive particles are chosen to enhance adhesion of the polyamide substrate to the coating and/or to enhance the UV light stability of the polyamide substrate.
  • polyester denotes homopolymers, copolymers and polymer blends of polyethylene terephthalate (PET) and polyethylene naphthalate (PEN).
  • PET polyethylene terephthalate
  • PEN polyethylene naphthalate
  • the PEN polymer preferably contains at least about 85 mol percent polyethylene naphthalate.
  • This polyester may inco ⁇ orate as copolymer units minor amounts of units derived from one or more ester-forming ingredients other than ethylene glycol and 2,6-naphthalene dicarboxylic acid or their derivatives.
  • ester forming ingredients which may be copolymerized with the polyethylene naphthalate units include glycols such as 1,3- propanediol, 1,4-butanediol, 1,6-hexanediol, etc., and dicarboxylic acids such as terephthalic acid, isophthalic acid, hexahydroterephthalic acid, stilbene dicarboxylic acid, bibenzoic acid, adipic acid, sebacic acid, azelaic acid, etc. See U.S. Patent 5,397,527, hereby inco ⁇ orated by reference to the extent not inconsistent herewith.
  • the PET polymer preferably contains at least about 85 mol percent polyethylene terephthalate.
  • This polyester may inco ⁇ orate as copolymer units minor amounts of units derived from one or more ester-forming ingredients other than ethylene glycol and terephthalic acid or its derivatives.
  • ester-forming ingredients which may be copolymerized with the polyethylene terephthalate units include glycols such as diethylene glycol, trimethylene glycol, tetramethylene glycol, hexamethylene glycol, etc., and dicarboxylic acids such as isophthalic acid, hexahydroterephthalic acid, bibenzoic acid, adipic acid, sebacic acid, azelaic acid, etc. See U.S.
  • PET/PEN polymer blends with up to about 35 weight percent of PEN and about 65 to 100 weight percent PET, as PET and PEN are defined above, can be used.
  • the preferred polyester substrates are broad woven fabrics, especially air bags and awnings, where the additive particles are chosen to enhance light stability and adhesion to rubber; narrow woven fabrics, especially automotive seat belt webbing, where the additive particles are chosen to enhance light stability; and tire cordage where the additive particles are chosen to enhance adhesion of the fiber to a coating which in turn adheres the fiber to rubber.
  • polyolefin denotes polymers containing at least about 85 percent by weight of ethylene, propylene, or other olefin units.
  • the preferred polyolefins are polyethylene, polypropylene and polytetrafluoroethylene.
  • the preferred polyethylene substrate is a SPECTRA ⁇ SHIELD composite or a woven fabric where the additive particles are chosen to enhance light stability and/or flame retardance.
  • the preferred polypropylene substrates are fibers, ropes and films where the additive particles are chosen to enhance light stability.
  • polyvinyls denotes polymers containing a number of vinyl, CH 2 :CHX, groups units in a polymerized form.
  • Polyvinyl derivatives include polyacrylonitrile, polyacrylate, polyvinyl chloride, and polystyrene.
  • the preferred substrates are fibers or fabrics where the additive particles are chosen to enhance flame retardance or light stability.
  • the preferred polycarbonate substrates are molded objects, such as visors, headlamps, and tail light covers, where the additive particles are chosen to enhance light stability.
  • Table II below sets forth a preferred list of fibers useful in forming some of the polymer substrates of this invention. These fibers are commercially available from AlliedSignal Inc., and are described in greater detail in the AlliedSignal Fibers Industrial Fibers Guide (1994), hereby inco ⁇ orated by reference.
  • PRODUCTS FIBER POLYMERS PRODUCT DESIGNATION nylon 6 1D70, 1G81, 1R70, 1R79, 1R86, 1R88 polyethylene 1W70, 1W72, 1W86, 1X30, 1X40, 1X50, 1X90 terephthalate polyethylene SPECTRA®900, SPECTRA®1000
  • melting point of the polymer in the substrate is meant the temperature at which the first principal endotherm is seen which is attributable to the major polymer constituent in the substrate.
  • melting point of the particles is meant the temperature at which the solid and liquid states of the additive material coexist in equilibrium.
  • the glass transition temperature, T g of the polymer substrate is the approximate midpoint of the temperature range over which the glass transition takes place, and is measured using a differential scanning calorimeter (DSC) (See ASTM D883 and E1356-91, and Peyser, "Glass Transition Temperatures of Polymers," Polymer Handbook. 3d Ed., John Wiley & Sons, Inc., pVI-209 et seq. (1989). Melting points of various polymers can be found in the Polymer Handbook and are typically available from the particular manufacturer of the polymer or polymer substrate.
  • the T g ranges from about 60 to about 85°C
  • the melting point ranges from about 240 to about 255°C.
  • T ranges from about room temperature to about 60°C, depending on the humidity and the melting point ranges from about 210 to about 225°C. (measured @ 20°CJmin. heating rate by DSC).
