WO1996025548A1 - Tissus presentant une stabilite amelioree aux rayons ultraviolets - Google Patents

Tissus presentant une stabilite amelioree aux rayons ultraviolets Download PDF

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Publication number
WO1996025548A1
WO1996025548A1 PCT/US1996/001299 US9601299W WO9625548A1 WO 1996025548 A1 WO1996025548 A1 WO 1996025548A1 US 9601299 W US9601299 W US 9601299W WO 9625548 A1 WO9625548 A1 WO 9625548A1
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Prior art keywords
fabric
spunbond
coated fabric
meltblown
weight percent
Prior art date
Application number
PCT/US1996/001299
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English (en)
Inventor
Mary Lou Delucia
Robert Leslie Hudson
Robert Emil Weber
Original Assignee
Kimberly-Clark Worldwide,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 Kimberly-Clark Worldwide,Inc. filed Critical Kimberly-Clark Worldwide,Inc.
Priority to AU49688/96A priority Critical patent/AU4968896A/en
Publication of WO1996025548A1 publication Critical patent/WO1996025548A1/fr

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Classifications

    • 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
    • D06N3/0056—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof characterised by the compounding ingredients of the macro-molecular coating

Definitions

  • Fabrics in general and nonwoven fabrics in particular are used for a wide variety of applications from baby wipes and diapers to automobile covers. These applications call for materials having diverse properties and attributes. Some applications call for fabrics which are highly wettable, i.e. quickly allow liquids to pass through them, e.g. liners for diapers and feminine hygiene products, and soft, while others require strength, e.g. protective fabrics like car and boat covers. It is the latter class of products with which this invention is concerned, specifically, materials which have some barrier properties and which hold up well when exposed to the elements in outdoor usage.
  • a coated fabric having improved ultraviolet radiation stability comprising a fabric having outer surfaces and a cured, water-based coating mixture on at least one of the outer surfaces which is comprised of latex polymer and ultraviolet radiation stabilizer.
  • the mixture may also contain a cure promoter and a viscosity modifier.
  • the mixture may be applied to the fabric as an aqueous mixture with a pre-cure pH adjusted to above 8 using a fugitive alkali, a pre-cure viscosity of between about 500 and 1000 centipoise, and then cured at a temperature below the fabric's melting temperature.
  • Figure 1 is a scanning electron microscope (SEM) picture of a nonwoven fabric which has been coated with the coating of the present invention. The magnification of the photograph is 80X. This picture shows the spunbond layer having the coating in the top area, the finer fiber meltblown layer below the upper spunbond layer, and part of the other outer spunbond layer in the bottom of the picture.
  • SEM scanning electron microscope
  • Figure 2 is an SEM picture of a nonwoven fabric which has been coated with the coating of the present invention. The magnification of the photograph is 250X. This picture clearly shows the penetration of the coating slightly into the spunbond layer, completely encasing some upper fibers.
  • nonwoven fabric or web means a web having a structure of individual fibers or threads which are interlaid, but not in an identifiable manner as in a knitted fabric.
  • Nonwoven fabrics or webs have been formed from many processes such as for example, meltblowing processes, spunbonding processes, and bonded carded web processes.
  • the basis weight of nonwoven fabrics is usually expressed in ounces of material per square yard (osy) or grams per square meter (gs ) and the fiber diameters useful are usually expressed in microns. (Note that to convert from osy to gsm, multiply osy by 33.91) .
  • icrofibers means small diameter fibers having an average diameter not greater than about 75 microns, for example, having an average diameter of from about 0.5 microns to about 50 microns, or more particularly, microfibers may have an average diameter of from about 2 microns to about 40 microns.
