WO1993011286A1 - Polymere mate par le dioxyde de titane anatase et dote d'une photostabilite amelioree - Google Patents

Polymere mate par le dioxyde de titane anatase et dote d'une photostabilite amelioree Download PDF

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Publication number
WO1993011286A1
WO1993011286A1 PCT/US1992/010105 US9210105W WO9311286A1 WO 1993011286 A1 WO1993011286 A1 WO 1993011286A1 US 9210105 W US9210105 W US 9210105W WO 9311286 A1 WO9311286 A1 WO 9311286A1
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Prior art keywords
titanium dioxide
silica
anatase titanium
dioxide particles
suspension
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PCT/US1992/010105
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English (en)
Inventor
Frederick Robert Hopf
Rodney Lee Wells
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Allied-Signal Inc.
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Application filed by Allied-Signal Inc. filed Critical Allied-Signal Inc.
Publication of WO1993011286A1 publication Critical patent/WO1993011286A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK  ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
    • C09C1/00—Treatment of specific inorganic materials other than fibrous fillers; Preparation of carbon black
    • C09C1/36—Compounds of titanium
    • C09C1/3607—Titanium dioxide
    • C09C1/3653—Treatment with inorganic compounds
    • C09C1/3661—Coating
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F1/00—General methods for the manufacture of artificial filaments or the like
    • D01F1/02—Addition of substances to the spinning solution or to the melt
    • D01F1/04—Pigments
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/60—Particles characterised by their size
    • C01P2004/62—Submicrometer sized, i.e. from 0.1-1 micrometer
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/80—Particles consisting of a mixture of two or more inorganic phases
    • C01P2004/82—Particles consisting of a mixture of two or more inorganic phases two phases having the same anion, e.g. both oxidic phases
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2006/00—Physical properties of inorganic compounds
    • C01P2006/60—Optical properties, e.g. expressed in CIELAB-values
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2006/00—Physical properties of inorganic compounds
    • C01P2006/80—Compositional purity

