Abstract:
An article of clothing is coated or impregnated with a coating that contains thermochromic pigment. The pigment is constructed to change color when wet with water, and/or to provide a hyperthermic warning when a person wearing the clothing is over-warm.

Description:
RELATED APPLICATIONS 
     This application claims the benefit of priority of U.S. Provisional Application Ser. No. 61/836,563, filed Jun. 18, 2013, which is incorporated herein by reference in its entirety. 
    
    
     BACKGROUND 
     1. Field of the Invention 
     The presently disclosed instrumentalities pertain to thermochromic pigments in materials and articles that may be worn by a person or applied to a substrate. In particular, the pigments have a color activation temperature ranging from about 40° C. to 45° C. 
     2. Description of the Related Art 
     Chemicals that change color over a range of temperatures are known as thermochromic systems. Thermochromic chemicals can be manufactured to have a color change that is reversible or irreversible. U.S. Pat. No. 5,591,255, entitled “Thermochromic Ink Formulations, Nail Lacquer and Methods of Use,” issued Jan. 7, 1997, to Small et al., discloses methods of producing thermochromic coating formulations without ingredients known to be harmful to thermochromic inks. The use of distilled water as a fountain solution for off-set printing using thermochromic ink is also disclosed. 
     Thermochromic systems use colorants that are either liquid crystals or leuco dyes. Liquid crystals are used less frequently than leuco dyes because they are very difficult to work with and require highly specialized printing and handling techniques. Thermochromic pigments are a system of interacting parts. Leuco dyes act as colorants, while weak organic acids act as color developers. Solvents or waxes variably interact with the leuco dyes according to the temperature of the system. As is known in the art, thermochromic systems are microencapsulated in a protective coating to protect the contents from undesired effects from the environment. Each microcapsule is self-contained, having all of the components of the entire system that are required for the color change. The components of the system interact with one another differently at different temperatures. Generally, the system is ordered and colored below a temperature corresponding to the full color point. The system becomes increasingly unordered and starts to lose its color at a temperature corresponding to an activation temperature. 
     Below the activation temperature, the system is usually colored. Above the activation temperature the system is usually clear or lightly colored. The activation temperature corresponds to a range of temperatures at which the transition is taking place between the full color point and the clearing point. Generally, the activation temperature is the temperature at which the human eye can perceive that the system is starting to lose color, or alternatively, starting to gain color. Presently, thermochromic systems are designed to have activation temperatures over a broad range, from about −20° C. to about 80° C. or more. With heating, the system becomes increasingly unordered and continues to lose color until it reaches a level of disorder at a temperature corresponding to a clearing point. At the clearing point, the system lacks any recognizable color. 
     In this manner, thermochromic pigments change from a specific color to clear upon the application of thermal energy or heat in a thermally-driven cycle exhibiting well-known hysteresis behavior. Thermochromic pigments come in a variety of colors. When applied to a substrate, such as paper, the pigment exhibits the color of the dye at the core of the microcapsules. In one example, when heat is applied generally in the range of 30 to 32° C., the ink changes from the color of the pigment to clear. When the substrate is allowed to return to a temperature under approximately 30° C., the ink returns to the original color of the pigment. 
     Temperature changes in thermochromic systems are associated with color changes. If this change is plotted on a graph having axes of temperature and color, the curves do not align and are offset between the heating cycle and the cooling cycle. The entire color versus temperature curve has the form of a loop. See generally  FIG. 1  where the extent of color change presents a gap  100  that differs between color change that occurs upon heating  102  to an ultimate clearing point  104  versus cooing  106  to an ultimate full color point  108 . This shows that the color of a thermochromic system does not depend only on temperature, but also on the thermal history, i.e. whether the particular level of color was reached during heating or during cooling. This phenomenon is generally referred to as a hysteresis cycle and specifically referred to herein as color hysteresis or the hysteresis window. Decreasing the width of this hysteresis window to approximately zero allows for a single value for the full color point and a single value for the clearing point. This would allow for a reliable color transition to be observed regardless of whether the system is being heated or cooled. 