  • spunbonded fibers refers to small diameter fibers which are formed by extruding molten thermoplastic material as filaments from a plurality of fine, usually circular capillaries of a spinnerette with the diameter of the extruded filaments then being rapidly reduced as by, for example, in U.S. Patent no. 4,340,563 to Appel et al., and U.S. Patent no. 3,692,618 to Dorschner et al., U.S. Patent no. 3,802,817 to Matsuki et al., U.S. Patent nos. 3,338,992 and 3,341,394 to Kinney, U.S. Patent no. 2,502,763 to Hartman, U.S.
  • Spunbond fibers are generally not tacky when they are deposited onto a collecting surface. Spunbond fibers are generally continuous and often have diameters larger than 7 microns, more particularly, between about 10 and 20 microns.
  • meltblown fibers means fibers formed by extruding a molten thermoplastic material through a plurality of fine, usually circular, die capillaries as molten threads or filaments into converging high velocity gas (e.g. air) streams which attenuate the filaments of molten thermoplastic material to reduce their diameter, which may be to microfiber diameter. Thereafter, the meltblown fibers are carried by the high velocity gas stream and are deposited on a collecting surface to form a web of randomly disbursed meltblown fibers.
  • high velocity gas e.g. air
  • polymer generally includes but is not limited to, homopolymers, copolymers, such as for example, block, graft, random and alternating copolymers, terpolymers, etc. and blends and modifications thereof. Furthermore, unless otherwise specifically limited, the term “polymer” shall include all possible geometrical configuration of the material. These configurations include, but are not limited to isotactic, syndiotactic and random symmetries.
  • onocomponent fiber refers to a fiber formed from one or more extruders using only one polymer. This is not meant to exclude fibers formed from one polymer to which small amounts of additives have been added for coloration, anti-static properties, lubrication, hydrophilicity, etc. These additives, e.g. titanium dioxide for coloration, are generally present in an amount less than 5 weight percent and more typically about 2 weight percent.
  • conjugate fibers refers to fibers which have been formed from at least two polymers extruded from separate extruders but spun together to form one fiber. Conjugate fibers are also sometimes referred to as multicomponent or bicomponent fibers.
  • the polymers are usually different from each other though conjugate fibers may be monocomponent fibers.
  • the polymers are arranged in substantially constantly positioned distinct zones across the cross-section of the conjugate fibers and extend continuously along the length of the conjugate fibers.
  • the configuration of such a conjugate fiber may be, for example, a sheath/core arrangement wherein one polymer is surrounded by another or may be a side by side arrangement or an "islands-in-the-sea" arrangement.
  • Conjugate fibers are taught in U.S. Patent 5,108,820 to Kaneko et al., U.S. Patent 5,336,552 to Strack et al., and U.S. Patent 5,382,400 to Pike et al.
  • the polymers may be present in ratios of 75/25, 50/50, 25/75 or any other desired ratios.
  • biconstituent fibers refers to fibers which have been formed from at least two polymers extruded from the same extruder as a blend.
  • blend is defined below. Biconstituent fibers do not have the various polymer components arranged in relatively constantly positioned distinct zones across the cross-sectional area of the fiber and the various polymers are usually not continuous along the entire length of the fiber, instead usually forming fibrils or protofibrils which start and end at random. Biconstituent fibers are sometimes also referred to as multiconstituent fibers. Fibers of this general type are discussed in, for example, U.S. Patent 5,108,827 to Gessner.
  • blend means a mixture of two or more polymers while the term “alloy” means a sub-class of blends wherein the components are immiscible but have been compatibilized.
  • miscibility and miscibility are defined as blends having negative and positive values, respectively, for the free energy of mixing.
  • compatibilization is defined as the process of modifying the interfacial properties of an immiscible polymer blend in order to make an alloy.
  • TAB through air bonding
  • a nonwoven conjugate fiber web which is wound at least partially around a perforated roller which is enclosed in a hood.