Definitions

  • the present invention relates to a process of coating anatase titanium dioxide for use as a synthetic polymer additive, particularly for use as a delusterant for polymers subjected to a low pH aftertreatment, especially carpet fibers or yarns treated with stain resist agents.
  • Finely divided anatase titanium dioxide has long been used as a material for delustering synthetic polymers, especially filament-forming polymers such as linear polyamides which are used as textile components. Its desirable properties include a high index of refraction, adequate dispersability and good chemical stability.
  • UV ultra-violet
  • Highly reactive free radicals are formed which may attack the polymer chains, causing embrittlement and strength loss.
  • the titanium dioxide surface can then reabsorb oxygen and atmospheric moisture and again be photoactivated; hence, the titanium dioxide functions as a photocatalyst for degradation of polymers and the dyes contained in polymers.
  • UV light stabilizers have been proposed to alleviate the problem of photodegradation caused by anatase-delustered polymers, among which manganese compounds have been found to act as particularly effective passivating ions. These stabilizers are added to the polymer-forming composition or to the finished filament or other polymeric object. The quantities of manganese-based stabilizer which can be used are limited by the tendency of the stabilizers to discolor the polymeric products.
  • titanium dioxide-delustered compositions to low pH aqueous conditions, however, effectively removes substantially all or most of the passivating manganese ions from such materials.
  • This is particularly pertinent with respect to titanium dioxide-delustered, dyed fibers of synthetic polymers such as polyamides.
  • relatively low pH (about 2) aqueous aftertreatments of fibers to impart improved stain resistance has caused the removal of much of the manganese ions from the fibers, with the consequent lowering of their photostability.
  • U.S. Patent No. 2,885,366 discloses a process for applying an amorphous silica film to a titanium dioxide particle, which is said to be useful as a delusterant for nylon. During the process the pH is maintained between about 8 and 11. The patent does not indicate whether the titanium dioxide is of the anatase or rutile form.
  • U.S. Patent No. 3,437,502 discloses a process for applying a silica/alumina coating to rutile titanium dioxide paint pigment .
  • TJ . S . Patent No . 5, 041,162 discloses a process of coating titanium dioxide with an inner coating of amorphous silica and an outer coating of alumina.
  • the process should provide photostability to the anatase titanium dioxide even if the polymer textile component is subjected to a low pH stain resist aftertreatment.
  • Further objects of the present invention are to provide a textile component which includes anatase titanium dioxide that does not cause photodegradation of the textile component and a carpet and a fiber produced from this textile component.
  • a process for imparting improved deluster quality to a polymer textile component comprising (a) dispersing a plurality of anatase titanium dioxide particles in water, (b) introducing a silica source material to the resultant dispersion to form a suspension, (c) lowering the pH of the suspension to below about 6.0 to precipitate silica from the silica source material and form an amorphous silica coating on the anatase titanium dioxide particles, (d) blending the silica-coated anatase titanium dioxide particles with a polymer resin and (e) extruding the resultant blend to form a textile component.
  • the process further comprises between steps (c) and (d) a step (c # ) of adding an alumina source material to the suspension and a step
  • polymer textile component which includes anatase titanium dioxide particles having an amorphous silica coating formed according to the above-described process.
  • a carpet with enhanced UV light stability comprising a dyed fiber or dyed yarn which has been subjected to an acidic aftertreatment to impart improved stain resistance, the fiber or yarn comprising at least one polymer and a plurality of anatase titanium dioxide particles, wherein the anatase titanium dioxide particles are coated with amorphous silica, the coating having a thickness of about 0.005 to 0.01 microns.
  • a dyed fiber with enhanced UV light stability which has been subjected to an acidic aftertreatment to impart improved stain resistance
  • the fiber comprising at least one polymer and a plurality of anatase titanium dioxide particles, wherein the anatase titanium dioxide particles are coated with amorphous silica, the coating having a thickness of about 0.005 to 0.01 microns.
  • Figure 1 is a graphic representation showing the relative reactivity ratios of titanium dioxide samples.
  • polyamide denotes nylon 6, - nylon 66, nylon 4, nylon 12 and other polymers containing the (C-N) structure along with the (CH 2 ) X chain as described in Cook, J., Handbook of Textile Fibres. Merrow Publishing Co., pp. 194-327 (1984) .
  • Nylon 6 and 66 are preferred.
  • Texttile component denotes tape, fiber, yarn or other profile which has been typically tufted, woven, or otherwise constructed into fabric suitable for final use in home furnishings, particularly as floor covering or upholstery fabric.
  • “Fiber” denotes continuous filament of a running or extremely long length, or cut or otherwise short fiber known as staple.
  • Carpet “yarn” may be made of multiple continuous filaments or -spun staple fiber, both typically pretextured for increased bulk.
  • a low pH antistain aftertreatment is understood to denote the application of a stain resist substance, i.e , a stain blocker, under acidic conditions to the surface of the polyamide fibers before or after they have been dyed. This stain resist treatment is applied to protect against staining of the polyamide fibers by acid dye colorants commonly found in household items such as beverages, foods, cosmetics and medicines and other stain-causing substances such as coffee.