  • the workpiece or in this instance the substrate, is exposed to a cloud of electrostatically charged particles with the substrate at an electrical potential effective to attract the particles of the cloud thereto to form a coating.
  • the substrate can be exposed by passing it over or through a fluidized bed of the particles, or the particles can be projected toward the substrate by using a spray gun especially adapted for that pu ⁇ ose.
  • the preferred application is via an electrostatic fluidized bed process with the substrate at ground potential.
  • a single surface or all surfaces of the substrate can be powder coated in this manner, as preferred.
  • the particles must be dry, i.e., amenable to electrostatic spray deposition without the use of solvents or other liquid carriers. This is not meant to preclude an absence of all moisture since tacky substances are contemplated for use, so long as they can be fluidized.
  • Powder is defined in accordance with the British Standards Institution, Chemical Dictionary. 5th ed. (1958), as discrete particles of dry material, the maximum dimension of which is less than 1,000 ⁇ .
  • Average particle size in the powder preferably is less than about 250 ⁇ , more preferably less than about lOO ⁇ .
  • the additive particles be heat fusible, which means that they are capable of being reduced to a liquid or molten state by sufficient heat.
  • the melting point of the particles must be below that of the polymer(s) in the substrate so that the particles can be substantially diffused into a surface of the substrate without degradation of the substrate.
  • the molecular weight of the additive(s) is such that the particles can be substantially diffused into a surface of the substrate; a range of up to about 3000 is acceptable, more preferably about 200 to about 1000, and most preferably about 200 to about 800.
  • substantially diffused is meant the molecular migration of the molten particles into the polymer substrate. This is in contrast to fusion of the particles to form a continuous boundary layer on the surface of the substrate wherein the fused boundary layer is contiguous to and adheres to but does not penetrate the surface of the substrate.
  • the diffusion is thermally induced by the heating step.
  • the heating step preferably takes advantage of an existing heating step during the manufacture of the polymer substrate.
  • the heat of the thermosol fabric dyeing process is preferably utilized to heat treat polyester seat belt webbing onto which additives have been deposited in accordance with this invention; a hot air oven or steam cans are typical thermosol heating devices (see detailed description of process in U.S. Patent 4,376,802, hereby inco ⁇ orated by reference).
  • the heating step is part of an existing continuous process - the continuous length of seat belt webbing is maintained under tension in the treating zone to avoid curling or shrinkage and to permit diffusion of the additives thereinto.
  • Preferred tension on the webbing is from about 445 to about 6670 N, more preferably from about 1110 to about 5560 N, and most preferably from about 2200 to about 4450 N.
  • the entire process can occur between thermosol dyeing and overcoating, as an independent step or as a separate process.
  • the heat of a drawing step can be utilized to heat treat undrawn polyester fiber onto which adhesion promoting additives have been deposited in accordance with this invention; heated rolls or a draw point localizing jet are typical drawing devices. Heating may, however, be by any appropriate means, and convection (hot air), conduction (contact), irradiation (infrared), induction heating, and the like, are all contemplated as within the scope of the present invention.
  • the heating temperatures and duration of treatment are dependent to a large degree on the particular polymer substrate.
  • heating temperatures of about 200 to about 250°C, more preferably about 210 to 240°C, for a time period of about 1 to about 6, more preferably about 1.5 to 3.5, minutes, is effective to melt the additive particles and cause the melt to substantially diffuse into the fabric.
  • These correspond to the thermosol process heating conditions for polyester seat belt webbing.
  • lower temperatures correspond to longer treatment times while higher temperatures correspond to shorter treatment times. These temperatures would be too high, however, for heat treating a polyethylene or polypropylene surface, due to their lower melting points. Appropriate adjustment of heat treatment temperatures and durations to accommodate the different substrates should be made.
  • the additives to be applied as well as the loading will depend on the particular polymer substrate.
  • the products of the present invention preferably are characterized by having the additive particles diffused therein at a loading of from about 0.01 to about 10 weight percent, more preferably from about 0.1 to about 5 0 weight percent, and most preferably from about 0.1 to about 2.0 weight percent. Because the additive can be distributed in selected surface regions of the substrate to modify surface properties, lower weight percentages are possible.
  • Stabilizers increase the lifespan of resin and plastic substrates by preventing their degradation by environmental factors.
  • End-use modifying additives are self defining - they modify the substrate according to the end use. Both types of additives are encompassed by this invention.
  • Stabilizing additives contemplated for use in this invention include heat stabilizers, preservatives, and light stabilizers.
  • End-use modifying additives contemplated for use in this invention include antistatic agents; antisoiling agents; antistain agents; colorants; adhesion promoters; and flame retardants.
  • Useful heat stabilizers include the mixed metal stabilizers; organotin and mercaptotin compounds; lead salts; and antimony mercaptides.
  • Preservatives which prevent biological degradation of plastics by microorganisms, can include bactericides; bacteriostats; fungicides; and fungistats.