  • Air which is sufficiently hot to melt one of the polymers of which the fibers of the web are made is forced from the hood, through the web and into the perforated roller.
  • the air velocity is between 100 and 500 feet per minute and the dwell time may be as long as 6 seconds.
  • the melting and resolidification of the polymer provides the bonding.
  • Through air bonding has restricted variability and is generally regarded a second step bonding process. Since TAB requires the melting of at least one component to accomplish bonding, it is generally restricted to conjugate webs though it may be used with adhesive webs also.
  • thermal point bonding means a process of bonding which involves passing a fabric or web of fibers to be bonded between a heated calender roll and an anvil roll. This method of bonding is quite common.
  • the calender roll is usually patterned in some way so that the entire fabric is not bonded across its entire surface.
  • various patterns for calender rolls have been developed for functional as well as aesthetic reasons.
  • One example is the expanded Hansen Pennings pattern with about a 15% bond area with about 100 bonds/square inch as taught in U.S. Patent 3,855,046 to Hansen and Pennings.
  • Another common pattern is a diamond pattern with repeating and slightly offset diamonds.
  • machine direction means the length of a fabric in the direction in which it is produced, i.e., the direction of travel of the forming wire onto which spunbond and meltblown fabrics are typically formed.
  • cross machine direction means the width of fabric, i.e. a direction generally .rpendicular to the MD.
  • marine fabric means fabric which may be used in a service which is primarily on boats or otherwise in proximity to water, such as curtains for boats boat covers, boat seat material and cover material, bimini top material, covers for various boat equipment, e.g. crank covers, sail covers, engine covers and steering wheel covers, and other marine applications.
  • the term "protective cover” means a cover for vehicles such as cars, trucks, boats, airplanes, motorcycles, bicycles, golf carts, etc., covers for equipment often left outdoors like grills, yard and garden equipment (mowers, roto-tillers, etc.) and lawn furniture, as well as floor coverings, table cloths and picnic area covers.
  • Hydrohead A measure of the liquid barrier properties of a fabric is the hydrohead test.
  • the hydrohead test determines the pressure of water (in millibars) which the fabric will support before a predetermined amount of liquid passes through.
  • a fabric with a higher hydrohead reading indicates it has a greater barrier to liquid penetration than a fabric with a lower hydrohead.
  • the hydrohead test is performed according to Federal Test Standard No. 191A, Method 5514, dated July 20, 1978.
  • Tensile The tensile strength of a fabric may be measured according to the ASTM test D-1682-64. This test measures the strength in pounds and elongation in percent of a fabric. The results are expressed in pounds to break and percent stretch before breakage. Higher numbers indicate a stronger, more stretchable fabric.
  • load means the maximum load or force, expressed in units of weight, required to break or rupture the specimen in a tensile test.
  • strain or “total energy” means the total energy under a load versus elongation curve as expressed in weight-length units.
  • BAD ORIGINAL tf "elongation” means the increase in length of a specimen during a tensile test.
  • One particular type of tensile test is the Modified Strip Tensile or Modified Zero Span test.
  • a 1 inch (25 mm) by 4 inch (102 mm) sample is placed between clamps with a 0.5 inch (12.7 mm) separation and pulled apart at a rate of 2 inches/minute (51 mm/min.) using a dynamometer, such as for example, an Instron Model TM available from the Instron Corporation, 2500 Washington St., Canton, MA 02021, or a Thwing-Albert Model INTELLECT II available from the Thwing-Albert Instrument Co. , 10960 Dutton Rd. , Phila. , PA 19154, or a Sintech 2/S using Testworks software available from Sintech, a division of MTS Systems Corporation, 1001 Sheldon Dr., Cary, NC 27513. Test results are given in pounds.
