MXPA05012267A - Laser-markable fibers or fiber products - Google Patents

Abstract

The present invention provides a fiber or fiber product comprising an artificial fiber and filler incorporated therein, the filler being a filler whose own color changes or a filler mixture whose entire color appears to change by irradiation with a laser beam. The filler whose own color changes by irradiation with a laser beam is preferably barium sulfate or diantimony. The filler is usually in the form of particles with a mean particle diameter of not more than about 15µm. When the fiber or fiber product of the invention is irradiated with a laser beam, the fiber changes color in the irradiated portion, so that a minute mark can be produced on the individual spun yarns or filament yarns of the fiber or fiber product.

Description

FIBERS OR FIBER PRODUCTS MARCHABLE WITH LASER TECHNICAL FIELD The present invention relates to a fiber or a laser-markable fiber product.

PREVIOUS TECHNIQUE The methods generally used to mark a fiber or fiber product with a pattern or a mark such as a letter or symbol include printing the fiber or fiber product using a dye, pigment or the like and printing on the fiber or product of fiber using an inkjet printer, etc. (see, for example, Japanese Unexamined Patent Publications Nos. 1990-411480 and 1995-336466). However, the above methods can not be used to produce minute marks such as letters or symbols on fibers or fiber products. Therefore, it has been impossible to mark individual threads with these marks.

BRIEF DESCRIPTION OF THE INVENTION An object of the invention is to provide a fiber or fiber product wherein the individual yarns can be marked with minute markings. In this description "individual yarns" include spun yarns, single filament yarns, multi-filament yarns and the compounds thereof. The inventors of the present one made a very intense investigation to develop a fiber or fiber product in which the individual threads can be marked with a tiny mark, which can be letters or symbols. As a result, the inventors found that a fiber or fiber product that achieves the above objective can be produced by kneading an artificial fiber with a filling whose own color changes or a filling mixture whose full color appears to change by irradiation with a laser beam. The present invention has been achieved based on this finding. The invention provides the following fibers, fiber products and methods: 1. A fiber or fiber product comprising an artificial fiber and a filler incorporated therein, the filling is a filler whose own color changes or a mixture of filler whose color complete seems to change by irradiation with a laser beam. 2. A fiber or product according to item 1, wherein the filler whose own color changes by irradiation with a laser beam is at least one member selected from the group consisting of mica, barium sulfate, zinc sulphide , diantimony trioxide, copper phosphate and tocopherols. 3. A fiber or fiber product according to item 1, wherein the filling mixture whose complete color appears to change by irradiation with a laser beam is a mixture of a filler whose own color changes by irradiation with a laser beam and a white pigment or a mixture of a white filler and a black pigment. 4. A fiber or fiber product according to item 3, wherein the white pigment is titanium dioxide. 5.- A fiber or fiber product according to item 3, where the black pigment is carbon black. 6.- A fiber or fiber product according to item 3, where the white filling is barium sulfate. 7.- A fiber or fiber product in accordance with the point 1, wherein the filler is in an amount of about 0.01 to about 10% by weight, relative to the total weight of artificial fiber and filler. 8. A fiber or fiber product according to item 1 wherein the filler is in the form of particles with a mean particle diameter of no more than about 15 μm. 9. A fiber or fiber product according to item 1, wherein the artificial fiber is a polyester.

. - A method for producing an artificial fiber containing a filler whose own color changes or a filling mixture whose full color appears to change by irradiation with a laser beam, comprising: Mixing and dispersing the filler in a foundry or solution of the raw material of artificial fiber; and Spin the dispersion to turn it into a fiber. 11. A method for marking a fiber or fiber product with a mark or pattern, comprising irradiating with a laser beam the fiber or fiber product of any of points 1 to 9. 12.- A method to distinguish whether a fiber or fiber product is labeled or unlabeled, which comprises checking the presence of a marked or marked pattern on the fiber or fiber product of any of items 1 to 9.