  • the stain blocker is applied by preparing an aqueous dispersion or solution of the stain blocker, causing the stain blocker dispersion or solution to contact and coat the fiber and then heating the coated fiber.
  • low pH antistain aftertreatments can be utilized in conjunction with any conventional dyeing methods such as beck dyeing, continuous dyeing and pad dyeing.
  • the stain blocker also can be applied with known foam techniques or during carpet shampooing. For example, if beck dyeing is used to dye the carpet yarn, a preferred method for preparing the aqueous dispersion or solution is to add the stain blocker substance directly to the exhausted dye bath.
  • Known stain blocker compositions which are applied under low pH or acidic conditions include a combination of (a) sulfonated aromatic condensate and (b) polymethacrylic acid and/or copolymers of methacrylic acid as described in U.S. Patent No. 4,822,373, a hydrolyzed aromatic-containing vinyl ether maleic anhydride copolymer and/or a half ester of an aromatic-containing vinyl ether maleic anhydride copolymer as described in commonly assigned U.S. Patent Application Serial No. 716,163 (filed June 17, 1991), an aromatic-containing acrylate copolymerized with acrylic acid or maleic acid as described in commonly assigned U.S. Patent Application Serial No. 716,163 (filed June 17, 1991) and a mixture of sulfonated novolak resin and a water-soluble divalent metal salt as described in U.S. Patent 4,875,901.
  • the titanium dioxide utilized in the present invention is of the anatase form rather than the rutile form.
  • Anatase titanium dioxide is available commercially from manufacturers such as Kemira, Inc.
  • Rutile is not used as a fiber delusterant due to its high abrasiveness which damages the equipment used to produce the fiber.
  • Titanium dioxide particles having average diameters ranging from about 0.1 to 1.0 microns are of exemplary size for use in the present invention. It is understood that particle sizes outside this range also could be used, provided they do not lead to processing difficulties.
  • the silica coating according to the present invention comprises an amorphous silica and is of sufficient thickness, density and uniformity to act as an impervious barrier between the titanium dioxide surface and its surroundings.
  • a coating thickness of about 0.005 to 0.01 microns can be obtained.
  • the destructive radical species are confined by the silica coating to the titanium dioxide surface and effectively prevented from destroying surrounding dye or polymer molecules.
  • the silica source for the coating can be any silicate or silicic material which, in aqueous solution undergoes hydrolysis as the solution is acidified to form amorphous silica.
  • Sodium silicate preferably having a Na 2 0:Si0 2 mole ratio of 2.5 to 4:1, preferably 3;1 is the preferred source of silica but other orthosilicate or metasilicate salts also can be employed.
  • the silica-coated titanium particles also are treated with precipitated hydrous alumina.
  • the applied alumina can form a discrete layer, the thickness and uniformity of which can vary, a discrete, continuous layer is not necessary and the alumina may mix with the silica.
  • the alumina acts as a dispersant aid in that it assists to maintain the dispersion of titanium particles until drying by preventing the agglomeration of the coated titanium particles.
  • the alumina source can be any aluminum salt that is soluble in water.
  • examples of such salts include aluminum nitrate, aluminum chloride, aluminum chloride hexahydrate, aluminum ammonium sulfate, aluminum sulfate and the hydrates thereof, with particular preference given to aluminum sulfate, which is readily available as Al 2 (SO 4 ) 3 °18H 2 0.
  • a silica or silica/alumina coating is applied to anatase titanium dioxide particles.
  • the coated particles then are blended with a polymer and the polymer blend is formed into a textile component.
  • a titanium dioxide/water dispersion is formed initially.
  • a predetermined amount of titanium dioxide is introduced with vigorous stirring to a container or reactor vessel which holds a predetermined amount of water at room temperature.
  • the concentration of titanium dioxide in the dispersion should be selected so that vigorous stirring of the dispersion can be maintained throughout the coating process. If too much titanium dioxide is dispersed, it would be difficult to stir the dispersion and attain rapid equilibration as subsequent reagents were added.
  • the titanium dioxide concentration ranges from about 10 to 30 weight percent, based on the weight of the dispersion.
  • the titanium dioxide/water dispersion can be formed via a batch process.
  • the total amount of titanium dioxide preferably is added to and completely dispersed in an amount of water which is smaller than the desired final amount. The additional amount of water can then be added to the dispersion. Alternatively, the full amount of titanium dioxide can be added to and dispersed in the desired final amount of water. If a more continuous process is desired, a plant process stream which already contains the appropriate concentration of titanium dioxide in an aqueous slurry can be utilized as the titanium dioxide/water dispersion. A predetermined amount of at least one of the previously described silica source materials then is added to the titanium dioxide dispersion over a relatively short time period, i.e., about 20 minutes, to form a suspension.
  • the concentration of the added silica source material in the dispersion depends on the desired amount of silica coating on the titanium particle.
  • the coated particle includes about 2 to 20 weight %, more preferably about 6 to 10 weight , and most preferably about 8 weight % • silica, based on the total weight of the coated particle.
  • the silica source material can be in any physical form, e.g., powder, granules, aqueous solution etc. , when it is mixed with the titanium dioxide dispersion.