  • Light stabilizers are used in a variety of polymers which are either highly susceptible to degradation by light or are frequently used in outdoor service, e.g., polyolefins, polycarbonates, polystyrenes, polyesters, polyamides, and polyvinyl chlorides.
  • the most typical light stabilizers include antioxidants, UV light absorbers, radical scavengers, nickel organics, benzoates, salicylates, and acrylates.
  • Useful antioxidants include the phenolics, e.g., simple phenols, bisphenols, thiobisphenols and polyphenols; aromatic amines, e.g., largely p-phenylenediamines and diphenylamines; thioesters, e.g., reaction products of fatty alcohols and an organic sulfide, typically thiodipropionates; phosphorous based antioxidants, e.g., phosphites; and others, such as the hydroquinones.
  • phenolics e.g., simple phenols, bisphenols, thiobisphenols and polyphenols
  • aromatic amines e.g., largely p-phenylenediamines and diphenylamines
  • thioesters e.g., reaction products of fatty alcohols and an organic sulfide, typically thiodipropionates
  • phosphorous based antioxidants e.g.,
  • the UV light absorbers include hydroxybenzophenones (also sulfonated); benzotriazoles (also sulfonated); cinnamates; cinnamamides; oxanilides; and combinations thereof.
  • Useful radical scavengers include hindered amine light stabilizers; and singlet oxygen scavengers such as 1,3-diphenylisobenzofuran and carotenoids.
  • organic nickel complexes examples include nickel dialkyldithiophosphates; nickel xanthates; nickel dibutyldithiocarbamates; nickel schiff base chelates; nickel oxime chelates; nickel hydrazone chelates; nickel salicylates; and nickel pyrazole chelates.
  • a useful benzoate includes resorcinol monobenzoate. See Rabek, J., Photostabilization of Polymers Principles and Applications. Elsevier Applied Science, New York, 1990, hereby inco ⁇ orated by reference.
  • the most preferred light stabilizers are the UV light absorbers, especially the hydroxybenzophenones and benzotriazoles; excellent results have been obtained with 2,4-dihydroxy-benzophenone (UVINUL®3000, BASF Co ⁇ .); 2,2'-dihydroxy-4,4'-dimethoxybenzophenone (UVTNUL®3049, BASF Co ⁇ .); and TINUVTN 326 PST, a benzotriazole (CAS 107-21-1, CIBA- Geigy Co ⁇ .).
  • Antistatic additives function to reduce the accumulation or increase the rate of dissipation of electrical charge on the surface of polymers.
  • Useful antistatic agents include the amines;tensides; quaternary ammonium compounds; anionic surface active agents, e.g., sulfonates phosphates; and others such as glycol esters, sulfated waxes, fatty amides, and polyhydric alcohol derivatives.
  • Antisoiling agents useful in the processes of this invention include fluorocarbonylimino biurets; fluoroesters; and fluoroester carbamates. See U.S. Patent 5, 153,046, hereby inco ⁇ orated by reference.
  • Antistain agents useful in the processes of this invention include sulfonated aromatic condensates and polymers and copolymers of maleic anhydride. Naturally, these additives must be of sufficiently low molecular weight that diffusion occurs at a reasonable rate.
  • Colorants useful in this invention include the organic pigments, e.g., phthalocyanine blues, phthalocyanine greens, organic reds, organic yellows; disperse dyes, e.g., azo dyes, bis-azo dyes, nigrosines, anthraquinones, xanthenes, sulfonamide dyes, nitro-aromatic dyes; optical brighteners; fluorescents; phosphorescents; and pearlescents.
  • disperse dyes are used as additives in the present invention, they are coupled in a powder with other additives.
  • Adhesion promoting additives that can be used in the processes of this invention include epoxides, like Epon 1001 F available from Shell; epoxy silanes; isocyanates, like caprolactam blocked isophorouediisocyanate available from Huls AG; polyhydroxyl compounds; and chlorinated organics.
  • these adhesion promoters can be applied at any part of the fiber production process; typically, application would occur just prior to drawing or winding.
  • the adhesion promoters could also be applied after fiber production in processes in the fiber plant such as wa ⁇ ing, be-uning, and rewinding, or further downstream in the process like twisting or weaving.
  • the key is that application of the adhesion promoter must occur prior to application of the coating to which the fiber is to adhere.
  • the coating is applied to the fiber for adhesion to a secondary substrate.
  • an epoxide would be applied to a polyester fiber to improve adhesion of the fiber to a resorcinol-formaldehyde-latex (RFL) coating, which in tum would adhere the fiber to rubber (secondary substrate) which subsequently undergoes vulcanization.
  • RTL resorcinol-formaldehyde-latex
  • the adhesion promoter is applied, preferably subsequent to weaving, to improve adhesion of the fabric to protective coatings such as polyvinyl chloride, polyurethane, or rubber, which enhance end-use performance of the fabric.