FIBERS OR FIBER PRODUCTS OF THE INVENTION The fiber or fiber product of the invention comprises an artificial fiber and a filler incorporated therein. The filling is a filling whose own color changes or a mixture of filling whose full color seems to change by irradiation with a laser beam. Any of a wide range of artificial fibers known as the artificial fiber of the invention may be used as long as a filler whose own color changes or a mixture of fillers whose full color appears to change by irradiation with a laser beam may be incorporated therein. Examples of said artificial fibers include synthetic fibers, semi-synthetic fibers, regenerated fibers, inorganic fibers and the like. Examples of usable synthetic fibers include polyesters, aliphatic polyamides, aromatic polyamides, polyethylene, tarpaulins, acrylics, polyvinyl alcohols, polyurethanes and the like. Examples of usable semi-synthetic fibers include acetates, triacetates, promix and the like. Examples of usable regenerated fibers include rayon, cupra and the like. Examples of usable inorganic fibers include carbon fibers, ceramic fibers and the like. Among artificial fibers, synthetic fibers are preferred and polyesters are more preferable. Specific examples of polyesters include polyethylene terephthalate, polytrimethylene terephthalate, polytetramethylene terephthalate, and the like. Examples of artificial fibers include slotted yarns, produced by grooving a plastic film such as polyethylene terephthalate, polyethylene or polypropylene. Such grooved threads usually have a width of about 0.1 to about 0.8 mm and preferably about 0.15 to about 0.37 mm and usually have a thickness of about 20 microns or less and preferably about 2 to about 12 microns.

The artificial fibers of the invention can be used on their own or spun, folded or stretched. Artificial fibers can have a core-shell structure. Examples of artificial fibers with a core-shell structure include those produced using a core-slit yarn and winding another fiber (spun yarn or filament yarn) around it, those produced by using a spun yarn or filament yarn as the core and winding a slotted thread around it and those comprising a single filament thread with a core-shell internal structure. The artificial fibers may have a uniform or non-uniform thickness. The cut of artificial fibers can have any shape that can be circular, elliptical, Y-shaped, cross-shaped, W-shaped, L-shaped, T-shaped, hollow, triangular, flat, star shape, in the form of a cocoon, the shape of an 8, in the form of bone (or weight), etc. The fiber of the invention includes not only these fibers but also the primary processed products thereof, such as yarns, fabrics, woven fabrics, knitted fabrics, non-woven fabrics and the like. The artificial fiber of the invention may be a blend fabric of natural fibers such as cellulose fibers, animal hair fibers, silks and the like. In this description a "fiber product" refers to a product obtained by additional processing of a fiber. Examples of such products include outerwear, intermediate clothing, underwear and the like, accessories for beds and bedrooms, interior accessories and the like. Specific examples of fiber products of the invention include clothing such as coats, jackets, pants, skirts, shirts, knit shirts, blouses, sweaters, cardigans, nightwear, underwear, supports, socks, hats, scarves, covers mouths, gloves, clothing coatings, garment hardeners, cotton padding for clothing, work clothes, sanitary garments, uniforms, prison uniforms, school uniforms and the like, bed and bedroom accessories such as mattress covers, cotton mattress covers, pillow covers, sheets and the like, interior accessories such as curtains , rugs, carpets, cushions, stuffed toys and the like, sophisticated articles such as towels, handkerchiefs and the like, yarn products such as machine sewing threads, embroidery threads, pleated cords, ribbons, bands, fishing lines and baits artificial, labels for merchandise, non-woven paper products, bags, materials for electronic products and construction materials. Specific examples of paper products include securities such as stocks, national bonds, local vouchers, gift certificates, money orders, checks, stamps, income stamps, stamps for certificates and admission tickets, vouchers such as coupons and lottery tickets, paper currency, various types of certificates and the like. Examples of the filler whose own color changes by irradiation with a laser beam are mica, barium sulfate (BaSO), zinc sulphide (ZnS) diantimony trioxide (Sb2? 3), copper phosphate (Cu3 (P? 4) 2) , tocopherols, lithopone and the like. These fillers can be used on their own or in combinations of two or more. Among them, barium sulfate and diantimony trioxide are preferred. Tocopherols (vitamin E) include α-tocopherol and β-tocopherol. Bright pigments containing mica can preferably be used as mica. Said bright pigments are sold, for example, by Merck under the trademark Iriodin LS. The filling is preferably in the form of particles. The average particle diameter is normally not more than about microns and preferably no more than about one miera. The particle diameter can be measured, for example, by laser diffraction methods. Examples of the filler mixture whose full color appears to change by irradiation with a laser beam are a mixture of a filler whose own color changes by irradiation with a laser beam and a white pigment, a mixture of a white filler and a black pigment, and so on. . Of these fillings, mica, zinc sulphide, diantimony trioxide and tocopherols are preferred, which change color from white to black. These fillers can be used in combination with a white pigment that acts as a white base in a fiber. The full color of said mixture of a filler and a white pigment changes color from white to black.