  • the preferred silica source material is an aqueous solution of sodium silicate with a Na20:SiO2 mole ratio of approximately 3:1.
  • the temperature of the resulting suspension is raised to about 85 to 95 °C, preferably about 90 ° C, over a relatively short time period, i.e., from about 15 to 60 minutes. At this point, the temperature of the suspension is stabilized and maintained and the pH should be greater than 10. Prior to raising the temperature-, additional water can be added to the suspension to adjust the titanium dioxide and silica source material concentrations if desired. The silica source material then is precipitated by lowering the pH of the suspension to below about 6.0 while maintaining the elevated temperature. If alumina is added according to the preferred embodiment, the pH should be lowered to about 3 to 4, preferably below about 3.5.
  • the pH can be lowered by any conventional method such as the addition of a relatively dilute aqueous acid solution as described in U.S. Patent No. 3,437,502.
  • a concentrated acid such as sulfuric acid
  • An amount of acid sufficient to ensure the desired amount of silica precipitation is added to the suspension.
  • the acid is added in steady, approximately 15 equal-sized doses or in a controlled continuous stream. After the addition of the acid, the stirred suspension is kept at about 90°C for an additional time period to ensure the desired precipitation of the silica source material.
  • an alumina source material as described previously is added to the suspension after the silica precipitation step.
  • the desired concentration of the added alumina source material in the suspension depends on the end use of the product.
  • the amount of the alumina source material in the suspension should be sufficient to result in the coated particle having about 0.5 to 5.0 weight % alumina, preferably about 2.0 weight % alumina, based on the weight of the coated particle.
  • the alumina source material can be added in steady approximately equal-sized doses or in a controlled continuous stream.
  • the temperature and pH of the suspension should be maintained, respectively, at about 90°C and below about 3.5.
  • the alumina source material can be in any physical state when it is mixed with the suspension. If the alumina source material is aluminum sulfate, an aqueous aluminum sulfate solution having a pH of about 2 to 5, preferably lower than about 3.5, can be prepared separately then added to the suspension.
  • the pH of the suspension is raised to about 7.0 or higher via any conventional method after the alumina source is added to the suspension.
  • the most effective method for raising the pH in the present invention is through the addition of an alkaline earth oxide, hydroxide or salt solution, an alkali metal oxide, hydroxide or salt solution, or aqueous ammonia to the titanium dioxide suspension.
  • useful pH-raising materials include solutions of sodium hydroxide, potassium hydroxide, ammonia and similar materials.
  • the temperature of the suspension is allowed to fall to near room temperature and the stirring is stopped.
  • the suspended coated titanium dioxide particles then are recovered via conventional means, such as, for example, filtration and vacuum drying or convection heating.
  • the reactor or vessel used to perform the coating must be of sufficient size to contain the final volume of dispersion.
  • the reactor is equipped to provide vigorous stirring of the reaction volume and ensure heating to a temperature of up to about 955 C.
  • the reactor also must be able to receive water to compensate for evaporation losses.
  • the coated anatase titanium dioxide according to the present invention is most useful as a delusterant for polyamide fibers which are subjected to a low pH antistain aftertreatment.
  • the anatase titanium dioxide particles are blended with polyamide resin via conventional techniques.
  • Other known polyamide additives can be included in the blend.
  • the blend then is extruded to form a fiber.
  • the fiber, or yarn formed from the fiber is dyed according to conventional methods and subjected to a low pH antistain aftertreatment as described previously.
  • the dyed fiber or yarn can be used in carpet or apparel.
  • a preferred method for mixing the coated titanium dioxide powder or particles with the nylon resin includes-the utilization of the well-known masterbatch technique and, in this invention, the masterbatch should include about 10 weight % titanium dioxide.
  • Zinc stearate or- light mineral oil can be added to the masterbatch to promote the adherence of the coated titanium dioxide powder or particles to the nylon chips.
  • the titanium dioxide-containing masterbatch then is dry blended with the feed nylon resin prior to extrusion to attain a titanium dioxide distribution of about 0.05 to 0.5 weight %, preferably 0.05 to 0.25 weight %, based on the weight of the blend, for carpet fibers and about 0.1 to 2 weight , preferably 0.25 to 1.0 weight %, based on the weight of the blend, for apparel fibers.
  • anatase Ti0 2 (Unitane 0-310, available from Ke ira, Inc.) are dispersed in 250 mL of water in a reactor capable of heating the final volume of dispersion to 100°C, and capable of mechanical stirring at speeds up to about 600 rpm. The dispersion is stirred vigorously. After suspension is complete, an additional 100 mL of water are added to the vigorously stirred dispersion. If the pH of the dispersion is not above about 8.5, concentrated aqueous ammonia is added to adjust the pH to about 9.1.
  • a solution of 13.27 grams of A12(S04) 18 H20 in 100 mL water is prepared. Several drops of concentrated sulfuric acid are added to ensure that the pH of the solution is below 3.5.
  • the aluminum sulfate solution is added to the particle suspension at a fast dropwise rate. After addition of the aluminum sulfate solution is complete, 50% aqueous sodium hydroxide solution is added dropwise to the heated, stirred suspension to adjust the pH to near 7.0. The stirred reactor temperature is kept at 90°C for an additional 30 minutes after the sodium hydroxide addition is complete.
