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WO2013192549A1 - Indicateur thermochromique de niveau - Google Patents

Indicateur thermochromique de niveau Download PDF

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Publication number
WO2013192549A1
WO2013192549A1 PCT/US2013/047108 US2013047108W WO2013192549A1 WO 2013192549 A1 WO2013192549 A1 WO 2013192549A1 US 2013047108 W US2013047108 W US 2013047108W WO 2013192549 A1 WO2013192549 A1 WO 2013192549A1
Authority
WO
WIPO (PCT)
Prior art keywords
thermochromic
housing
level
matter
ink
Prior art date
Application number
PCT/US2013/047108
Other languages
English (en)
Inventor
Terrill Scott CLAYTON
Timothy J. OWEN
Original Assignee
Chromatic Technologies Inc.
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Chromatic Technologies Inc. filed Critical Chromatic Technologies Inc.
Priority to EP13735507.9A priority Critical patent/EP2864740A1/fr
Publication of WO2013192549A1 publication Critical patent/WO2013192549A1/fr

Links

Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B65—CONVEYING; PACKING; STORING; HANDLING THIN OR FILAMENTARY MATERIAL
    • B65D—CONTAINERS FOR STORAGE OR TRANSPORT OF ARTICLES OR MATERIALS, e.g. BAGS, BARRELS, BOTTLES, BOXES, CANS, CARTONS, CRATES, DRUMS, JARS, TANKS, HOPPERS, FORWARDING CONTAINERS; ACCESSORIES, CLOSURES, OR FITTINGS THEREFOR; PACKAGING ELEMENTS; PACKAGES
    • B65D25/00—Details of other kinds or types of rigid or semi-rigid containers
    • B65D25/54—Inspection openings or windows
    • B65D25/56—Inspection openings or windows with means for indicating level of contents
    • A—HUMAN NECESSITIES
    • A47—FURNITURE; DOMESTIC ARTICLES OR APPLIANCES; COFFEE MILLS; SPICE MILLS; SUCTION CLEANERS IN GENERAL
    • A47G—HOUSEHOLD OR TABLE EQUIPMENT
    • A47G19/00—Table service
    • A47G19/22—Drinking vessels or saucers used for table service
    • A47G19/2205—Drinking glasses or vessels
    • A47G19/2227—Drinking glasses or vessels with means for amusing or giving information to the user
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01F—MEASURING VOLUME, VOLUME FLOW, MASS FLOW OR LIQUID LEVEL; METERING BY VOLUME
    • G01F23/00—Indicating or measuring liquid level or level of fluent solid material, e.g. indicating in terms of volume or indicating by means of an alarm
    • G01F23/0007—Indicating or measuring liquid level or level of fluent solid material, e.g. indicating in terms of volume or indicating by means of an alarm for discrete indicating and measuring
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01F—MEASURING VOLUME, VOLUME FLOW, MASS FLOW OR LIQUID LEVEL; METERING BY VOLUME
    • G01F23/00—Indicating or measuring liquid level or level of fluent solid material, e.g. indicating in terms of volume or indicating by means of an alarm
    • G01F23/22—Indicating or measuring liquid level or level of fluent solid material, e.g. indicating in terms of volume or indicating by means of an alarm by measuring physical variables, other than linear dimensions, pressure or weight, dependent on the level to be measured, e.g. by difference of heat transfer of steam or water
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01F—MEASURING VOLUME, VOLUME FLOW, MASS FLOW OR LIQUID LEVEL; METERING BY VOLUME
    • G01F23/00—Indicating or measuring liquid level or level of fluent solid material, e.g. indicating in terms of volume or indicating by means of an alarm
    • G01F23/22—Indicating or measuring liquid level or level of fluent solid material, e.g. indicating in terms of volume or indicating by means of an alarm by measuring physical variables, other than linear dimensions, pressure or weight, dependent on the level to be measured, e.g. by difference of heat transfer of steam or water
    • G01F23/24—Indicating or measuring liquid level or level of fluent solid material, e.g. indicating in terms of volume or indicating by means of an alarm by measuring physical variables, other than linear dimensions, pressure or weight, dependent on the level to be measured, e.g. by difference of heat transfer of steam or water by measuring variations of resistance of resistors due to contact with conductor fluid