  • Flame retardants are used to reduce the combustibility of plastics.
  • Useful retardants include the inorganics; nonreactive organics, e.g., bromine compounds, chlorinated paraffins and cycloaliphatics, and phosphate esters; and reactive organics such as epoxy intermediates, polycarbonate intermediates, polyester intermediates, and urethane intermediates.
  • Several additives may be inco ⁇ orated within the polymer substrate via a single powder so long as the particles of the powder can be fluidized and the melting points of the various additives are compatible, i.e., not so disparate that at the higher temperatures required to melt the higher melting additive particles the lower melting additive particles degrade, volatilize or otherwise become unsuitable for use.
  • Preferred powder mixtures include light stabilizers with antisoiling agents, antistain agents, slip or grip modifiers, and colorants for seat belt webbing.
  • Products made in accordance with the processes of the present invention have a multitude of uses.
  • Applications where weathering or exposure to sunlight are a major concern include, by way of example, outdoor clothing, interior automotive fabrics, marine fabrics, marine slings, marine ropes, cordage, agricultural fabrics, awnings, canopies, tents, flags, banners, outdoor furniture, sports equipment, personal flotation devices, sails, parachutes, soft-sided luggage, geotextiles, animal control webbings, cargo tie-downs, industrial lifting slings, military webbings, parachute harnesses, seat belt webbing, and automotive molded parts such as headlamps and tail light covers.
  • Other applications where adhesion is a major concern include coated fabrics (e.g., soft truck panels) and industrial fabrics, as well as reinforcement for tires, conveyor belts, hoses, and V-belts.
  • the preferred process of the present invention is a solvent-free, continuous process for rendering a polyester surface of a length of seat belt webbing resistant to fading and degradation.
  • Additives are placed asymmetrically on upper yam bundles and not uniformly dispersed throughout the seat belt webbing.
  • the seat belt webbing construction is a woven 2/2 twill, knitted lock stitch, nominally about 2.0 inches (about 5 cm) in width with a thickness of about 0.047 inch (about 0.12 cm).
  • Approximately eight webbings are fed in parallel at a speed of up to about 20 yds/min (about 18 m/min) through a treating zone under tension of from about 445 to about 6670 N, more preferably from about 1110 to about 556 N, most preferably from about 2200 to about 4450 N. Maintaining the webbings under tension prevents curling or shrinkage.
  • Tension is preferably provided by running the take-up rollers at the exit end of the treatment zone at a slightly faster speed than the feed rollers to the treatment zone.
  • the feed webbing preferably is pre- dried and dyestuff-coated (unfixed) as described in more detail in Example 1 below.
  • An effective amount of a powder containing a plurality of dry, heat fusible, UV light absorbing particles is deposited on all exterior surfaces of the webbing via a vertical fluidized bed electrostatic powder coater.
  • the preferred UV light absorber is a hydroxybenzophenone or a benzotriazole, more preferably the former.
  • the powder add-on weight is at a loading of from about 0.01 to about 10 weight percent, more preferably from about 0.1 to about 5.0 weight percent, and most preferably from 0.1 to about 2.0 weight percent. The objective, clearly, is to add the minimum amount of UV light absorber necessary to render the seat belt webbing resistant to fading and degradation by light.
  • the dyestuff-coated and additive-coated webbings are then heat treated by exposure to a temperature of about 200 to about 250°C, more preferably about 210 to about 240°C, for about 1 to about 6, more preferably about 1.5 to about 3.5, minutes in the treating zone.
  • the time and temperature are sufficient to melt the powder particles and cause the resulting melt to diffuse into the webbings.
  • the dyes are heat set.
  • the webbings may then be neutralized, washed with detergent, rinsed, dried, and taken up.
  • the webbings can then be overcoated with an aqueous dispersion (e.g., ODM- 1 and ODM-FT, commercially available from Dooley Chemical) followed by drying and take-up, all as is well known in the art.
  • an aqueous dispersion e.g., ODM- 1 and ODM-FT, commercially available from Dooley Chemical
  • the product of this process is a dyed, woven polyester seat belt webbing comprising a plurality of multi-filament wa ⁇ and multi-filament weft yam bundles.
  • the weight ratio of the UV light absorber within a multi-filament wa ⁇ yam bundle to that within a multi-filament weft yam bundle ranges from a minimum of about 1 to 1 and up, with higher ratios being preferred.
  • the typical weight ratio ranges from about 1.5 to about 3.5 to 1.
  • the UV light absorber is diffused at intermittent regions along the length of the wa ⁇ filaments.
  • the UV light absorber can be selectively placed primarily on the surface filaments of the peak fiber bundles where weathering occurs, and thus avoid the waste of uniform concentration of UV light absorber throughout all multi-filament ya bundles.
  • the maximum migration of the UV light absorber into the seat belt webbing is about 40 ⁇ .