Examples of white pigments include calcium carbonate, titanium dioxide (titanium white), zinc oxide and the like. A preferable white pigment is titanium dioxide. Said white pigments can be used on their own or in combination of two or more. The average particle diameter of the white pigment is usually selected from a wide range of about 10 nanometers to about 3 μm and preferably about 10 nanometers to about one miera. The white pigment is usually used in an amount of about 5 to about 90% by weight and preferably about 10 to about 70% by weight, relative to the weight of the filler whose own color changes by irradiation with a laser beam. In the case that the filler whose own color changes by irradiation with a laser beam is a white filler, the white filler can be used in combination with a black pigment that acts as a black base in a fiber. The full color of the white filling mixture and the black pigment changes from black to white during phase separation of the black pigment, bubble formation and so on. Examples of white fillers include mica, barium sulfate and the like. A preferable white filler is barium sulfate. Said white fillers can be used by themselves or in combination of two or more. Examples of usable black pigments include carbon black (acetylene black, lamp black, thermal black, oven black, channel black, Ketjenblack, etc.), graphite, titanium black, black iron oxide and the like. Among these, carbon black is preferred because of its dispersibility and cost. Said black pigments can be used on their own or in combination of two or more. The carbon black can be classified into acetylene black, black oil, gas black, etc., in accordance with the raw material and any carbon black can be used. The average particle diameter of the black pigment is usually selected from a wide range of about 10 nanometers to about three microns and preferably about 10 nanometers to about one millimeter. When the black pigment is a carbon black, it is preferable to have an average particle diameter of about 50 to about 30 nanometers. The amount of black pigment is usually in a range of about 0.1 to about 80% by weight and preferably about 10 to about 50% by weight relative to the weight of the white filler. The filling (the filler whose own color changes or filling mixture whose full color appears to change by irradiation with a laser beam) is normally contained in the fiber or fiber product of the invention in an amount of about 0.01 to about 10% by weight , preferably about 0.3 to about 3% by weight and more preferably about 0.6 to about 1.2% by weight, relative to the total weight of the artificial fiber and the filler.

The fiber or fiber product of the invention may optionally contain other components such as known antimicrobial agents, ultraviolet light absorbers, ultraviolet light reflecting, (e.g., non-black, non-white) pigments and the like.

Method for Producing the Fiber or Fiber Product of the Invention The fiber of the invention comprising a filler whose own color changes or a filler mixture whose full color appears to change by irradiation with a laser beam can be produced by kneading the filler into the fiber during the process of spinning the fiber raw material to turn it into a fiber. When the artificial fiber has a core-shell structure, the filling can be kneaded in one or both of the core and shell. The fiber of the invention is produced, for example, by mixing and dispersing in a melt or solution of the raw material of artificial fiber a filler whose own "color changes or a mixture of filler whose complete color seems to change by irradiation with a laser beam and then spin the resulting dispersion into a fiber.The filling is preferably mixed and dispersed in the raw material of the fiber in the form of a master batch.A wide variety of known spinning methods can be used as fusion methods. Spinning, dry spinning methods and wet spinning methods as a spinning method The spinning method to be used depends on the type of raw material used for the fiber.