    • G01F23/246—Indicating or measuring liquid level or level of fluent solid material, e.g. indicating in terms of volume or indicating by means of an alarm by measuring physical variables, other than linear dimensions, pressure or weight, dependent on the level to be measured, e.g. by difference of heat transfer of steam or water by measuring variations of resistance of resistors due to contact with conductor fluid thermal devices
    • G01F23/247—Indicating or measuring liquid level or level of fluent solid material, e.g. indicating in terms of volume or indicating by means of an alarm by measuring physical variables, other than linear dimensions, pressure or weight, dependent on the level to be measured, e.g. by difference of heat transfer of steam or water by measuring variations of resistance of resistors due to contact with conductor fluid thermal devices for discrete levels
    • G01F23/248—Constructional details; Mounting of probes
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B65—CONVEYING; PACKING; STORING; HANDLING THIN OR FILAMENTARY MATERIAL
    • B65D—CONTAINERS FOR STORAGE OR TRANSPORT OF ARTICLES OR MATERIALS, e.g. BAGS, BARRELS, BOTTLES, BOXES, CANS, CARTONS, CRATES, DRUMS, JARS, TANKS, HOPPERS, FORWARDING CONTAINERS; ACCESSORIES, CLOSURES, OR FITTINGS THEREFOR; PACKAGING ELEMENTS; PACKAGES
    • B65D2203/00—Decoration means, markings, information elements, contents indicators
    • B65D2203/04—Level indicators

Definitions

  • Thermochromic and photochromic encapsulated dyes undergo a color change over a specific temperature range.
  • a dye may change from a particular color at low temperature to colorless at a high temperature, such as red at 85°F and colorless at above 90°F.
  • the color change temperature is controllable, such that the color-change can take place at different temperatures.
  • the color change may occur at a temperature just below a person's external body temperature so that a color change occurs in response to a human touch.
  • thermochromic encapsulated dye results from selected materials and manufacturing processes.
  • One technique used to produce the thermochromic encapsulated dye is to combine water, dye, and oil, with melamine formaldehyde resin and agitate to create a very fine emulsification. Interfacial tensions are such that the oil and dye end up on the inside of a melamine formaldehyde capsule distributed in primarily the water phase. The melamine formaldehyde substance, while very hard and resistant to breakdown at high temperature, is permeable.
  • thermochromic inks may be purchased on commercial order, for example, from Chromatic Technologies, Inc. of Colorado Springs, Colorado.
  • thermochromic materials both state that thermochromic inks can be made with "conventional additives used to improve conventional printing inks.” Nonetheless, there are concerns over what additives may be added to these inks.
  • thermochromic pigments having a large molecular weight (i.e. greater than 100) generally are compatible with the thermochromic pigments.
  • the acid content of the formulation may also be adjusted to a value of less than 20 or adjusted to be neutral in the range from 6.5-7.5 pH. These adjustments allow the thermochromic dyes to be added to the formulation without a loss of its color change properties.
  • thermochromic dye is often sold in a slurry of encapsulated dye in a water base. It happens that the pH of this slurry is most often neutral in a range from 6.5 to 7.5. When thermochromic dye is added to a formulation that has a pH outside this range, the color change properties are often always lost. This is an irreversible effect and therefore, it is important to adjust the pH prior to adding the thermochromic dye.
  • the vehicle carries the pigment to the substrate and binds the pigment to the substrate.
  • the correct combination of vehicle ingredients will result in the wetting of an ink. This wetting means that the vehicle forms an absorbed film around the pigment particles.
  • the main ingredient in an ink is the binder. This may be a resin, lacquer or varnish or some other polymer.
  • the binder characteristics vary depending on the type of printing that is being done and the desired final product.
  • the second main ingredient is the colorant itself, for example, as described above.