  • seat belt webbing construction was as follows. A 2/2 twill, knitted lock stitch, seat belt webbing was woven utilizing a commercially available Mueller needle loom, Model ND, to be nominally 2.0 inches in width with a thickness of 0.047 inch.
  • the webbing construction consisted of 342 warp ends of 1300 denier, 100 filaments, zero twist polyester yam with a filling ya (weft end) consisting of 16.7 double insertion picks per inch of 840 denier, 70 filaments, zero twist polyester yam.
  • the knitted lock stitch consisted of 500 denier, 70 filaments, zero twist polyester yam.
  • the yams used were polyethylene terephthalate yams commercially available from AlliedSignal, Inc., as, respectively, 1300-100-00- 1W70; 840-70-00- 1W70; and 500-70-00-1W70.
  • the aqueous dye baths all contained 4.0 g L Hostapur DAD, a nonionic alkyl alcohol polyglycol ether wetting agent, commercially available from Hoechst-Celanese Co ⁇ oration; 10.0 g/L Hyonic OP- 5 , a nonionic dispersing agent, commercially available from and proprietary to Henkel Process Chemicals, Inc.; dyes (as detailed in Table III, hereafter); and acetic acid to maintain pH of the bath at 4.8 - 5.0.
  • Hostapur DAD a nonionic alkyl alcohol polyglycol ether wetting agent, commercially available from Hoechst-Celanese Co ⁇ oration
  • 10.0 g/L Hyonic OP- 5 a nonionic dispersing agent, commercially available from and proprietary to Henkel Process Chemicals, Inc.
  • dyes as detailed in Table III, hereafter
  • acetic acid to maintain pH of the bath at 4.8 - 5.0.
  • thermosol process for dyeing fabric or seat belt webbing made with polyester yam is set forth in U.S. Patent 4,376,802, hereby inco ⁇ orated by reference.
  • PET seat belt webbing was woven as previously described.
  • the standard disperse dye solutions described above and in Table m were padded on the greige PET seat belt webbing.
  • the dye was applied from a dye bath via a single dip/single squeeze process and the webbing was then passed through an air convection predrier at a temperature of 60°C. with a nominal residence time of two minutes on a lab scale Benz thermosol range.
  • the predried, dyestuff-coated webbing was then powder coated with a UV light absorber, 2,4-dihydroxybenzophenone (UVINUL 3000, commercially available from BASF; mean particle size: volume - 28.3 microns; number - 4.68 microns with a particle geometric diameter range from ca.
  • UVINUL 3000 2,4-dihydroxybenzophenone
  • powder add-on wt% was estimated at this stage by sampling and weighing the webbing and comparing to uncoated pieces of webbing of the same length.
  • the weight of the additive deposited on the webbing was estimated to vary from 0 to over 2.5 wt% (based on fiber weight) by a variation in the voltage setting of the electrostatic coater. Typical voltage ranges utilized were 30 to 62kV with resulting estimated add-on percentages between 1.0 and 2.5wt%.
  • Powder coating was carried out at speeds up to 20 yds/min.
  • the samples prepared in Table IV were run at 8 yds/min.
  • the dyestuff-coated (unfixed) and additive- coated web was then passed through a rubber pinch braking roller and into an electric air convection thermosol oven heated at 215°C. at a speed of 1 ydJmin. to complete the dyeing of the webbing and to diffuse the UV light absorber additive into the polyethylene terephthalate filaments of the webbing.
  • the webbing residence time in the thermosol oven was between 1.5 - 2.0 min. with the webbing under a net stretch of about 0.5 to 1.5%.
  • the dyed web with the additive diffused therein was then neutralized in a clearing bath of 2 g/L sodium hydrosulfite at 27°C, washed with detergent in two separate baths at 96-100°C, rinsed with hot water at 96-100°C, and then rinsed in a cold solution of 5 g/L acetic acid (pH 4.5- 5.0).
  • the webbing was then dried by passing over two steam cans and was taken up for testing of dye lightfastness, breaking strength retention (BSR), wet and dry crocking, and water spotting. Control samples were prepared in the same manner but without the addition of any of the UV absorber.
  • Samples 8 and 14 utilized a voltage setting of 30 kV (estimated 1.0% loading), while Samples 2, 4, 6 and 10 utilized a voltage setting of 35 kV (estimated 1.5% loading), and Samples 12 utilized a voltage setting of 40 kV (estimated 1.9-2.0% loading).
  • Loadings as measured by extraction and gas chromatography analysis, are set forth in the column headed UV3000 wt%.
  • the scarlet samples (5 and 6) represent the average of two samples. Samples 1 through 6 passed water spotting test; the other samples were not tested. All of the samples passed the wet and dry crocking test.
  • Breaking strength retention (SAE J1885, 225 kJ/m 2 ) showed improvement for Samples 2, 4 and 6, and a slight downturn (from 75 to 73%) for Sample 12; comparative data was not measured for the other samples. Note the improvement both for Gray Scale (GS) and delta E values at 225kJ/m 2 and 450kJ/m 2 . Measurements were not taken for Samples 7 - 14 for the 450kJ/m 2 .
