MXPA96004318A - Article of dress that takes applications or ornaments retrorreflecti - Google Patents

Abstract

The present invention relates to an article of clothing (10) carrying a retroreflective application or ornament (12) having a binder layer (14) on which a retroreflective layer (19) is placed. The retroreflective layer (19) includes a layer of optical elements (16) and a metal reflecting layer (18), and the binder layer (14) includes a thermoplastic copolymer that includes carboxyl group containing units. A retroreflective application, which uses such a binder layer, in conjunction with optical elements coated with aluminum or coated with silver, demonstrates very good durability to the ca

Description

ARTICLE D? DRESS THAT BRINGS RETRORREEL APPLICATIONS OR ORNAMENTS? TECHNICAL FIELD The present invention relates to a clothing article exhibiting or presenting a retroreflective application or ornament and to a method for manufacturing the same.

BACKGROUND OF THE INVENTION Retrograde applications or ornaments have the ability to return a substantial portion of incident light in the direction in which the light originated. This unique ability has led to the widespread use of retro-reflective applications on articles of clothing. People who work or exercise near motor vehicle traffic need to be conspicuously visible so that they are not hit by passing vehicles. Retroreflective applications serve for the purpose of highlighting or highlighting a person's presence when retroreflecting light from the headlights of a motor vehicle. A retroreflective application typically REF: 23031 comprises a layer and optical elements, a polymeric binder layer and a specular reflective layer. The optical elements are usually transparent microspheres that are partially embedded in the polymeric binder layer such that a substantial portion of each microsphere protrudes from the polymeric binder layer. The specular reflective layer typically comprises aluminum, silver or a dielectric mirror, and this reflective layer is placed on the portion of the transparent microsphere, which is embedded in the polymeric binder layer. The light hits the front surface of the retroreflective application, passes through the transparent microspheres, is reflected by the specular reflective layer and is aligned by the transparent microspheres to travel back in the direction of the light source. Retrograde classroom applications must be able to withstand washing conditions when exposed on the article of clothing. If the retroreflective application is not durable to washing and its retroreflectivity becomes substantially diminished after repeating the washing, the article of clothing can not continue to serve its safety function by highlighting the presence of the user. Researchers in the technique of retroreflective application have pursued a progressive objective of developing retroreflective applications, which are durable to washing, so that people who wear the retroreflective article of clothing can continue to be noticeably visible after the article of clothing. dress has been used and cleaned many times. In U.S. Patent No. 4,763,985 issued to Bingham, a retroreflective, washable application is described and comprises a transparent microsphere layer, a specular reflective layer optically connected to each microsphere and a binder layer on which the microspheres are partially embedded. Resins described as being suitable for use as binders include polyurethane, polyesters, polyvinyl acetate, polyvinyl chloride, acrylics, or combinations thereof. The specular reflective layers are composed of two subsequent layers of dielectric material. The layers have varying refractive indices and are composed of a variety of binary metal compounds including oxides, sulfides and fluorides. Although the retroreflective application of U.S. Patent No. 763,985 is described to be durable under washing conditions, durability is provided only for the applications employing dielectric reflectors. The patent does not disclose how to provide a retroreflective sheet that can be washed, which employs a reflector of elementary aluminum metal or elemental silver. In U.S. Patent No. 5,200,262 issued to Li, a retroreflective, washable application is described, which employs a reflector comprising elemental aluminum or elemental silver on the back of the microspheres. The application comprises - a monolayer of microspheres coated with metal partially embedded inand partially protruding from a binder layer comprising a flexible polymer having hydrogen functionalities and one or more functional silane coupling agents with isocyanate. The described flexible polymers possessing hydrogen functionalities are flexible, cross-linked urethane-based polymers. such as polymers cured with isocyanate or one or two polyurethanes and component polyols. This retroreflective application can provide excellent wash durability: it can withstand industrial washing conditions, involving wash temperatures as high as 40 to 90 ° C (105 to 190 ° F) and pH values of 10 to 12.5- Although the application demonstrates durability to the superior wash, this does not do it without a cost. The materials used in the binder layer are relatively expensive, and they are typically coated in solution on the microspheres, which requires the use of an solvent that is added to the processing costs and that must be recovered or disposed of. In an environmentally safe manner, US Patent No. 5,283,101 issued to Li discloses a washable retroreflective application, which comprises a binder layer formed of a curable polymer with an electron beam and typically one or more crosslinkers and silane coupling agents The electron beam curable polymers described in the Li patent include chlorosulfonated polyethylenes, ethylene copolymers comprising at least about 70 weight percent polyethylene such as ethylene / ethylene acetate, ethylene / acrylate and ethylene / acrylic acid, and poly (ethylene-co-propylene-co-diene) polymers. Rustan in the cured binder layer, and a layer of reflective metal is placed, speculating on the embedded portions thereof. Retroreflective applications have been shown to be durable under industrial washing conditions; however, the binder layer of the application typically includes a crosslinker and a coupling agent and requires the step of curing the polymer with an electron beam. Additionally, a solvent is used to coat the binder layer on the microspheres, which needs to be recovered or disposed of in an environmentally safe manner.