  • the remaining ingredients are added to enhance the color and printing characteristics of the binder and the colorant. These remaining ingredients may include reducers (solvents), waxes, surfactant, thickeners, driers, and/or UV inhibitors.
  • scented inks may be produced using microcapsules to prolong the life of the scent. These scented inks do not use thermochromic materials and may be microencapsulated using an
  • microemulsion that contains a water soluble polymer selected from the group consisting of acrylic, styrenated maleic anhydride, sulfonated polyester, polyamide, and polyurethane or monomers thereof; (ii) a colorant; (iii) water and (iv) scented oil.
  • a water soluble polymer selected from the group consisting of acrylic, styrenated maleic anhydride, sulfonated polyester, polyamide, and polyurethane or monomers thereof.
  • Perfumes and other scented materials generally contain ketones and aldehydes that contribute significantly to the scent.
  • Diols such as glycerol
  • Lithography depends upon the separation of oil and water.
  • the oil is the ink and the water is the fountain solution.
  • the fountain solution is acidic to minimize the emulsification of ink.
  • the higher the pH the more scumming occurs; i.e. the movement of ink into areas of the image that are supposed to by free of ink.
  • the acid and other components in fountain solutions destroy the color change
  • thermochromic pigments exhibit characteristics of the thermochromic pigments.
  • thermochromic inks for metal decoration is an area of special concern. Most metal beverage cans made in the United States are
  • Aluminum cans may contain an internal coating to protect the aluminum from beverage corrosion. Chemical compounds used in the internal coating of the can include types of epoxy resin.
  • Beverage cans are usually filled before the top is crimped in place.
  • the filling and sealing operations are fast and precise.
  • the filling head centers over the can and discharges the beverage to flow down the sides of the can.
  • the lid is placed on the can then crimped in two operations.
  • a seaming head engages the lid from above while a seaming roller to the side curls the edge of the lid around the edge of the can body.
  • the head and roller spin the can in a complete circle to seal all the way around.
  • a pressure roller next drives the two edges together under pressure to make a gas-tight seal.
  • Filled cans usually have pressurized gas inside, which stiffens the filled cans for subsequent handling.
  • Aluminum cans may be produced through a mechanical cold forming process starting with punching a flat blank from very stiff cold-rolled sheet. This sheet is often made of a material called alloy 3104-H19 or 3004-H19. This material is aluminum with about 1% manganese and 1% magnesium for strength and formability.
  • a flat blank is first formed into a cup about three inches in diameter. This cup is then pushed through a forming process called "ironing" which forms the can. The bottom of the can is also shaped at this time. The malleable metal deforms into the shape of an open-top can.
  • Plain lids are stamped from a coil of aluminum, typically alloy 5182-H48, and transferred to another press that converts the stamped materials into easy-open ends.
  • the conversion press forms an integral rivet button in the lid and scores the opening, while concurrently forming the tabs in another die from a separate strip of aluminum.
  • the tab is pushed over the button, which is then flattened to form the rivet that attaches the tab to the lid.
  • the top rim of the can is trimmed and pressed inward or "necked" to form a taper conical where the can will later be filled and the lid (usually made of an aluminum alloy with magnesium) attached.
  • the lid components, especially the tabs, may be coated before they are subjected to such manufacturing processes as riveting.
  • Exterior surfaces of the cans may be coated with inks as shown, by way of example, in United States Patent 6,494,950.
  • Polyester resins are often favored for use on the sides of the cans.
  • Epoxy resins are favored for use on the lids, especially where there is a need for improved durability of the coatings.
  • Thermochromic inks may be used as indicators to assess when beverages have reached a particular temperature, such as when a soft drink or a beer is at a temperature that is particularly pleasing to the palate.
  • a particular temperature such as when a soft drink or a beer is at a temperature that is particularly pleasing to the palate.
  • a variety of polyester-based thermochromic inks are commercially available for coating the sides of the cans. Practically speaking, epoxy-based thermochromic inks are not widely available.
  • thermochromic coatings formed as level indicators overcomes the problems outlined above and advances the art by providing thermochromic coatings formed as level indicators.