  • the suspension is cooled to about 50°C, filtered and washed with a total of about 900 mL of water.
  • the residue is dried to constant weight at 180-200°C. The residue is then cooled and ground to eliminate aggregates.
  • the residue comprises a powder of silica/alumina coated titanium dioxide particles that is ready for use as a polymer delusterant.
  • Unitane 0-520 typically consists of 94.4 weight % Tio 2 , 3.3 weight % A1 2 0 3 , 0.5 weight % Si0 2 and 0.3 weight % P 2 0 5 .
  • a leuco dye oxidation test was used to evaluate the titanium dioxide samples obtained according to the previously described procedures. This test utilizes the ability of Ti0 2 to act as a photocatalytic oxidant of * organic molecules in the presence of oxygen and water. Benzene solutions of a readily oxidizable leuco form of a triphenylmethane dye are employed. The leuco dye is oxidized to a colored form which is extracted into methanol and measured quantitatively.
  • the UV irradiation source is a GE HSP-100, 100 watt mercury arc spotlamp directed at the solutions to be tested from a distance of approximately fifty centimeters.
  • the filtered light source emits primarily 366 nanometer wavelength radiation.
  • the test procedure followed is a modification of the procedure outlined in G. Irick, Jr., G.C. Newland and R.H.S. Wong, "Effect of Metal Salts on the Photoactivity of Titanium Dioxide", Photostabilization and Photodegxadation of Coatings, ed. by Winslow and Pappas, American Chemical Society Symposium Series #151 (1981) .
  • the first step of the specific procedure is the preparation of a solution of leuco crystal violet by dissolving 0.0366 grams of the leuco dye in 100 milliliters of benzene (solution kept in a dark glass container--all work done in dark or under yellow lights) .
  • Each test tube with a stirrer bar rotating at a reproducible rate of about 1000 rpm, is placed in position to be irradiated behind a light blocking shutter, then irradiated for an accurately measured time (from about 5- 180 seconds. The shutter is closed, and the tubes are kept in darkness for further processing.
  • Sets of tubes are centrifuged until the Ti0 2 has completely settled, then the benzene solution is carefully decanted. Five milliliter aliquots of methanol are added to each tube, followed by mechanical stirring to ensure equilibration and extraction of dye by the methanol.
  • Sets of methanol/Ti0 2 tubes are centrifuged, then the methanol extracts are decanted into 10 milliliter volumetric flasks.
  • the methanol extraction steps are repeated for each test tube. Methanol is added to bring the liquid levels to 10 milliliters in each of the volumetric flasks..
  • a visible spectrophotometer is used to measure the absorption of the methanol extracts from about 800-400 nanometers for the various samples. The absorbance at the maximum is determined for the control and test samples. The absorbance of the various test samples is compared to the control sample to obtain a relative reactivity ratio, i-e-, A ⁇ iamp ⁇ _/ - mtI0i , corrected for irradiation times.
  • the control therefore, has a relative reactivity of 1.0 and test samples are compared to the control.
  • Comparative Example 1 is Unitane 0-310 which has not been subjected to the silica coating treatment of the present invention or a low pH treatment.
  • Comparative Example 2 is Unitane 0-310 which has not been subjected to the silica coating treatment of the present invention but which has undergone a low pH treatment. Comparative Examples 1 and 2 include up to about 2 weight % alumina.
  • Example 3 is Unitane 0-310 coated according to the exemplified embodiment of the present invention but not subjected to a low pH treatment.
  • Example 4 is Unitane 0-310 coated according to the exemplified embodiment of the present invention and subjected to a low pH treatment.
  • Comparative Example 2 and Example 4 The pH of a 100 mL sample of distilled water was adjusted with sulfamic acid to a pH of 2. Then 20 grams of either Comparative Example 2 or Example 4 were dispersed in pH 2 water with vigorous stirring (500 rpm) on a stirrer/hotplate. The temperature of the stirred dispersion is raised to about 71°C and held constant for 30 minutes. The solution is allowed to cool to room temperature with stirring. The suspension is filtered on a fine glass fritted disc then dried to constant weight in an oven at temperatures lower than 190°C.
  • the relative reactivity ratio data illustrated in Figure 1 indicates the photoreactivity of the anatase titanium dioxide samples.
  • the relative reactivity ratio is directly proportional to the photoreactivity. It is clear from Figure 1 that coating anatase titanium dioxide particles according to the present invention significantly lowers the photoreactivity of the particles. A lower photoreactivity results in the lowering of the photodegradation of any polymers into which the coated particles are incorporated.
  • Each blend was spun using a laboratory extruder with an exit polymer temperature of 254-255 °C, a 20 rpm pump speed, a screw speed of 65 rpm, and a yarn take up speed of 990 feet per minute (fpm) .
  • the fibers were spun as an asymmetric trilobal ("Y") cross section.
  • the spun yarns were drawn to a final denier of ca.1130- 1145 at a 3.2 draw ratio.
  • the spun yarns were texturized with superheated steam at a super heater temperature of 425°, booster heater temperature of 370°C, and steam pressure of 30-36 psi.
  • the yarn speed was 1100 feet per minute (fpm) in and 840 fpm out of the texturizer tube.
  • the drawn/texturized yarns were plied 3.5 S X 3.5 Z and then heat set by autoclaving at 280 °F. Ply twisting of yarns is well-known and is described, for example, in Moncrieff, R.W., Man-Made Fibers. Heywood Books, pp 6-8 (4th ed. 1963) . These heat set yarns were knitted into sleeves for 5 testing lightfastness.