BRIEF DESCRIPTION OF THE INVENTION The present invention provides a new article of clothing that exhibits or exhibits a retroreflective application or ornament that has good durability to washing. The retroreflective application can resist washing at home, repeated, and this can be done without using a dielectric reflector or a relatively expensive binder layer. In addition, the application can be done through the process that does not use solvents. In a brief summary, the article of clothing of the invention comprises: (a) a retroreflective application or ornament that includes: (i) a binder layer comprising a thermoplastic copolymer comprising units containing carboxyl groups; (ii) a layer of optical elements having portions embedded in the binder layer; and (iii) a reflective layer of metal that is placed below the embedded portions of the optical elements; and (b) a substrate forming part of the outer portion of the article of clothing, the retroreflective application is secured to the substrate. The present invention differs from the retroreflective, wash-off applications of the prior art, by using a binder layer comprising a thermoplastic copolymer containing units which possess carboxyl groups, as the term is used herein "carbo-15-xyl group" means a group consisting of a carbonyl group and a hydroxyl group bonded to a carbon atom of the carbonyl group, specifically, the -COOH group.The binder layer of the application is in a thermoplastic state when The term "thermoplastic" is used in all respects to mean that the copolymer is in a morphology that allows it to be heated reversibly and repeatedly to a liquid state without substantially altering the melting point 25 of the copolymer Previous retroreflective applications have employed non-thermoplastic polymers, -retic ions, crosslinkers, and functional silane or isocyanate coupling agents in the binder layers. .The retroreflective applications also have used a solvent to apply the binder layer on the microspheres. Although the known non-thermoplastic binder layers have provided a durability to washing, excellent for retroreflective applications, the binder layers have also contributed significantly to the cost of the resulting product. The present invention is advantageous over known retroreflective applications where acceptable home wash durability can be provided by the use of a The relatively cheap binder layer can be molded onto the application without the use of potentially harmful crosslinkers, coupling agents and solvents. Although the wash durability provided by the invention may not be so great as to To withstand the more stringent industrial washing conditions, the articles of clothing of the invention demonstrate good durability under washing conditions at home, which are the most common type of laundry for everyday clothing. Typically, only the article of clothing that is subject to the most extreme. Environmental conditions, such as a fireman's jacket, are washed under the most stringent industrial conditions, and in this way the present invention is able to meet the demand for the most commonly used retroreflective clothing article that is washed at home. The foregoing and other advantages of the invention are shown and described in more detail in the drawings and the detailed description of this invention, where like reference numbers are used to represent similar parts. However, it should be understood that the drawings and description are for illustration purposes only and should not be read in a way that unduly limits the scope of this invention. * BRIEF DESCRIPTION OF THE DRAWINGS FIGURE 1 is a cross section of a portion of a garment article 10 according to the present invention having a retroreflective application or ornament 12 secured thereto. FIGURE 2 illustrates an article 28 used to form a retroreflective application or ornament 12.

FIGURE 3 illustrates a clothing article 30 according to the present invention exhibiting or presenting a retroreflective application or ornament 32.