     Prior art reveals that the color transition range of microencapsulated thermochromic systems may be adjusted by shifting the full color point upward toward the clearing point, or shifting the clearing point downward toward the full color point, as explained in U.S. Pat. No. 6,494,950. These shifts are accomplished by adding high melting point materials to increase the full color point or, alternatively, by adding low melting point materials to the system to decrease the clearing point. Thus, the full color point or clearing point may be lowered or raised, but the overall temperature range between the two points remains unchanged because the amount of separation or width across the hysteresis window is left largely unaffected. 
     Specific thermochromic coating formulations are known in the art. See, for example, U.S. Pat. Nos. 4,720,301, 5,219,625, 5,558,700, 5,591,255, 5,997,849, 6,139,779, 6,494,950 and 7,494,537, all of which are expressly incorporated herein by reference. These thermochromic coatings are known to use various components in their formulations, and are generally reversible in their color change. Thermochromic; pigments for use in these coatings are commercially available in various colors, with various activation temperatures, clearing points and full color points. Thermochromic coatings may be printed by offset litho, dry offset, letterpress, gravure, flexo and screen processes, among other techniques 
     Microencapsulated thermochromic pigments may be formulated on commercial order and incorporated in coatings that change color in response to changes in temperature. By way of example, U.S. Pat. No. 5,281,570, issued to Hasegawa et al., teaches how to form microencapsulated thermochromic pigments that may be used directly or microencapsulated. The microencapsulated system is preferred and includes a leuco dye system that is mixed with longer chain alcohols, caprates, stearates, palmitates, etc., that are selected for melting point to control the color transition temperature of the pigments. These materials form the core of a microcapsule that may be microencapsulated by a wall of resin, such as an amine resin. Microencapsulated thermochromic pigments having a variety of colors and color transition temperatures may be purchased on commercial order from suppliers, such as Chromatic Technologies, Inc. of Colorado Springs, Colo. 
     SUMMARY 
     The presently disclosed instrumentalities advance the art by providing articles of clothing that are made of fabric which have been coated or impregnated with thermochromic pigment. It is particularly useful that the pigment is constructed such that the pigment changes color in response to cooling that results from the fabric being wet with water, and/or upon heating that dries the fabric after the fabric is wet with water. Alternatively, providing the pigment with an even greater clearing point provides an indicator of hyperthermic risk. 
     In one aspect, the application of water to a pigment with full color point (FC) of preferably from 13° C. to 19° C. and more preferably from 17° C. to 18° C., so that the clothing article will only appear in the colored state when cooled by the effect of cold water. In another aspect, when worn on the body in a dry condition, the thermochromic pigment will not be color activated if it is at a temperature above the clearing point which is preferably from about 23° C. to 26° C., which may be achieved by drying the clothing article after it is wet. The color change may indicate continuing wetness, for example, in a sporting context, or as an indicator of hypothermic risk. 
     In one aspect, heating of a pigment with a higher clearing point (CP) 40° C. to 45° C. indicates hyperthermic risk, such as a warning or hyperthermia or of a need for hydration or a hyperthermia indicator. 
     The thermochromic pigment may be mixed with a non-thermochromic material such that there is a blending of colors or a background color. 
     In one aspect, the thermochromic pigments may be incorporated in an adhesive cloth or a face paint that may be applied to the body to indicate degrees of heat stress. This may be, for example, a wax (beeswax) color stick with pigment that transitions form black to non-black in color. The thermochromic materials may also be incorporated as a design on a Band-Aid® type of strip. 
     In one example, blue thermochromic pigment with a clearing point from 40° C. to 45° C. blue is mixed with a pink and yellow pigmented base coat to form a black to orange coating. These materials are available for mixture in various formulations on commercial order from CTI. 
     In one embodiment, an adhesive tape is manufactured with a thermochromic coating over an image or text that informs a consumer to drink a particular beverage when the consumer sweats to produce a cooling action upon the thermochromic coating. The image or text is not limited to a beverage, but any advertising may suffice, such as advertising for sports teams, military, children&#39;s products, or extreme exercise. 
     In one aspect, the formulations may be provided for fair skinned people to use bright colors and dark-skinned people to use contrasting colors, such as orange, yellow or pink. 
     In particular, a water activated polyurethane vehicle ink with a tetradecanol has a full color point of from FC 17° C. to 18° C. This develops color sharply when wet with water and has no color at room temperature. Clothing and other materials that may be color-activated when wet with water and which incorporates this pigment include, for example, t-shirts, screen-printed designs, pants, hats, super-soaker game wear, and packaging To remove the color and erase the image, dry t-shirts in home laundry cycle drier, use hair dryer or expose to gentle heat source to dry body wear. 
    