  • Nonwovens fabrics in particular are generally made from thermoplastic polymers, the most common thermoplastics for this application being polyolefins, particularly polypropylene and polyethylene and copolymers and blends thereof. Other materials such as polyesters, polyetheresters, polyamides and polyurethanes are also used to form nonwoven fabrics.
  • HALS hindered amine light stabilizer
  • a film coating for a fabric has the advantage of allowing all of the UV protectant to be located on the outside surface of the fabric where it is most needed. This method also avoids the problem of compatibility of the UV protectant with the polymer of the nonwoven fabric, which may be a problem when the two are mixed.
  • MO 63167 This material is sold under the trade name
  • SORBALITE* polymeric UN blockers e.g. SORBALITE* 154B
  • SORBALITE* polymeric UN blockers e.g. SORBALITE* 154B
  • the exact chemical identification of SORBALITE* polymer is a trade secret of Monsanto.
  • Monsanto recommends a SORBALITE ® UV blocker film thickness of about 2 microns.
  • the inventors have found that, unfortunately, such a film is quite difficult to produce commercially. They have also found that such a thin film, when applied to a nonwoven or woven fabric, does not adhere well to the fabric's surface. These fabric's surfaces are quite rough and do not provide a good substrate upon which to adhere a film, especially such a thin one. As a result, the inventors have found an alternative, and, they believe, superior method of application.
  • the inventors have found that a coating containing a small amount of a UN blocker provides a surprisingly great amount of
  • the stabilizing coating is applied to the fabric as a latex polymer based liquid which is applied as evenly as possible across the surface of the fabric and which penetrates slightly into the surface.
  • the coating of this invention also provides extra abrasion resistance to the fabric due to its penetration down into the fabric's surface.
  • U.S. Patent 5,370,132 requires a topical liquid repellent treatment prior to applying a liquid barrier coating in order to maintain the coating in a film-like condition, i.e., without penetration into the fabric, to form an impervious barrier. No such topical treatment may be used in the practice of the instant invention and such an impervious barrier is not formed.
  • Samples were prepared in order to prove the efficacy of the instant invention with a coating at three concentrations of UN blocker, one control without UV stabilizer and one control without a coating.
  • the fabric onto which the UN blocker containing latex solution was coated in the samples was in the form of 5 inch by
  • the fabric used in the tests was formed from layers as follows: A spunbond layer having a basis weight of 85 gsm formed from polypropylene designated PF-305 by the Himont
  • Chimassorb ® 944 FL hindered amine light stabilizer available from the Ciba-Geigy Corporation of Hawthorne, New York, and pigment in an amount of 2 weight percent.
  • Two meltblown layers each having a basis weight of 17 gsm and formed from PF-015 polypropylene, a 1 weight percent Chimassorb ® 944 FL hindered amine light stabilizer, and 2 weight percent pigment.
  • a second spunbond layer having a basis weight of 44 gsm and formed from polypropylene designated PF-305 by Himont, 1.25 weight percent Chimassorb ® 944 FL hindered amine light stabilizer, and 2 weight percent pigment.
  • fabrics may be used in the practice of this invention such as a bonded carded web, woven fabrics, spunbond fabrics or meltblown fabrics alone and the fabrics may also be made from conjugate or biconstituent fibers.
  • fabrics may be a single layer embodiment or as a component of a multilayer laminate such as that used in the test and may be formed by a number of different laminating techniques including but not limited to using adhesive, needle punching, thermal point bonding, through air bonding and any other method known in the art.
  • An SMMS laminate like that used in the examples may have a basis weight for example, between 68 and 105 gsm for the first spunbond layer, a basis weight of between about 10 and 25 gsm for each meltblown layer and a basis weight of between 27 and 60 gsm for the last spunbond layer.
  • the layer may, for example, contain from 0.5 to 2.5 weight percent of a hindered amine light stabilizer and between 0.25 and 5 weight percent of pigment.