DETAILED DESCRIPTION OF THE PREFERRED MODALITIES In the description of the preferred embodiments of the invention, specific terminology is used for a reason of clarity. However, the invention is not intended to be limited to the specific terms selected, and it should be understood that each term thus selected includes all technical equivalents that operate in a similar manner. In the practice of the present invention, an article of clothing having a retroreflective appliqué or ornament attached thereto that demonstrates good durability under washing conditions at home is provided. FIGURE 1 illustrates a portion of an article of clothing 10 of the invention, having a retroreflective application 12 secured thereto. the retroreflective application 12 includes a binder layer 14-, optical elements which may be a monolayer of microspheres 16, and a reflective layer of metal 18. The microspheres 16 and the metal reflecting layer 18 together form a retroreflective portion. 19 capable of returning a substantial amount of incident light to its source. The retroreflective application 12 can be applied to a substrate 20 that is part of an article of clothing 10. An adhesive 21 can be used to secure the application 12 to the substrate 20. The binder layer 14- includes a thermoplastic copolymer comprising units which contain carboxyl groups. the microspheres 16 are partially embedded in, and partially protrude from the binder layer 14 .. The metal reflective layer 18 is placed over the embedded portion of the microspheres 16. The binder layer is typically a sheet-like, polymeric layer , impermeable to the fluid, continuous, which has a thickness of approximately 1 to 250 microns. Preferably, the thickness is about 25 to 75 microns. A thickness of less than 25 microns may be too thin to adhere to both the substrate and the optical elements, and a thickness greater than 75 microns may unnecessarily harden the application and add to its cost. The thermoplastic copolymers that can be used in the binder layer of this invention include carboxyl group-containing units, including carboxylic, ethylenically unsaturated carboxylic acid monomers, such as acrylic acid, methacrylic acid, itaconic acid, citraconic acid, acid paleico, fumaric acid, and co-nations thereof. Thermoplastic copolymers containing acrylic acid and / or methacrylic acid units are preferred. Acidic monomers can be copolymerized with, for example, one or more of the following ethylenically unsaturated monomers: ethylene; propylene, butadiene, isoprene, isobutylene; acrylonitrile; chloroprene; vinyl halides such as vinyl chloride, vinylidene halides, vinyl acrylate, vinyl acetate; vinylalkyl acrylates; wherein the alkyl group contains 8 or fewer carbon atoms, such as methyl vinyl acrylate, vinylethyl acrylate and vinyl butyl acrylate; vinylalkyl methacrylates, wherein the alkyl group contains 8 or fewer carbon atoms, such as vinylmethyl methacrylate, vinylethyl methacrylate and vinylbutyl methacrylate; vinyl stylus; vinyl alcohol; alkyl cyanoacrylate, wherein the alkyl group contains 8 or fewer carbon atoms; and acrylamide. Preferred thermoplastic copolymers include poly (ethylene-co-acrylic acid) (EAA) and poly (ethylene-co-methacrylic acid) (EMAA). Preferentially, units containing carboxyl groups comprise about 2 to 30 weight percent of the copolymer. More preferably, the units containing carboxyl groups comprise about 4 to 20 weight percent of the copolymer. Therefore, the remaining comonomer units (s) preferably comprise from 70 to 98 weight percent of the copolymer, and more preferably from 80 to 96 weight percent. Thus, preferred ethylene copolymers comprise about 70 to 98 weight percent of ethylene units and 2 to 30 weight percent of units containing acrylic acid and methacrylic acid, and more preferably comprise 80 to 96. percent by weight of ethylene units and 4 to 20 weight percent of units containing acrylic acid or methacrylic acid. Combinations of the various copolymers containing carboxyl functionality can also be employed. The carboxylic acid groups can also be incorporated into thermoplastic polyurethane, polyester and polyamide polymers. Examples of commercially available copolymers which may be particularly suitable as binder layers in this invention include: Primacor 34''0 and 5980, and Dow Adhesive Films (DAF) 803 and 808, all available from Dow Chemical of Midland, Michigan; and Nucrel ™ 599 and 699 and Surlyn ™ 1702, available from E.l. Dupont from 'Nemours of Wilmington Dela? Are. The binder layer may also contain one or more additives such as dyes (e.g., pigments, dyes, flakes or m-etal flakes), fillers, stabilizers (e.g., thermal stabilizers and antioxidants such as phenols or hinders and stabilizers). of light such as impeded amines, or ultraviolet light stabilizers), flow modifying flame retardants (e.g., surfactants such as fluoropolymeric silicones), plasticizers and elastomers. Care must be taken when selecting such additives because some may detrimentally affect the durability to washing. It has been found that the use of a substantial amount of some pigments, for example, titanium dioxide, can adversely affect retroreflectivity after washing. However, other additives can improve the durability to washing. For example, it has been found that plasticizers such as di-octylterephthalate (DOTP), di-isodecylphthalate (DIDP), and alkylbenzyl phthalate, can improve wash durability. It has also been found that elastomers can be used in the binder layer, and good results can be achieved. Such elastomers may include Hypalon-20 S (available from El Dupont de Nemours and Company, Wilmington, Del.), Polysar EPM 306 P (available from Miles, Inc., Polysar Rubbe ^ Division, A ron, Ohio), and Nipol VT 4555 (available from Zeon, Chemicals, Rolling Meadows, Illinois). Preferably, the additives are resistant to the degradation or leaching of the binder layer during washing. A colorant may be used to disguise the discoloration of the binder material and / or to give the appearance of environmental color desired to the application Typically, a black colorant is preferred because it provides the most effective disguise of the binder material. An application comprising micro spheres with aluminum reflectors as retroreflective elements and a black dye will typically exhibit a pleasing silver appearance.The preferred dyes are black dyes or colorants, for example, azo metal dyes such as azo dyes or dyes. The binder layer typically contains from 0.01 to about 2.0 percent by weight, preferably from about 0.1 to about 0.5 percent by weight of dye, and supported by the binder layer, the 5 optical elements are able to align the light so that , in conjunction with the specular reflective layer, the incoming light can be reflected. As above, the optical elements used in the application of this invention may be microspheres, which, preferably, are substantially spherical in shape, in order to provide more uniform and efficient retroreflection. The microspheres are also preferably substantially transparent to minimize lume absorption so that a large percentage of the incident light is retroreflected. The microspheres are often substantially colorless but may be colored or inked in some other way. The microspheres can be made of glass, a non-vitrea ceramic composition, or a synthetic resin. In general, glass microspheres are preferred because they tend to be less expensive, harder, and more durable than microspheres made of synthetic resin. Examples of microspheres that may be useful in this invention are described in the following North American patents: 1,175,224, 2,461,011, 2,726,161, 2,842,446, 2,853,393, 2,870,030, 2,939,797, 2,965,921, 2,992,122, 3,468,681, 3,946,130, 4,192,576, 4,367,919, 4,564,556, 4,758,469, 4,772,511 , and 4,931,414. The descriptions of these patents are incorporated herein by reference.