  • Each sleeve was dyed in three critical shades using typical acid dyes used for nylon 6. The shades were Argent Gray, Rose and Blue. A portion of each sleeve was aftertreated with a stain blocker comprising about six parts methacrylic copolymer and one part sulfonated aromatic condensate at pH 2.0 (adjusted with sulfamic acid), at 100 °F, for 20 minutes, and a liquor to goods ratio of 30 to 1.
  • the dyed and dyed + aftertreated sleeves were analyzed for % Tio2 and xenon lightfastness by American Association of Textile Chemists and Colorists t"AATCC") Method 16E graded by Gray Scale.
  • AATCC Method 16E provides an indication of the propensity of a fabric to fade under specified conditions of exposure to UV light. The results are listed in Table 1. "SFU" denotes Standard Fading Units.
  • Example A Comparative Example I, which include approximately the same amounts of Ti0 2 , demonstrates a surprising improvement in lightfastness using the coated anatase Ti0 2 over the commercially available anatase Ti0 2 (which was without the normally added manganese) .
  • a comparison between Example A and Comparative Example I, which include approximately the same amounts of Ti0 2 demonstrates a surprising improvement in lightfastness using the coated anatase Ti0 2 over the commercially available anatase Ti0 2 (which was without the normally added manganese) .
  • Example B and Comparative Example II which include approximately the same amounts of Ti0 2 , shows a similar improvement.
  • a Gray Scale value of 5 signifies no visible fading and a Gray Scale value of 1 signifies a complete loss of color
  • the difference between a Gray Scale values of 2 and 3 is significant.
  • a dry blend was made of 3.494 pounds of titanium dioxide coated according to the exemplified embodiment of the present invention with 35 pounds of nylon chip and 0.04 pounds of zinc stearate (used as a binder for the Ti0 2 powder and the nylon chips) .
  • the predried nylon 6 chips were warmed to about 80 °C, the zinc stearate was added and allowed to melt and mixed for one hour, then the Ti0 2 powder was added and mixing continued for 0.5 hour. Then the blend was packed out and sealed closed. This blend subsequently was melt extruded through a twin screw extruder.
  • the extruder was operated at 260 °C zone temperature, a screw rpm of 230, and
  • Inventive Example C was made up of 4.80 pounds of the 9.40 weight % Tio2 masterbatch which contained the coated Ti0 2 and 175.2 pounds of substantially pure nylon. This was tumble blended, dried and packed out. The calculated amount of Ti0 2 in this sample was 0.256 weight % Ti0 2 .
  • Comparative Example III consisted of 5.10 pounds of the 8.85 weight % Ti0 2 masterbatch with 174.9 pounds of nylon. This also was dried and packed out for spinning. This sample had a calculated value of 0.251 weight % Ti0 2
  • the nylon chip samples were spun at 38 pounds per hour on a standard extruder , using a spinnerette with trilobal shaped holes of dimension 0.006 x (0.030)3 x 0.20 inches, with a total of 60 holes.
  • the extruder block temperature was 260 °C.
  • the yarn product target was 1200 denier yarn with a modification ratio of 3.1.
  • the undrawn denier target was 3040 ⁇ 30.
  • the undrawn yarn was taken up as 40 pound packages and subsequently drawn and textured with a 19 minute cycle to give a 10 pound drawn/textured package.
  • the textured inventive and comparative samples were tested for the physical properties listed below in Table 2:
  • CEBB crimp elongation before boil.
  • CEAB crimp elongation after boil.
  • the textured yarns were plied 4.75 S x 4.75 Z and the SUPERBA heat set at 275°F. with 39 psi air pressure, 445 meters per minute coil speed, pre-steam temperature of 200°F. and a belt speed of 10 meters per minute.
  • the SUPERBA treatment is a know heat setting method by which twisted yarns are set with steam at an elevated temperature to lock in the twist of the yarns.
  • the SUPERBA unit typically is run so that the yarn temperature is 275 °F.
  • the heat set yarns were used to tuft a carpet with 38 ounces per square yard weight of face fiber, using a 1/10 gage tufting machine and 7/16 inch pile height, as a cut pile Saxony fabric.
  • the carpets were dyed in two typical carpet shades that can be used to show lightfastness effects. These were Argent Gray and Beige shades. The dyeing was done on a Saucier apparatus using a 9 inch x 72 inch piece of unbacked carpet.
  • the Saucier apparatus is a small apparatus which simulates a commercial beck dyeing range. In this apparatus, a small length of carpet or knitted sleeve is stitched into a loop and allowed to revolve ⁇ through an aqueous dye bath which contains the appropriate dyes, wetting agents and other auxiliaries.
  • the dye bath liquor temperature can be raised under controlled 20 conditions and held at the boil as desired.
  • the Saucier bath can hold 10 to 15 liters.
  • An Ahiba unit is a small laboratory dyeing unit which allows small scale dyeing under carefully controlled conditions.
  • the samples are attached to a sample holder which rotates the sample vertically and in a circular direction to allow thorough contact between the sample and the bath.
  • the bath volume can be 0.2 to 4.0 liters.
  • the Ahiba unit typically can hold as many as 12 samples at a time.
  • the aftertreatment was done at pH 2.0 using sulfa ic acid to adjust the pH, 3.0% owg (on weight of goods) of a stain blocker comprising about six parts methacrylic copolymer and one part sulfonated aromatic condensate, and 4.0% owg Epsom salt.
  • the aftertreatment bath with each carpet sample, was held at 160°F for 20 minutes. The carpet samples were then extracted and dried.
  • the DYED set of data of Table 3 demonstrate that carpets containing the inventive coated anatase titanium dioxide do not require a manganese additive to avoid the photoactivation by UV light.
  • the dyed (but not aftertreated) inventive carpet example exhibited the same xenon lightfastness as the comparative carpet example even though the inventive example did not contain any added manqanese.