  • a housing is provided with a thermochromic level indicator.
  • the housing mat be, for example, a beverage can or bottle.
  • the housing may also be a gas can, an oil container, a drum of chemicals, a fire extinguisher or other container for functional fluids.
  • the housing has a wall presenting an interior space capable of retaining matter at a first level within the wall.
  • the housing also has an opening or lid that may be opened to permit the matter to exit from within the wall or enter into the wall such that the matter assumes a second level.
  • the wall supports a level indicator, which is formed of thermochromic ink.
  • thermochromic ink has a color transition temperature capable of acting as a level indicator by sensing temperature of the matter retained within the wall in an intended environment of use as the matter transitions between the first level and the second level.
  • the matter may be a beverage and the wall forms at least part of a beverage container.
  • the level indicator may be printed as an indicia representing an image of an object.
  • the image may be, for example, that of a glass, a thermometer, a rainbow, or a vertically oriented line.
  • the level indicator may be printed directly onto the housing or a label that adheres to the housing.
  • the housing described above may be used in a method of sensing the level of matter within the housing. This is done by filling the housing with the matter to the first level, chilling the housing to a temperature exceeding a color transition temperature of the thermochromic ink, and removing matter from the housing to arrive at the second level in an environment such that the environmental temperature warms a portion of the thermochromic ink above the second level to a level above the color transition temperature. The color change may then be observed to assess an approximate level of the matter within the housing.
  • Thermochromic system A mixture of dyes, developers, solvents, and additives (encapsulated or non-encapsulated) that can undergo reversible color change in response to temperature changes.
  • thermochromic ink A mixture of dyes, developers, solvents, and additives (encapsulated or non-encapsulated) that can undergo reversible color change in response to temperature changes.
  • a thermochromic ink is an example of a thermochromic system.
  • Photochromic ink - A mixture of dyes, developers, solvents, and additives (encapsulated or non-encapsulated) that can undergo reversible color change in response to exposure to light of various wavelengths.
  • thermochromic system has achieved maximum color density upon cooling and appears to gain no further color density if cooled to a lower temperature.
  • Activation temperature The temperature above which a thermochromic system has almost achieved its final clear or light color end point. The color starts to fade at approximately 4 °C below the activation temperature and will be in between colors within the activation temperature range.
  • Clearing point The temperature at which the color of a thermochromic system is diminished to a minimal amount and appears to lose no further color density upon further heating.
  • Hysteresis The difference in the temperature profile of a thermo chromic system when heated from the system when cooled.
  • Hysteresis window The temperature difference in terms of degrees that a thermochromic system is shifted as measured between the derivative plot of chroma of a spectrophotometer reading between the cooling curve and the heating curve.
  • Leuco dye - A leuco dye is a dye whose molecules can acquire two forms, one of which is colorless.
  • Thermochromic inks useful on beverage containers and the like contain microcapsules, which encapsulate a thermochromic system mixed with a solvent.
  • the thermochromic system has a material property of a thermally conditional hysteresis window that presents a thermal separation.
  • These inks may be improved according to the instrumentalities described herein by using a co- solvent that is combined with the thermochromic system and selected from the group consisting of derivatives of mysristic acid, derivatives of behenyl acid, derivatives of palmytic acid and combinations thereof.
  • This material may be provided in an effective amount to reduce the thermal separation in the overall ink to a level less than eighty percent of separation that would otherwise occur if the material were not added. This effective amount may range, for example from the 12% to 15% by weight of the composition.
  • thermochromic system may contain, for example, at least one chromatic organic compound and co-solvents.
  • complexes form between the dye and the weak acid developer that allow the lactone ring structure of the leuco dye to be opened.
  • the nature of the complex is such that the hydroxyl groups of the phenolic developer interact with the open lactone ring structure forming a supra-molecular structure that orders the dyes and developers such that a color is formed. Color forms from this supra-molecular structure because the dye molecule in the ring open structure is cationic in nature and the molecule has extended conjugation allowing absorption in the visible spectrum thus producing a colored species. The color that is perceived by the eye is what visible light is not absorbed by the complex.