The microspheres used in the present invention typically have an average diameter in the range of about 30 to 200 microns. Microspheres smaller than this range tend to provide lower levels of retroreflection, and microspheres larger than this range can give a rough texture, undesirable to the application or can undesirably reduce its flexibility. The microspheres used in the present invention typically have a refractive index of about 1.7 to about 2.0, the range typically considered to be useful in retroreflective products based on microspheres where the front surfaces of the microspheres are exposed to the environment, Specifically, air. Retroreflective items that have microspheres exposed to the environment are commonly referred to as "retroreflective sheets of exposed lenses." As mentioned above, the optical elements used in this invention may have a metal reflecting layer placed below the embedded portions of the optical elements. Preferably, the metal reflective layer is placed on the embedded or rear portions of the optical elements. The term "metal reflective layer" is used herein to give -a to understand a layer comprising an elemental metal that is capable of reflecting light, preferably reflecting light specularly. A variety of metals can be used to provide a reflective, specular metal layer. These include aluminum, silver, chromium, nickel, magnesium and the like, in elemental form. Aluminum and silver are the preferred metals for use in the reflective layer. The metal can be a continuous coating *** as produced by vacuum deposition, vaporization coating, chemical deposition, or coating by chemical reaction. It should be understood that in the case of aluminum, some of the metal may be in the form of oxide and / or metal hydroxide. Aluminum metals and silver are preferred because they tend to provide the highest reflective brightness. The metal layer must be thick enough to reflect the incoming light. Typically, the metal reflective layer is approximately 50 to 150 nanometers thick.

Although the reflective color of a silver coating may be brighter than an aluminum coating, an aluminum layer is usually more preferred, because it can provide better wash durability when it is adhered to a glass optical element.