  • EXAMPLE 2 In this Example, PET seat belt webbings were woven and fully dyed in accordance with the procedure set forth in Example 1 (pad dyeing without electrostatic deposition of additives). In Table V, the odd numbered samples represent the controls for this Example. The fully dyed webbings of the even numbered samples were electrostatically coated with UVINUL 3000 UV light absorber and heat treated in accordance with the procedure of Example 1 (post treatment). With reference to Table V, Samples 2 and 4 utilized a voltage setting of 65 kV (1.0% loading), while Samples 6 and 8 utilized a voltage setting of 50 kV (0.5% loading). UV testing for fade resistance was then carried out. Note the improvement for both Gray Scale and delta E values at 225 kJ/m 2 . EXAMPLE 3
  • greige (undyed) polyethylene terephthalate seat belt webbing of the same construction as that used for the webbings of Example 1 was powder coated with UVINUL 3000 powder using an ETI Model 602 fluidized-bed, powder-coating apparatus. Fumed silica (0.2wt%) was added to the powder to aid in fluidization.
  • the greige webbing was coated at a speed of 8 yds/min with individual high voltage settings of 36k V, 50kV and 64kV on the high voltage grid of the fluidized bed to create three separate webbing samples having low, medium and high loadings of the powdered additive.
  • the three powder coated samples were then thermosoled according to the method described for the dyed webbing of Example 1 including all wash steps.
  • the concentration of UVINUL 3000 in each sample of greige webbing was determined by extraction and GC analysis. Two 70 - 75 mg samples were cut from each of the greige webbing samples (low, medium, high concentrations), one from the right hand side and one from the left hand side. Each sample was extracted with 2mL of chloroform at ca. 60°C. for 16 h. Gas chromatographic analysis on a 15m OV17 megabore column (1 micron film) using a 20°C/min. temperature ramp starting at 240°C. with a 5 min. hold at the final temperature of 260°C. followed by comparison of the integrated peak intensities with a standard UW-JUL 3000 calibration curve allowed for the determination of the additive add-on wt%. The wt% loadings are summarized in Table VI. A repeat extraction of a sample that had been through one extraction cycle yielded less than 10% additional UVINUL 3000, thus showing that greater than 90% of the UVINUL 3000 is removed in a single extraction.
  • the spatial asymmetry of the UVINUL 3000 distribution in the webbing was demonstrated via extraction-GC analysis of the wa ⁇ and weft fibers separately (Table VI under sample location).
  • the high concentration greige webbing was disassembled and a series of wa ⁇ yams were selected for extraction analysis. Similarly samples of weft yams were selected for a separate extraction analysis.
  • the concentration of UVINUL 3000 in the wa ⁇ fiber was found to be 2.17 times that in the weft (fill) fiber.
  • the medium, low, and control (zero) concentration greige webbings were also disassembled for extraction analysis of their respective wa ⁇ and weft yams.
  • the concentration ratio for the medium concentration webbing wa ⁇ fiber was 2.90 times that in the weft fiber, and the concentration ratio for the low concentration webbing wa ⁇ fiber was 2.83 times that in the weft fiber.
  • Each greige webbing sample was then examined via UV microscopy.
  • samples of wa ⁇ filaments for cross-sectioning were prepared to contain a small number of filaments from several wa ⁇ yams.
  • Weft filament samples were prepared by potting single weft yam bundles. Each set of filaments was potted in PMMA and four, 10 micron sections were microtomed from each and mounted on quartz slides. Control filaments of each type were prepared simultaneously and also mounted on quartz slides.
  • wa ⁇ or weft yam bundles were placed between dark absorbing yams and compressed in a metal holder which allowed thick sections to be cut. These latter samples were then placed directly on the Olympus microscope stage for viewing at 100X, 200X and 400X.
  • the observations of the spatial distributions for the high and medium loading greige webbing samples are summarized below. The presence of the UVINUL 3000 was indicated by abso ⁇ tion of the 357nm light used for the microscopy.
  • Weft filament cross sections were lighter than similar thickness cross sections of wa ⁇ filaments, consistent with the lower loading of UVINUL 3000 observed in the extraction data reported in Table VI. Some individual filaments were observed to be as strongly absorbing as the average wa ⁇ filament. The distribution of the UVINUL 3000 within the individual wa ⁇ filaments was observed to be uniform across any given filament as measured by a line scan taken through the gray-scale imaged cross section data. Thick cross sections (>200 microns) of both wa ⁇ and weft yam bundles showed an apparent uniform distribution of the UVINUL 3000 from filament to filament within each yam bundle and across any given filament. See Figure 2B.
  • the UVINUL 3000 can be uniformly distributed across a given filament, yet be asymmetrically placed with respect to the filaments within the yam. See Figures 2C and 2D.