When the raw material of the fiber can be melted in a thermally and chemically stable form, it is preferable to use melt spinning. In this case, a predetermined amount of filler can be mixed and dispersed in the melt of the raw material of the fiber. The fiber of the invention can be produced by ejection of the fiber raw material melt with mixed filler and dispersed there through a thin nozzle into the air, followed by air cooling and solidification of the molten filament while attenuating and then it pulls at a constant speed. Suitable fibers for spunbonding are, for example, polyesters, aliphatic polyamides, polyethylenes and polypropylenes. When the raw material of the fiber is stable at high temperatures and can be dissolved in a volatile solvent, it is preferable to use dry spinning. In this case, a predetermined amount can be mixed and dispersed in a volatile solvent solution of the raw material of the fiber. The fiber of the invention can be produced by ejection of the raw material solution from the fiber with a mixed filler and dispersed there through a thin nozzle into a hot gas and then solidifying the solution to convert it into a fiber while evaporating the volatile solvent. Fibers suitable for centrifugation in dry are acrylics, acetates and the like. When the raw material of the fiber only dissolves in low volatility solvents or unstable solvents at high temperatures, it is preferable to use wet spinning. In this case, a predetermined amount of filler in a solution of the raw material of the fiber can be mixed and dispersed. The fiber of the invention can be produced by ejecting the raw material solution from the fiber with a mixed filler and dispersed there through a thin nozzle into a coagulation bath containing a non-solvent and then solidifying it to convert it into a fiber while the solvent is removed. Suitable fibers for wet spinning are, for example, polyvinyl alcohols and Rayon. When the fiber of the invention is in the form of slotted yarns, it can be produced by grooving the following plastic films or multi-layer films using a counter which can be a micro-router, tape router, etc.: A plastic film (for example polyethylene terephthalate, polyethylene, polypropylene, etc.) to which a filling has been incorporated whose own color changes or a filling mixture whose complete color seems to change by irradiation with a laser beam, a plastic film (for example , polyethylene terephthalate, polyethylene, polypropylene, etc.) coated with a composition comprising a filler whose own color changes or a filler mixture whose full color appears to change by irradiation with a laser beam or multi-layer films produced by lamination of other films (for example, polyethylene terephthalate) on the above plastic films. Using a fiber of the invention produced by the above method, a fiber product of the invention can be produced by known methods such as sewing.

When the fiber product of the invention is a paper product, the paper product can be produced by spooning the fiber produced by the above methods with a fine mesh filter. The fibers or fiber products of the invention can be dyed using dyes or pigments appropriate for the raw material of the fiber.