A retroreflective application 12 can be made by first forming the article 28 shown in FIGURE 2. In forming the article 28, a monolayer of optical elements is first made by, for example, cascading microspheres 16 onto a carrier fabric 22. The carrier fabric 22 secures the microspheres 16 thereon in a desired, temporary arrangement. The microspheres 16 are preferably packaged as tightly as possible on the carrier web * > _ '_ 22, and can be arranged by any convenient process, such as stamping, screening, pouring in cascade or with a hot brass roller. Carrier web 22 may include a heat-softenable polymer layer 24 on a paper web 5 26. Examples of useful polymer layers 24 for carrier web 22 include: polyvinyl chloride; polyolefins such as polyethylene, polypropylene, and polybutylene; and polyesters; etc. For a further discussion of the application of microspheres to the carrier fabric, see U.S. Patent Nos. 4,763,985; 5,128,804; and 5,200,262, the descriptions of which are incorporated herein by reference. In cooling, the polymeric layer 24 keeps the microspheres 16 in the desired array. 5 Depending in part on the characteristics of the carrier fabric 22 and microspheres 16It may be desirable to condition the carrier fabric 22 and / or microspheres 16 by applying selected release agents or adhesion promoters to achieve desired release properties of the carrier fabric. The metal reflective layer 18 is then applied to the carrier fabric 22 on the side where the exposed portions of the microspheres protrude to form a retroreflective portion 19- The size of the microspheres 16, indicated by the surface portion of the microspheres covered with the metal reflective layer 18 can be controlled in part by controlling the depth at which the microspheres 16 are embedded in the carrier fabric prior to the application of the metal reflective layer 18. After the formation of the retroreflective portion 19 , the binder layer 14 can be formed on the specular reflective layer to form the article 28 illustrated in FIGURE 2. In the practice of the present invention, the binder layer 14 can be placed on the protruding, metal-coated portions of the microspheres 16 without the use of a solvent. This avoids problems of solvent processing, recovery and disposal of the solvent and facilitates the field application of the retroreflective application. A sheet of thermoplastic copolymer containing carboxyl groups can be fixed to the microspheres embedded in the carrier fabric by placing the thermoplastic sheet on the exposed portions of the microspheres and by heating the sheet until it softens and becomes bound to the specular reflector material. and until the microspheres 16. After the formation of the article 28,1a carrier fabric 22 it can then be removed from the structure, leaving the microspheres 16 embedded in the binder layer 14 as shown in FIGURE 1. When using the technique described above, the thermoplastic binder layer 14 can be applied in a variety of ways, resembling signs or characters. This allows the microspheres 16 and the mirror reflective metal 18 to be selectively removed from the carrier web 22 so that the application 12 can retroreflectively display or present the desired shape, sign or characters. In an alternative form of forming a retroreflective application according to the invention, a sheet of a thermoplastic copolymer containing carboxyl groups can first be adhered to a substrate (eg, a fabric) which subsequently becomes part of a article of clothing of the invention, and then the carrier fabric 22 supporting the microspheres 16'and the metal reflective layer 18 can be applied thereto, heated and subsequently removed. The applications of the invention can be applied to a substrate using a variety of methods. In one method, the binder layer of the application 14 is heat laminated directly to the adjacent substrate. Alternatively, the application 12 can be mechanically secured to the substrate by, for example, weaving work. However, in some applications, it is desirable to ensure application to the substrate by the use of an adhesive layer, seen in FIGURE 1 by the number 21. The adhesive layer may be a pressure sensitive adhesive, a heat activated adhesive, or an adhesive activated by ultraviolet light. For example, a plate application may be provided by using a layer of melting thermoplastic material, suitably. Although, many adhesive resins may not adhere well to a layer of EAA or EMAA, it has been found that an EAA layer prepared with a NeoRez urethane (available from ICI Resins of Wilmington, Massachusetts) can demonstrate good adhesion to a melt adhesive film. hot polyester / urethane such as Esta e 52213 (available from BF Goodrich of Cleveland, Ohio). An adhesive layer can sometimes be unnecessary because the binder layer can act as its own adhesive. The substrate to which the retroreflective application can be fixed can be any substrate that is subsequently located on the outer surface of the article of clothing, so that the application is displayed or presented when the article of clothing is used in its normal orientation on the person. The substrate can be, for example: a flat or non-flat fabric such as a cotton fabric; a polymeric layer including nylon, olefins, polyesters, cellulose fibers, urethanes, vinyls, acrylics, rubber; leather; and similar. FIGURE 3 illustrates an example of an article of clothing, a security jacket 30, exhibiting a retroreflective application 32. Although a security vest 30 has been selected by illustration, the article of clothing of the invention may be developed in a variety of ways. shapes. As used herein, the term "article of clothing" means a piece of clothing that ST can wash dirasionally and configured to be worn or worn by a person. Other examples of clothing items that may exhibit retroreflective applications according to the invention include: shirts, sweaters, jackets, jackets, pants, shoes, calendars, gloves, belts, hats, suits, one-piece body garments, bags, - backpacks, etc. Advantages and properties of this invention are further illustrated in the following Examples. However, it should be explicitly understood that while the examples serve this purpose, the particular ingredients and amounts used as well as other conditions and details should not be constructed in a manner that would unduly limit the scope of this invention.