    
     
       BRIEF DESCRIPTION OF THE DRAWINGS 
         FIG. 1  shows a hysteresis curve according to the prior art. 
         FIG. 2  shows a shirt made of fabric that has been coated with a coating which contains a thermochromic pigment. 
         FIG. 3  shows the shirt of  FIG. 2  in a state that is partially wet with water to induce cooling that results in a visible color change. 
     
    
    
     DETAILED DESCRIPTION 
       FIG. 2  shows a shirt  200  that may be a cotton T-shirt or another type of shirt made out of any fabric. It will be appreciated that the instrumentalities shown herein may utilize any type of clothing, such as pants, gloves, hats, socks, or undergarments. As shown in  FIG. 2 , a sprayer  202  is applying coating  204  that contains a thermochromic pigment. This coating  204  becomes permanent when dried on shirt  200 . Any mode of application may be used, such as screen printing or saturation on a vat. The shirt  200  has an optional message  206 , in this case “Drink Tea.” This message  206  is hidden or concealed when the coating  204  on shirt  200  has developed full color. 
     The thermochromic pigment of coating  206  may have, for example, full color development (FC) at 17° C. to 18° C. This type of pigment may be color-activated by the use of water, for example, from a hose, squirt gun, water balloon, or other source of water. The color change may facilitate creative games played, such as pretend war, cops and robbers, and other games. By way of example, a squirt gun can make marks appear, such as red for blood or green for alien blood. A variety of colors can be used for Team games. This is a low cost and clean alternative to paint ball games. Thus,  FIG. 3  shows shirt  300 , which has been with thermochromic pigment in like manner with respect to shirt  200 . Shirt  300  has been wet by use of a squirt gun to product indicia of ‘hits’  302 ,  304 . If the wearer would jump into a body of water, such as a swimming pool, shirt  300  would entirely change to the color of hits  302 ,  304 . 
     The indicia  206  may contain an advertisement or warning that reveals as a person perspires or as the shirt  200  dries after being wet. Thus, interactive exercise wear may show the level of physical activity by turning color or revealing messages or graphics as the person perspires. This happens because evaporative cooling activates the body wear. By way of example, multiple thermochromic pigments and non-thermochromic pigments may be combined to produce color changes with various meanings: Black that clears to reveal an orange background may be used to communicate a warning to rehydrate. Where yellow thermochromic pigment in the orange clears at a slightly higher temperature to show as red, this may indicate a more serious hyperthermic warning (CP40-CP45) that an athlete needs to take a break. Alternatively, the pigment may function as a hypothermia indicator when it has a full color point of FC8-FC12. 
     The coating  204  is preferably water-activated to produce a color change by thermochromic action. This action depends on a reduction from ambient temperature to an activation temperature to effect the color change. When water evaporates, the heat loss from the transition from liquid to gas sufficiently reduces the temperature to activate the thermochromic microcapsules. 
     The thermochromic pigments may be commercially ordered such that the activation temperature is engineered to occur from 13° C. to 19° C., so that the clothing article will only appear in the colored state when cooled by the effect of cold water. In another aspect, when worn on the body in a dry condition, the thermochromic pigment will not be color activated if it is at a temperature above the clearing point which is preferably from about 23° C. to 26° C. 
     With these parameters built into the thermochromic pigment, cold water below the full color point (activation temperature) is observed to produce a dramatic and immediate color change. Warmer water that cools the fabric via evaporation causes a delayed color change to occur over a period of about 1-3 minutes. The color development may take several minutes for the evaporative cooling process to cool the dyed fabric to its activation temperature. 
     Once the color is developed, the hysteresis effect or ‘memory’ in the thermochromic system permits the color development to persist until the fabric becomes dry. The wearer&#39;s body temperature accelerates the drying of the fabric. 
     The thermochromic shirts with this temperature profile have many uses. These may include, for example, exercise wear that changes color when the wearer sweats and then cools down causing evaporative cooling to occur. In another application, “water tag” is played with water guns just as paintball making it a safe and fun activity even for younger children. Safety equipment is not needed. 
     Artistic fashion wear may be painted with water. Multiple colors and images can be applied to the shirt via airbrushing, or the shirt may be tie-died to produce multiple colors when activated. 
     Promotional wear may be worn at water parks as swim wear or t shirts. Images or design changes will appear when the shirt becomes wet. 
     The thermochromic pigment is preferably mixed with a commercially available coating to achieve a desired color density and permanently affix the microencapsulated pigment to fabric. Coatings in the class of polyurethane binders are particularly preferred. This method of dying allows the fabric to possess extreme durability and withstand multiple washings without dramatic color loss. This dying process allows adhesion to natural fabrics like cotton, but also to synthetic fibers such as polyesters. The colors are bright and vivid when fully developed. 
     A variety of colors and color to color options are available from known leuco dye systems. Microencapsulated thermochromic pigments using these leuco dye systems may be used in combination with other dyes or pigments, such as fluorescent dyes or normal (nonfunctional) pigments or dyes. Thermochromically-driven color options include, for example; 
     Purple 
     Blue 
     Teal 
     Aqua 
     Red 
     Orange 
     Green 
     Black 
     Brown 
     Magenta 
     Orange to Yellow 
     Green to Yellow 
     Black to Orange, Green, or Pink 
     Purple to Pink 
     Red to Blue 
     Those skilled in the art will appreciate that what is shown and described herein may be subjected to insubstantial changes without departing from the true scope and spirit of the invention. Accordingly, the inventors state their intent to rely upon the Doctrine of Equivalents in protecting their full rights in the invention.