Method for using the fiber or fiber product of the invention When the fiber or fiber product of the invention is irradiated with a laser, impregnated with a filler that changes color by irradiation with a laser beam or has such a filler attached thereto , the filling changes color. Therefore it is possible to change the color of the fiber or fiber product only in the portions irradiated with the laser beam. When the filler incorporated into or annexed to the fiber or fiber product of the invention is a mixture of a white filler and a black pigment, a phase separation or other phenomena occurs in the black pigment and the white pigment appears on the surface of the fiber or fiber product. As a result it is possible to change the color of the fiber or fiber product only in the irradiated portions with laser beam. The lasers that can be used for the invention are YAG laser, excimer laser, CO2 laser and the like. Of these lasers, YAG lasers are preferred and Nd-YAG lasers are more preferred. There is no limitation on the laser wavelength as long as the color of the fill changes. In the case of Nd-YAG lasers it is preferable that the wavelength be about 354 nm, about 532 nm or about 1064 nm. The fiber or fiber product of the invention can be irradiated, for example, by using a scanning laser marking device. Since laser beam irradiation can be controlled by computer, a tiny distinctive mark (eg logos, code numbers, serial numbers, etc.) can be produced in a predetermined position on the fiber or fiber product. Grooved threads marked with a mark or pattern can be used as anti-counterfeit yarn for paper products such as those mentioned above. "Thread" as used herein includes film tapes, wires and other elongated elements suitable for inclusion in paper products. Therefore, when reviewing the presence of a marked or marked pattern on the fiber or fiber product, it can be distinguished if the fiber or fiber product is marked or not marked. More specifically, the fiber or fiber product of the invention is irradiated with a laser beam to produce a fiber or fiber product with a mark or pattern thereon. Fibers or branded fiber products can be checked for the presence of the brand or pattern to distinguish whether fiber or fiber products are genuine or fake. The previous revision can be done at sight, with a magnifying glass, microscope, etc.

EFFECTS OF THE INVENTION The invention provides fiber or fiber products in which individual yarns can be marked with a tiny mark. The invention further provides a method for producing fibers or fiber products wherein the individual yarns can be marked with a tiny mark. When the fiber or fiber product of the invention is irradiated with a laser beam, the irradiated portion changes color so that marks such as letters, symbols or patterns can be produced on the fiber or fiber product. As only the portion of the fiber of the invention irradiated with a laser beam changes color, individual threads of the fiber product of the invention can be marked with marks such as letters, symbols, etc. The branded products, made partly or totally of fiber of the invention can be marked with a mark or pattern of the mark that can not be distinguished with the naked eye but only under a magnifying glass or microscope, thus allowing to distinguish easily if the products marketed are authentic or false, thus effectively preventing the counterfeiting of branded products. The fiber product of the invention has the advantage that the product, when sold, can be quickly marked with the name of the buyer, desired patterns, symbols, etc. in the shop. The fiber or fiber product of the invention is expected to find several applications such as a substitute for embroidery.

PREFERRED MODALITY OF THE INVENTION The invention will now be described in greater detail with reference to examples.

EXAMPLE 1 A masterbatch of polyester (trade name: CESAf LASER NB94120503, product of Clariant International Ltd.) containing 10% by weight of barium sulfate (average particle size: 1 μm) and 10% by weight of carbon black were added in an amount of 5% by weight to a molten polyester (polyethylene terephthalate), prepared by heating to 295 ° C, such that the barium sulfate and the carbon black are dispersed in the polyester to give a polyester melt . The melt was ejected through a nozzle into the air and the thrown filaments were stretched up to 3 times their original length at 115 ° C, thus giving a polyester fiber (filament yarn, diameter: 100 μm) of the invention having barium sulfate and carbon black incorporated into it.

EXAMPLE 2 A master batch of polyester (trade name: CESAf LASER NB031205509, product of Clariant International Ltd.) containing 20% by weight of diantimony trioxide (average particle size: 1 μm) which changes from white to black by irradiation with laser beam was added in an amount of 5% by weight to a molten polyester (polyethylene terephthalate) prepared by heating at 295 ° C, such that the diantimony trioxide was dispersed in the polyester to give a polyester melt. The melt was ejected through an air nozzle and the melted filaments were drawn at 115 ° C to three times their original length, thus giving a polyester fiber (filament yarn, diameter: 100 μm) of the invention having trioxide of diantimony incorporated into it.

EXAMPLE 3 A film of biaxially transparent polyamide and 6 μm of thickness was micro-grooved to a width of 0.2 mm to give grooved threads. Fibers of the invention having a core-shell structure were produced using the barium sulfate-containing polyester fiber (filament yarn) obtained in Example 1 as the core and wrapping the above slotted yarn around it.