EXAMPLES Unless otherwise indicated, all material compositions are expressed in parts in this manner.

Example 1 This example illustrates how to embed a layer of retroreflective elements in a binder layer of the invention, where the binder layer is first attached to a tissue substrate. A base sheet comprising a monolayer of transparent glass microspheres is prepared by providing a carrier web consisting of a paper substrate and a 50 micron thick layer of polyethylene. The carrier fabric is placed in a generally horizontal orientation with the polyethylene layer placed on top. A monolayer of transparent glass microspheres (60-100 microns in diameter) is cascaded onto the polyethylene surface layer. Polyethylene • then heated to a temperature in the range of 107-148 ° C (225-300 ° F) to allow the microspheres to settle on the surface to a desired depth, and then allowed to cool. An 80-nanometer-thick layer of aluminum is coated by vaporization on the exposed surfaces of the glass microspheres. A thin sheet (50-75 microns thick) of Primacor 3460 (EAA) resin was then squeezed onto the surface of a 65/35 polyester / cotton fabric (65% polyester, 35% cotton) (Springs Mills "Excelerate" 20 brand), bonding the resin to the fabric as it cools. The resin surface of the resin-woven composite is then laminated to the aluminum vaporized side of the base sheet using a lamination temperature of 150 ° C. After the multilayer, laminated composite was allowed to cool, the paper / polyethylene carrier fabric was removed immediately, exposing the glass surfaces of the opposite microspheres of the aluminum-coated surfaces now embedded and bonded to the Primacor 5 E resin. Emplos 2-6 These examples illustrate how to mold a thermoplastic binder layer of the invention as a -, < / separate film and then heat laminate simultaneously a fabric and a carrier fabric of microspheres supported to the opposite surfaces of the binder layer. Examples 2-6 were prepared by extruding films of thermoplastic resins (Table 1) which have an acid functionality on a support film, of polyester, allow cooling to adjoining films, die-cut segments of adjacent films to approximate dimensions of 10.2 by 15.2 centimeters (cm) (4. inches by 6 inches), detach the segments of the thermoplastic resin film from the polyester support film, and place the segments of the thermoplastic resin film between a larger segment of polyester fabric /cotton of 65/35 and a base sheet comprising a monolayer of microspheres embedded in a polyethylene layer 50 microns thick, supported by a paper. An 80-nanometer-thick layer of vapor-coated aluminum was placed on the protruding portions of the microspheres, and the thermoplastic resin was placed in contact therewith. The fabric and the base sheet were laminated to opposite sides of the thermoplastic resin film in a HIX Model HA-8 laminator at a temperature of about 140 ° C for about 20 seconds. After the laminated composite structure was allowed to cool, the paper-supported carrier fabric immediately peeled off the remaining layers of the composite, exposing the glass surfaces of the retroreflective elements. The fabric layer was then cut to provide a band of about 2-5 c, and the sample application was sewn onto a 91 cm by 91 cm (36 inches by 36 inches) sheet consisting of a muslin fabric, bleached with approximately 65/35 polyester / aldogon fiber content. Five to ten different samples, each containing a different resin in the binder layer were baked to the same larger sheet to ensure the same exposure time interval and other test conditions. Each sample (Examples 2-6), while attached to the longer tissue carrier, was. placed in the retro-luminometer to measure its initial retroreflective brightness, in light candles, per square meter (CPL), in accordance with the normal method described in the North American Defensive Publication No. T987,003 at divergence angles of approximately 0.2 ° and angle of entry of -4 °. The values of retroreflective, initial brightness in CPL for Examples 2-6 are listed in Table I. Tissues having the samples bound thereto were then subjected to a series of house wash ratings, where each sample was subjected to a total of 25 washing cycles and a total of 5 drying cycles. The following valuation methods were used: each sample was washed for 5 consecutive cycles in a Maytag Model A208 automatic washing machine using the following settings: "regular" action (setting 10), "Large" load, "Regular" tissue, and Temperature "Hot / Cold". The washing machine was attached to a temperature controlled water supply that provides an initial water temperature of 43 ° C (110 ° F). Forty (40) grams of a normal detergent, obtained from the American Association of Textile Chemists and Colorists (AATCC) Technical Center, P.O., was used for each wash cycle. Box 12215, Research Triangle, North Carolina '27709. Each wash cycle was followed by a rinsing cycle with cold water. After each fifth wash / rinse cycle each sample was dried by spinning in a Maytag DE308 Scrubber, using machine settings of "Low" Temperature and "Regular" Fabric until the total load was dried. Each sample was then spun for a cooling period of 5-10 minutes in the tumble dryer with the quench turned off. After each drying cycle, each sample was placed back into the retro-luminometer to measure its remaining retroreflective brightness. The complete sequential procedure of 5 wash cycles followed by a drying cycle was repeated 5 times, and then the values for the remaining retroreflective brightness in CPL, listed in Table 1, were measured by the same procedures and equipment used to obtain the starting initials.