  • the weft filaments when viewed in thin cross section, appear generally to not contain any UVINUL 3000 (no abso ⁇ tion greater than control filaments as indicated by gray scale values of line scans through the digitized image). A few weft filaments have intermittent dark absorbing sections.
  • EXAMPLE 4 PET seat belt webbing was woven as previously described. Two powders were formed. The first powder comprised lwt% fumed silica and Scarlet dye powder (see Table III for components). The second powder comprised 75 wt% Scarlet dye powder (see Table m for components), 24wt% UVINUL 3000 UV light absorber, and lwt% fumed silica.
  • the cavity of a fluidized bed electrostatic coater was filled with the first powder and the voltage set at 75-100 kV.
  • the powder fluidized well.
  • Several one foot lengths of grounded webbing were hand-passed through the powder cloud above the fluidized bed to powder coat the webbings.
  • These powder coated lengths of webbing were then processed as in Example 1 subsequent to powder coating. This procedure was repeated for a second set of webbings and utilizing the second powder.
  • the seat belt webbing is woven as previously described for PET yams except that the yams used are PET/PEN yams.
  • the PET/PEN yams are a polymer mixture (90 PET: 10 PEN wt%) whereby the PET and PEN are chip blended and melt-spun into fiber in accordance with the teachings of U.K. Patent 1,343,628, hereby inco ⁇ orated by reference.
  • the seat belt webbing is treated as in Example 1. Similar results/data are anticipated.
  • EXAMPLE 6 An industrial webbing is woven utilizing a needle loom and the following PET yarns, commercially available from AlliedSignal, Inc.: wa ⁇ ends of 1300 denier/100 filament zero twist yarn 1300-100-00-1W70; weft yams of 840 denier/70 filament zero twist yam 840-70-00- 1W70; binder yam and lock stitch ya 500 denier/70 filament zero twist 500-70-00- 1W70; filling/stuffer yams 1000 denier/ 192 filament zero twist 1000-192-00- 1W70.
  • the webbing is woven using 342 wa ⁇ ends, 16.7 weft ends/inch, and a lock stitch to finish the edge.
  • the webbing is a tubular construction whereby the webbing is woven with two distinct sets of wa ⁇ yams (171 ends each) and a common filling yam.
  • the filling yam intersects with each set of wa ⁇ selvages to make the tube.
  • 150 "stuffer" ya s are embedded between the webbing face and back (in effect, to stuff the tube).
  • Approximately 10 evenly spaced binder yams are sewn down the length of the webbing to bind the webbing sandwich.
  • the final webbing is approximately 2 inches in width and 0.060 inch in thickness.
  • the woven webbing is then pigment dyed (water based dye pad) followed by drying in an air convection oven at a temperature of 140°C.
  • webbing for about 5 minutes. A portion of this webbing is reserved for testing as a control.
  • the balance of the webbing is powder coated with a UV light absorber and heat treated in accordance with Example 1 above. It is anticipated that the webbing with the light absorber diffused therein will have significantly better UV stability than the control webbing.
  • the stuffer yams could be made from PEN yams of 1000 denier/ 192 filament zero twist, generally made in accordance with the teachings of U.S. Patent 5,397,527. It is anticipated that similar results would be obtained.
  • the yams are twisted into 1000/3, 8.5 X 8.5 tpi cords, which are then treated with a conventional resorcinol- formaldehyde-latex coating (see U.S. Patent 4,054,634) and tensilized by a conventional tensilization procedure.
  • the adhesion between the resulting cord and rubber is tested by a peel adhesion test where the peel force and visual rating of the amount of rubber remaining on the cord is recorded. Any conventional test used by tire manufacturers is acceptable, e.g., the adhesion test disclosed in U.S. Patent 3,718,587 and further described in U.S. Patent 4,054,634, both of which are hereby inco ⁇ orated by reference. Peel adhesion is expected to be satisfactory.

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  • Engineering & Computer Science (AREA)
  • Textile Engineering (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Wood Science & Technology (AREA)
  • Mechanical Engineering (AREA)
  • Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)

Abstract

L'invention porte sur la fabrication d'un substrat polymérique stabilisé et/ou modifié grâce à un procédé de diffusion causée par un phénomène thermique, en l'absence de solvant. Le procédé se caractérise par une déposition électrostatique d'une quantité efficace d'un ou de plusieurs produits d'addition stabilisateurs et/ou modificateurs sous forme de poudre sur des surfaces sélectionnées d'un substrat, suivie du réchauffement de cette poudre à une température supérieure à la température de transition vitreuse du substrat ainsi qu'au point de fusion des produits d'addition jusqu'à fusion de la poudre et sa diffusion dans le substrat. Il est possible de fabriquer des tissus tissés inaltérables à la lumière, à base de polyester ou de polyamide, résistant au fanage et dont les couleurs ne se dégradent pas sous l'effet de la lumière, que l'on utilisera pour le tissage de ceintures de siège et le tissage industriel. Il est également possible de fabriquer du tissu pour bandages de roues à base de polyester ainsi que des tissus tissés à base de polyester ou de polyamide, pourvus d'un pouvoir d'adhérence renforcé à différents enduits, que l'on utilisera pour des pneus et des tissus enduits, respectivement.