  • SMS laminates may, for example, be an embodiment wherein some of the layers are spunbond and some meltblown such as a spunbond/meltblown/spunbond (SMS) laminate as disclosed in U.S. Patent no. 4,041,203 to Brock et al. and U.S. Patent no. 5,169,706 to Collier, et al or a SFS (spunbond, film, spunbond) construction.
  • SMS laminate may be made by sequentially depositing onto a moving forming belt first a spunbond fabric layer, then a meltblown fabric layer and last another spunbond layer and then bonding the laminate in a manner described above.
  • the fabric layers may be made individually, collected in rolls, and combined in a separate bonding step.
  • the fabric of this invention may also be laminated with, glass fibers, staple fibers, paper, and other web materials, provided, however, that the outer surface of the laminate onto which the coating is to be applied is a nonwoven fabric.
  • the nonwoven meltblown fibers or the film used in an intermediate layer may be made from non-elastomeric polymers such as polypropylene and polyethylene or may be made from an elastomeric thermoplastic polymer.
  • Elastomeric thermoplastic polymer may be those made from styrenic block copolymers, polyurethanes, polyamides, copolyesters, ethylene vinyl acetates (EVA) and the like.
  • EVA ethylene vinyl acetates
  • any suitable elastomeric fiber or film forming resins or blends containing the same may be utilized to form the nonwoven webs of elastomeric fibers or elastomeric film.
  • elastomeric copolymers are, for example, those known as KRATON ® materials which are available from Shell Chemical Company of Houston, Texas. KRATON* block copolymers are available in several different formulations, a number of which are identified in U.S. Patent 4,663,220, hereby incorporated by reference.
  • exemplary elastomeric materials which may be used to form an elastomeric layer include polyurethane elastomeric materials such as, for example, those available under the trademark ESTANE ® from B. F. Goodrich & Co., polyamide elastomeric materials such as, for example, those available under the trademark PEBAX ® from the Rilsan Company, and polyester elastomeric materials such as, for example, those available under the trade designation HYTREL ® from E. I. DuPont De Nemours & Company.
  • polyurethane elastomeric materials such as, for example, those available under the trademark ESTANE ® from B. F. Goodrich & Co.
  • polyamide elastomeric materials such as, for example, those available under the trademark PEBAX ® from the Rilsan Company
  • polyester elastomeric materials such as, for example, those available under the trade designation HYTREL ® from E. I. DuPont De Nemours & Company.
  • UV radiation stabilizer was added to a latex polymer base.
  • a cure promoter was added in order to allow curing of the coating at temperatures below that which would melt the polymer of the nonwoven web which generally includes polypropylene. The curing process is triggered by the loss of a fugitive alkali which was also part of the formulation.
  • latex polymers with internal :uring agents may be used.
  • a viscosity modifier was also part of the formulation.
  • An acceptable latex polymer system for use in this invention must be compatible with the UV blocker and generally have a saturated hydrocarbon backbone. They must be able to be crosslinked at room temperature or at slightly elevated temperatures, must be stable to ambient weather conditions and produce a flexible coating.
  • the latex polymer coating may also be elastic. Examples include polymers of ethylene vinyl acetates, ethylene vinyl chlorides, acrylates, and styrene- acrylate copolymers. Such latex polymers generally have a Tg in the range of -15 to +20 °C
  • One such suitable latex polymer composition is known as HYCAR ® 26084 from the B.F. Goodrich Company of Cleveland, OH.
  • Suitable latexes include HYCAR ® 2671, 26445 and 26469 from Goodrich, RHOPLEX ® B-15, HA- 8 and NW-1715 from Rohm & Haas and DUR-O-SET ® E-646 from National Starch & Chemical Co. of Bridgewater, N.J.
  • An acceptable UV blocker for use in this invention must block most of the UN radiation which impinges on it and must not be fugitive.
  • One suitable UN blocker is the SORBALITE* polymer mentioned above.
  • An acceptable cure promoter for use in this invention must cause or result in the crosslinking of the latex polymer in the coating to give it excellent water resistance properties, e.g. , to rain and sea water exposure.