Table 1 Example Thermoplastic Resin CPI Initial CPL Remaining 2 Primacor ™ 1430 EAA 572 511 3 Primacor ™ 3440 EAA 583 559 4 Primacor ™ 3460 EAA 580 558 5 Primacor ™ 3460 EAA 566 466 6 Primacor ™ 3460 EAA 565 443 The data in Table I demonstrate that retroreflective applications of the invention retain high retroreflective gloss after repeated washings.

Examples 7-14 Examples 7-14 were designed to compare the differences in degradation during the 25-cycle house wash ratings for various binder layer resins listed in Table II. Examples 7-14 were prepared as described in Examples 2-6 and were subjected to a series of 25 wash cycles and 5 drying cycles in a similar manner. The initial values of retroreflective brightness, and retroreflective brightness values remaining after the 25 wash cycles and 5 drying cycles were also measured in the same way using the same measuring equipment, with the percentage of the original value of the retroreflective brightness ( % of BR) remaining after 25 cycles of washing and drying at home reported in Table II.

Table I I Units Example Ra sine Acidics in% of B. R. Percent by weight MR 7 Primacor 1 430 EAA 9 93% 8 Primacor ™ 3440? AA 9 89% MR 9 Primacor 3460 EAA 9 98% PrimacorMR 5980 EAA 20 87% 11 Movie D? F 803 EAA? 92% 12 Film DAF 808 EAA'a 95% 13 NucrelMR 599 EMAA 10 84% 14 NucrelMR 699 EMAA 11 78% a Acidic Units in Percent in Weight are not known The data in Table II demonstrate that the retroreflective applications of this invention retain a high percentage of retroreflective gloss after repeated washings.

Examples 15-23 Examples 15-23 were designed to evaluate the effects of the additives on the performance of a retroreflective application. Examples 15 and 18 comprise substantially pure EAA or EMAA resins, and Examples 16-17 and 19-23 are based on the same base resins, respectively, but contain various modifying materials. Examples 15-23 were prepared using the steps and procedures of Examples 2-6 and were also subjected to a series of 25 washing cycles and 5 drying cycles. The initial values of the retroreflective brightness, and the values of the retroreflective brightness remaining after 25 washing cycles and 5 drying cycles, were measured using the same measuring equipment. Table III shows the composition of the binder layer for each of the samples 15-23 and its percentage of retroreflective brightness (% of B.R.) remaining of the original value after 25 cycles of washing and drying at home. Table III also lists the percentage of remaining retroreflective brightness (% Re), relative to control examples 15 and 18.