EXAMPLE 4 A 6 μm thick, biaxially stretched polyamide film was micro-grooved to a width of 0.2 mm to give grooved yarns. Fibers of the invention having a core-shell structure were produced by using the polyester fiber containing diantimony trioxide (filament yarn) obtained in Example 2 as the core and wrapping the above slotted yarn around it.

EXAMPLE 5 The filament yarn obtained in Example 1 was partially irradiated with an Nd-YAG laser (wavelength: 532 nm). In the irradiated portions, phase separation occurred in the carbon black and barium sulfate was presented on the surface of the filament yarn. As a result, the portion irradiated with the laser changed from black to white, which was clearly visible to the naked eye from the nuance of the portions that had not been irradiated with the laser.

EXAMPLE 6 The filament yarn obtained in Example 2 was partially irradiated with an Nd-YAG laser (wavelength: 532 nm). In the irradiated portions, the diantimony trioxide changed from white to black, which was clearly visible to the naked eye from the nuance of the portions that had not been irradiated with the laser.

EXAMPLE 7 The single filament yarn obtained in Example 1 was irradiated with a Nd-YAG laser beam (wavelength 1064 nm) using a scanning laser marking device (product of TAMPOPRINT AG, model number: WS + SK- 86) to make alphabetical marks (letter size: 80 μm x 80 μm). The single filament yarn was observed under a 200x optical microscope. The alphabetic marks were clearly recognizable.

EXAMPLE 8 The single filament yarn obtained in Example 2 was irradiated with a Nd-YAG laser beam (wavelength: 1064 nm) using a laser marking device by scanning (product of TAMPOPRINT AG, model number: WS + SK -86) to make alphabetical marks (letter size: 80 μm x 80 μm). The single filament yarn was observed under a 200x optical microscope. The alphabetic marks were clearly recognizable.

Claims (12)

NOVELTY OF THE INVENTION CLAIMS

1. - A fiber or fiber product comprising an artificial fiber and a filling incorporated therein, the filling is a filling whose own color changes or a filling mixture whose complete color seems to change by irradiation with a laser beam.

2. The fiber or fiber product according to claim 1, further characterized in that the filling whose own color changes by irradiation with a laser beam is at least one member selected from the group consisting of mica, barium sulfate, zinc sulfide, diantimony trioxide, copper phosphate and tocopherols.

3. The fiber or fiber product according to claim 1, further characterized in that the filling mixture whose complete color appears to change by irradiation with a laser beam is a mixture of the filler whose own color changes by irradiation with a laser beam and a white pigment or a mixture of a white filler and a black pigment.

4. The fiber or fiber product according to claim 3, further characterized in that the white pigment is titanium dioxide.

5. - The fiber or fiber product according to claim 3, further characterized in that the black pigment is carbon black.

6. The fiber or fiber product according to claim 3, further characterized in that the white filler is barium sulfate.

7. The fiber or fiber product according to claim 1, further characterized in that the filler is in an amount of about 0.01 to about 10% by weight relative to the total weight of artificial fiber and filler.

8. The fiber or fiber product according to claim 1, further characterized in that the filler is in the form of particles with a mean particle diameter of no more than about 15 μm.

9. The fiber or fiber product according to claim 1, further characterized in that the artificial fiber is a polyester

10. A method for producing an artificial fiber that contains a filler whose own color changes or a mixture of filler whose full color seems to change by irradiation with a laser beam, which comprises mixing and dispersing the filler in a melt or solution of the raw material of the artificial fiber and spinning the dispersion to convert it into a fiber.

11. - A method for marking a fiber or fiber product with a mark or pattern, comprising irradiating with a laser beam the fiber or fiber product according to any of claims 1 to 9. 12.- A method to distinguish whether a fiber or fiber product is labeled or unlabeled, which comprises checking the presence of a marked or marked pattern on the fiber or fiber product according to any of claims 1 to 9.