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  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Textile Engineering (AREA)
  • Organic Chemistry (AREA)
  • Chemical Or Physical Treatment Of Fibers (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

Un procédé permet de photostabiliser un composant textile à base de polymères matés par le dioxyde de titane anatase. Ce procédé consiste à disperser dans de l'eau de nombreuses particules de dioxyde de titane anatase, à introduire un matériau source de silice tel que le silicate de sodium dans la dispersion résultante pur former une suspension, à abaisser le pH de cette suspension à moins de 6 environ et de préférence à moins de 3,5 environ, à précipiter la silice provenant du matériau source et à former un revêtement en silice amorphe recouvrant les particules de dioxyde de titane anatase, à mélanger ces particules ainsi recouvertes avec une résine polymère et à extruder le mélange résultant pour former un composant textile. L'invention porte aussi sur un tapis produit avec ce composant textile. Dans une variante préférée, on dépose aussi de l'oxyde d'aluminium sur les particules de dioxyde de titane anatase recouvertes de silice. Ce procédé se révèle particulièrement efficace pour les composants textiles à base de polymères que l'on soumet à un traitement ultérieur anti-taches à faible pH.
PCT/US1992/010105 1991-12-04 1992-11-23 Polymere mate par le dioxyde de titane anatase et dote d'une photostabilite amelioree WO1993011286A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US80209891A 1991-12-04 1991-12-04
US802,098 1991-12-04