Table III Modifying resin example% of B.R. % I laughed 100% of Nucrel ™ 1214 75 100 16 80% Nucrel ™ 1214, 65 87 20% Elvax ™ 450 EVA 17 80% Nucrel ™ 1214, 2% 56 Elvax MR 40w EVA 18 * 100% Primacor ™ 3460 82 100 19 95% Primacor MR 3460, 5% 91 111 of Di-Iso Decyphthalate 20 80% of Primacor® 3460, 89 109 20% of Estane® 58271 21 80% of Primacor MR 3460, 87 106 20% of Rubber 1072 NBR 22 80% of Primacor 3460, 85 104 20% of polyester Bostik 4117 23 80% of Primacor 3460, 84 102 20% of Hypalon 20 24 * 100% of Primacor® 3460 91 100 50% of Hypalon 20S, 88 97 50% of Primacor® 3460 26 50% of Polysar® EMP 306P, 73 80 50% of PrimacorTM 3460 27 50% of NipolMR VT 4555, 84 92 50% of Primacor 3460 ^ Control sample The data in Table III demonstrate that some modifiers in the binder layer at some levels can improve the durability of washing, while others can have damaging effects on performance. This invention can accept various modifications and alterations without departing from the spirit and scope thereof. Accordingly, it should be understood that this invention should not be limited to that described above, but should be controlled by the limitations set forth in the following claims and any equivalent thereof.

It is noted that in relation to this date, the best method known to the applicant to carry out the aforementioned invention, is that which is clear from the present description of the invention.

Having described the invention as above, property is claimed as contained in the following:

Claims (10)

1. An article of clothing sized and configured to conform to a body of a person, characterized in that it comprises: (a) a retroreflective application or ornament that includes: (i) a binder layer comprising a thermoplastic copolymer comprising units which contain carbo groups - xyl; (ii) a layer of optical elements having portions embedded in the binder layer; and (iii) a metal reflecting layer that is positioned below the embedded portions of the optical elements; and (b) a substrate that forms part of the outer portion of the article of clothing, the retroreflective application that secures the substrate.

2. The article of clothing according to claim 1, characterized in that the thermoplastic copolymer contains: (i) units selected from the group consisting of acrylic acid, methacrylic acid, itaconic acid, citraconic acid, maleic acid, fumararipic acid, and combinations of the same; and (ii) units selected from the group consisting of ethylene, propylene, butadiene, isoprene, isobutylene, acrylonitrile, chloroprene, vinyl halides, vinylidene halides, vinyl alkyl acrylate, vinyl alkyl methacrylate, vinyl styrene, methyl styrene, alcohol vinyl acetate, vinyl acetate, acrylamide, alkyl cyano-acrylate, alkyl vinyl ether and combinations thereof, wherein the alkyl group in vinylalkyl acrylate, vinylalkyl methacrylate, alkyl cyano-acrylate and alkyl vinyl ether contains up to eight carbon atoms .

3. The article of clothing according to claim 2, characterized in that the binder layer contains units of acrylic acid, methacrylic acid or a combination thereof, and ethylene units.

4. The article of clothing according to claim 3, characterized in that the binder layer comprises poly (ethylene-co-acrylic acid), poly (ethylene-ca-methacrylic acid), or a combination thereof.

5. The article of clothing according to claim 3, characterized in that the units containing acidic functionality comprise 2 to 30 weight percent of the copolymer and the styrene units comprise from 70 to 98 weight percent of the copolymer.

6. The article of clothing according to claim 1, characterized in that the binder layer is a continuous, fluid impermeable layer of a thermoplastic copolymer containing poly (ethylene-co-acrylic acid), poly (ethylene-co-methacrylic acid), or a combination thereof, and wherein the metal reflective layer contains elemental aluminum.

7. The article of clothing according to claim 1, characterized in that the metal reflective layer is placed at least on a portion of the embedded portion of the optical elements, and wherein the metal reflective layer comprises elementary aluminum, elemental silver, or a combination of them. «

8. The article of clothing according to claim 7, characterized in that the metal reflecting layer comprises elementary aluminum.

9. The article of clothing in accordance with the claim! 1, characterized in that it is selected from the group consisting of a shirt, a sweater, a jacket, a trouser, a shoe, a sock, a glove, a belt, a hat, a suit, a one piece body garment, a vest, a bag and backpack.

10. A method of manufacturing an article of clothing, characterized in that it comprises: partially embedding reflective elements in a binder layer to form a retroreflective application, the retroreflective elements include optical elements and a specularly reflecting metal, aluminum, the binder layer it comprises a thermoplastic copolymer including units which contain carboxyl groups: and ensuring retroreflective application or ornament to the article of clothing, wherein the article of clothing is sized and configured to fit within a person's body, and the copolymer containing groups The carboxyl is in a thermoplastic state while the application is secured to the article of clothing.