  • Acceptable cure promoters allow the latex based coating to cure at room temperature or slightly above so that the nonwoven web does not need to be heated to a temperature at which it may begin to melt in order to cure the latex.
  • the preferred cure promoter becomes active at a pH which is neutral or acidic, therefore the composition must be kept at a pH of above 8 during mixing and application.
  • the pre-cure pH is kept above 8 by the use of a fugitive alkali such as, for example, ammonia. Fugitive alkalis remain in solution until driven off by heating. The loss of the alkali causes a drop in the pH of the composition which triggers the action of the cure promoter.
  • One such suitable cure promoter is
  • An acceptable viscosity modifier for use in this invention must have thickening properties with Newtonian flow characteristics.
  • One such suitable viscosity modifier is known as ACRYSOL ® RM-8 and is available from the Rohm & Haas Company of Philadelphia, PA.
  • the aqueous coating was prepared by adding the indicated amount of viscosity modifier to warm water and pouring this mixture into the latex. The pH was then adjusted with a fugitive alkali, in this case ammonia, to about 8.7. The UN blocker was then added and the pH rechecked and adjusted if necessary. Lastly, the cure promoter was added and the viscosity was checked and adjusted with viscosity modifier if necessary, to a final pre-cure viscosity of about 800 centipoise. The viscosity was tested using a Brookfield viscometer running at 30 rpm with a number 3 spindle.
  • the ingredients were mixed in a 1200 ml stainless steel beaker and lightly stirred with a stainless steel spatula.
  • the particular ingredients used were HYCAR ® 26084, SORBALITE ® 154B, XAMA ® -7, and ACRYSOL ® RM-8, ammonia and water.
  • the first column of Table 1 is the weight percent of Total Solids (T.S.) in the ingredient as used.
  • the A through D mixtures were coated onto the heavier basis weight side of the laminate using a number 32 Mayer rod, though any other effective method known to those skilled in the art such as spraying or dipping and squeezing may be used.
  • the coated nonwoven was dried in an air circulation oven at about 107"C for 3 minutes and cured at room temperature for about 30 minutes.
  • the coated weight of all dried and cured sample coatings ranged from 50 to 58 gsm.
  • the amount of coating on a fabric in the practice of this invention will depend on a number of factors such as the smoothness of the fabric, which is related to the thread count, and the UV stability or susceptibility of the fabric.
  • the amount of coating to be used in each instance would be the amount of coating which confers ultraviolet stability on the subject fabric.
  • a practical overall range for the coating on fabric would be a dry weight of from 25 to 100 gsm. More coating could probably be used in any case but any amount beyond that needed to meet the ultraviolet stability requirements of the fabric would be superfluous.
  • the samples were then exposed, coated side out, to solar ultraviolet radiation or light by way of open air southern exposure at an angle of 45* in Miami, Florida. The samples were tested every other month using the Modified Strip Tensile test for strength and for hydrohead on occasion.
  • the tensile results of the exposure are shown in Table 2 and the hydrohead results are shown in Table 3.
  • the samples on the left hand side of the tables correspond to the samples in Table 1, with the addition of a sample E which is a sample of the same fabric without any coating at all.
  • the first data column is the initial tensile (I.T.) strength and the initial hydrohead (I.H.) in Tables 2 and 3 respectively.
  • the months are then shown across the top of Tables 2 and 3 and the property measured is given as percent retention of the original property.
  • the coating according to this invention does not improve either the initial tensile strength or the initial hydrohead of the fabric.
  • the primary object of this invention was the prolongation of the retention of tensile strength upon exposure to UN radiation, not an improvement in tensile or barrier properties.
  • Such other embodiments may include, for example, a nonwoven laminate embodiment wherein all of the nonwoven layers are elastic and the latex coating is elastic as well.