PCT/US1996/005094 1995-04-12 1996-04-12 Substrat polymerique avec produits d'addition et procede de fabrication par diffusion causee par un phenomene thermique WO1996032529A1 (fr)

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WO2001027215A1 (fr) * 1999-10-07 2001-04-19 Saint-Gobain Abrasives, Inc. Formules pour depot electrostatique
WO2002002245A2 (fr) * 2000-06-29 2002-01-10 Johnson & Johnson Consumer Companies, Inc. Impregnation electrostatique de poudres sur des substrats
EP1232022A1 (fr) * 1999-07-16 2002-08-21 Ecoglo Limited Application de pigment photoluminescent
GB2417957A (en) * 2004-09-10 2006-03-15 Biocote Ltd Method of forming a resin composition with additives
CN103303067A (zh) * 2012-03-14 2013-09-18 固特异轮胎和橡胶公司 具有熔合帘线的充气轮胎
US9134471B2 (en) 2006-06-28 2015-09-15 3M Innovative Properties Company Oriented polymeric articles and method

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US4990368A (en) * 1989-06-13 1991-02-05 Burlington Industries, Inc. Process for flame retarding textiles
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WO1992015404A1 (fr) * 1991-03-01 1992-09-17 S.L. Electrostatic Technology, Inc. Procede de depot de poudre pour revetement electrostatique, en vue de produire des stratifies pour plaquettes a circuits imprimes et similaires
EP0608510A1 (fr) * 1993-01-23 1994-08-03 Hüls Aktiengesellschaft Procédé pour mélanger des stabilisants dans des polycondensats
EP0643996A1 (fr) * 1993-09-17 1995-03-22 Nippon Paint Co., Ltd. Procédé de revêtement

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Publication number Priority date Publication date Assignee Title
BE651292A (fr) *
FR1209311A (fr) * 1957-08-01 1960-03-01 Du Pont Structures polymères organiques stables vis-à-vis des rayons ultra-violets
DE2260213A1 (de) * 1971-12-10 1973-06-14 Stamicarbon Verfahren zum stabilisieren von polymerisaten
US4990368A (en) * 1989-06-13 1991-02-05 Burlington Industries, Inc. Process for flame retarding textiles
US5057338A (en) * 1990-05-16 1991-10-15 The United States Of America As Represented By The Administrator Of The National Aeronautics And Space Administration Process for application of powder particles to filamentary materials
WO1992015404A1 (fr) * 1991-03-01 1992-09-17 S.L. Electrostatic Technology, Inc. Procede de depot de poudre pour revetement electrostatique, en vue de produire des stratifies pour plaquettes a circuits imprimes et similaires
EP0608510A1 (fr) * 1993-01-23 1994-08-03 Hüls Aktiengesellschaft Procédé pour mélanger des stabilisants dans des polycondensats
EP0643996A1 (fr) * 1993-09-17 1995-03-22 Nippon Paint Co., Ltd. Procédé de revêtement

Cited By (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1232022A1 (fr) * 1999-07-16 2002-08-21 Ecoglo Limited Application de pigment photoluminescent
EP1232022A4 (fr) * 1999-07-16 2006-04-19 Ecoglo Ltd Application de pigment photoluminescent
WO2001027215A1 (fr) * 1999-10-07 2001-04-19 Saint-Gobain Abrasives, Inc. Formules pour depot electrostatique
WO2002002245A2 (fr) * 2000-06-29 2002-01-10 Johnson & Johnson Consumer Companies, Inc. Impregnation electrostatique de poudres sur des substrats
WO2002002245A3 (fr) * 2000-06-29 2002-05-16 Johnson & Johnson Consumer Impregnation electrostatique de poudres sur des substrats
GB2417957A (en) * 2004-09-10 2006-03-15 Biocote Ltd Method of forming a resin composition with additives
US9134471B2 (en) 2006-06-28 2015-09-15 3M Innovative Properties Company Oriented polymeric articles and method
US9259885B2 (en) 2006-06-28 2016-02-16 3M Innovative Properties Company Oriented polymeric articles and method
CN103303067A (zh) * 2012-03-14 2013-09-18 固特异轮胎和橡胶公司 具有熔合帘线的充气轮胎
JP2013189190A (ja) * 2012-03-14 2013-09-26 Goodyear Tire & Rubber Co:The 融着コードを有する空気入りタイヤ
EP2639081A3 (fr) * 2012-03-14 2014-09-10 The Goodyear Tire & Rubber Company Corde comprenant des fibres fusionnées par une solution d'isocyanate et pneumatique comprenant ladite corde

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