Publications (1)

Publication Number Publication Date
WO1993011286A1 true WO1993011286A1 (fr) 1993-06-10

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PCT/US1992/010105 WO1993011286A1 (fr) 1991-12-04 1992-11-23 Polymere mate par le dioxyde de titane anatase et dote d'une photostabilite amelioree

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WO (1) WO1993011286A1 (fr)

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1326908C (zh) * 2005-10-25 2007-07-18 辽宁银珠化纺集团有限公司 全消光聚酰胺66树脂及纤维的制造方法
CN101050278B (zh) * 2007-04-18 2010-12-08 沈有清 半消光锦纶切片及其生产方法
WO2013062781A1 (fr) * 2011-10-28 2013-05-02 E. I. Du Pont De Nemours And Company Pigments inorganiques traités présentant une dispersibilité améliorée et utilisation associée dans des compositions de revêtement
US9573108B2 (en) 2011-10-28 2017-02-21 The Chemours Company Tt, Llc Treated inorganic core particles having improved dispersability
CN106947296A (zh) * 2017-04-26 2017-07-14 攀钢集团研究院有限公司 高耐候性钛白粉及其制备方法

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3505088A (en) * 1965-08-05 1970-04-07 Titan Gmbh Process for the manufacture of a titanium dioxide pigment for the delustering of polyamide fibers
WO1983001780A1 (fr) * 1981-11-19 1983-05-26 Lerch, Erwin Pigment anatase post-traite et son utilisation
US4710535A (en) * 1985-06-13 1987-12-01 Rhone-Poulenc Fibres Masterbatches for delustring polyamides

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3505088A (en) * 1965-08-05 1970-04-07 Titan Gmbh Process for the manufacture of a titanium dioxide pigment for the delustering of polyamide fibers
WO1983001780A1 (fr) * 1981-11-19 1983-05-26 Lerch, Erwin Pigment anatase post-traite et son utilisation
US4710535A (en) * 1985-06-13 1987-12-01 Rhone-Poulenc Fibres Masterbatches for delustring polyamides

Cited By (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1326908C (zh) * 2005-10-25 2007-07-18 辽宁银珠化纺集团有限公司 全消光聚酰胺66树脂及纤维的制造方法
CN101050278B (zh) * 2007-04-18 2010-12-08 沈有清 半消光锦纶切片及其生产方法
WO2013062781A1 (fr) * 2011-10-28 2013-05-02 E. I. Du Pont De Nemours And Company Pigments inorganiques traités présentant une dispersibilité améliorée et utilisation associée dans des compositions de revêtement
CN103890104A (zh) * 2011-10-28 2014-06-25 纳幕尔杜邦公司 具有改善的分散性的处理过的无机颜料及其在涂料组合物中的用途
JP2014534314A (ja) * 2011-10-28 2014-12-18 イー・アイ・デュポン・ドウ・ヌムール・アンド・カンパニーＥ．Ｉ．Ｄｕ Ｐｏｎｔ Ｄｅ Ｎｅｍｏｕｒｓ Ａｎｄ Ｃｏｍｐａｎｙ 分散性の改善された処理済み無機顔料およびそのコーティング組成物における使用
CN103890104B (zh) * 2011-10-28 2016-11-23 纳幕尔杜邦公司 具有改善的分散性的处理过的无机颜料及其在涂料组合物中的用途
US9539557B2 (en) 2011-10-28 2017-01-10 The Chemours Company Tt, Llc Treated inorganic pigments having improved dispersability and use thereof in coating compositions
US9573108B2 (en) 2011-10-28 2017-02-21 The Chemours Company Tt, Llc Treated inorganic core particles having improved dispersability
CN106947296A (zh) * 2017-04-26 2017-07-14 攀钢集团研究院有限公司 高耐候性钛白粉及其制备方法

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