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  • Engineering & Computer Science (AREA)
  • Textile Engineering (AREA)
  • Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
  • Laminated Bodies (AREA)

Abstract

L'invention décrit un tissu enduit présentant une stabilité améliorée aux rayons ultraviolets comprenant un tissu ayant des surfaces extérieures et un mélange d'enduction à base d'eau cuit sur au moins l'une desdites surfaces extérieures, lequel est constitué de polymère latex et d'un stabilisateur aux rayons ultraviolets. Le mélange peut également contenir un initiateur de cuisson et un modificateur de viscosité. Il peut être appliqué sur le tissu sous forme de mélange aqueux présentant un pH de précuisson fixé à au-dessus de 8 à l'aide d'un alcalin fugitif, une viscosité de précuisson comprise entre environ 500 et 1000 centipoise, avant d'être cuit à une température inférieure à la température de fusion du tissu.
PCT/US1996/001299 1995-02-17 1996-02-02 Tissus presentant une stabilite amelioree aux rayons ultraviolets WO1996025548A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AU49688/96A AU4968896A (en) 1995-02-17 1996-02-02 Fabrics with improved ultraviolet radiation stability

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US39072395A 1995-02-17 1995-02-17
US08/390,723 1995-02-17

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WO1996025548A1 true WO1996025548A1 (fr) 1996-08-22

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Cited By (1)

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Publication number Priority date Publication date Assignee Title
EP0913518A1 (fr) * 1997-10-31 1999-05-06 DHJ International Support textile filtrant les rayons ultra-violets, son procédé de préparation, ses utilisations

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EP0057813A2 (fr) * 1981-01-23 1982-08-18 SKW Trostberg Aktiengesellschaft Dispersion aqueuse et procédé de revêtement de matériaux
WO1986001519A1 (fr) * 1984-09-03 1986-03-13 Commonwealth Scientific And Industrial Research Or Copolymeres d'emulsions acryliques
US4861651A (en) * 1988-06-02 1989-08-29 Goldenhersh Michael A Ultraviolet blocking material and method of making same
EP0447964A2 (fr) * 1990-03-22 1991-09-25 BASF Aktiengesellschaft Articles en formes de poly(éther-cétones) aromatiques stabilisés contre les rayons UV et procédé pour leur préparation
JPH04208102A (ja) * 1990-11-30 1992-07-29 Katona Japan Kk 日傘類用生地及びその製造方法
JPH04289268A (ja) * 1991-03-13 1992-10-14 Kanebo Ltd 紫外線透過防止加工布帛及びその製造方法
JPH04333662A (ja) * 1990-11-24 1992-11-20 Kanebo Ltd 紫外線透過防止加工布帛及びその製造方法
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Publication number Priority date Publication date Assignee Title
EP0057813A2 (fr) * 1981-01-23 1982-08-18 SKW Trostberg Aktiengesellschaft Dispersion aqueuse et procédé de revêtement de matériaux
WO1986001519A1 (fr) * 1984-09-03 1986-03-13 Commonwealth Scientific And Industrial Research Or Copolymeres d'emulsions acryliques
US4861651A (en) * 1988-06-02 1989-08-29 Goldenhersh Michael A Ultraviolet blocking material and method of making same
EP0447964A2 (fr) * 1990-03-22 1991-09-25 BASF Aktiengesellschaft Articles en formes de poly(éther-cétones) aromatiques stabilisés contre les rayons UV et procédé pour leur préparation
JPH04333662A (ja) * 1990-11-24 1992-11-20 Kanebo Ltd 紫外線透過防止加工布帛及びその製造方法
JPH04208102A (ja) * 1990-11-30 1992-07-29 Katona Japan Kk 日傘類用生地及びその製造方法
JPH04289268A (ja) * 1991-03-13 1992-10-14 Kanebo Ltd 紫外線透過防止加工布帛及びその製造方法
JPH059871A (ja) * 1991-07-02 1993-01-19 Kanebo Ltd 紫外線透過防止加工布帛の製造方法

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0913518A1 (fr) * 1997-10-31 1999-05-06 DHJ International Support textile filtrant les rayons ultra-violets, son procédé de préparation, ses utilisations
FR2770542A1 (fr) * 1997-10-31 1999-05-07 Dhj International Support textile filtrant les rayons ultra-violets, son procede de preparation, ses utilisations

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AU4968896A (en) 1996-09-04
PE45997A1 (es) 1997-12-30

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