  • the nature of the dye/developer complex depends on the molar ratio of dye and developer.
  • the stability of the colored complex is determined by the affinity of the solvent for itself, the developer or the dye/developer complex. In a solid state, below the full color point, the dye/developer complex is stable. In the molten state, the solvent destabilizes the dye/developer complex and the equilibrium is more favorably shifted towards a developer/solvent complex. This happens at temperatures above the full color point because the dye/developer complex is disrupted and the extended conjugation of the ⁇ € cloud electrons that allow for the absorption of visible light are destroyed.
  • the melting and crystallization profile of the solvent system determines the nature of the thermochromic system.
  • the full color point of the system occurs when the maximum amount of dye is developed.
  • the dye/developer complex is favored where the dye and developer exist in a unique crystallized structure, often intercalating with one another to create an extended conjugated ⁇ € system.
  • the solvent(s) in excess, have enough kinetic energy to disrupt the stability of the dye/developer complex, and the thermochromic system becomes decolorized.
  • thermochromic pigments having specific color change performance as a function of temperature may be purchased on commercial order from such companies as Chromatic Technologies of Colorado Springs, Colorado. 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. 1A where the extent of color change presents a gap 100a that differs between color change that occurs upon heating 102 versus cooing 103. FIG. IB presents a relatively larger gap 100b.
  • thermochromic system does not depend only on temperature, but also on the thermal history, i.e. whether the particular 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 would allow 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.
  • FIG. 1A shows a thermal hysteresis curve for a thermochromic pigment.
  • FIG. IB shows a hysteresis curve for a comparable pigment.
  • FIG. 2 compares beverage cans that are coated with a
  • thermochromic coating according to the present disclosure and chilled to different temperatures.
  • FIG. 3 shows a beverage can that is printed with a thermochromic ink to provide an indicator showing an approximate liquid level inside the beverage can.
  • Thermochromic level indicators for use on beverage containers utilize take the principle that beverages which are chilled for serving thereafter warm to ambient temperature.
  • the thermodynamic principles of heat transfer are such that the container wall at a level below the liquid level as the beverage is cooler that the container wall above the liquid level.
  • beverage manufacturers frequently specify a preferred serving temperature for their products. For example, it is commonly believed that a lager-type of beer should be chilled to about 40 °F (4° C) or less. Ales (including also pale ales), ambers, and browns have relatively complex flavors that are more easily ascertained if the beverage is served at a slightly warmer temperature, especially 45°F - 55°F (7° C to 13° C). Concerning soft drinks, PepsiCo publishes information indicating that their products are preferably served at an ideal temperature of 42° F (7° C + 1.8° C), while Coca Cola ® is preferably served at 39° F (4° C).
  • thermochromic microcapsules As compared to thermochromic microcapsules, scented
  • thermochromic deactivating materials including short chain aldehydes, ketones, and diols. Nonetheless, these materials may permeate to exit the microcapsules and enter into thermochromic microcapsules where they may impair the performance of the thermochromic system in embodiments that combine thermochromic microcapsules with scented
  • thermochromic ink may contain some of thermochromic deactivating materials in the core material of scented microcapsules, these materials in combination should not make up more than about 30% total weight of the scented thermochromic ink.
  • Solvents for diluting the scenting agent in the core material may suitably include those having low reactivity, large molecular weight (i.e. over 100), and which are relatively non-polar.
  • One solvent that fits this category is cyclohexane, which has low toxicity and works well.
  • the acid value may also be considered.
  • the acid value is defined as the number of milligrams of a 0.1 N KOH solution required to neutralize the alkali reactive groups in 1 gram of material under the conditions of ASTM Test Method D- 1639-70.
  • High acid number substances have inactivated the thermochromic pigments. Generally, the lower the acid number the better.
  • Ink formulations with an acid value below 20 and not including the harmful solvents described above generally work well without deactivating the thermochromic system.
  • Some higher acid value formulations may be possible but generally it is best to use vehicle ingredients with low acid numbers or to adjust the acid value by adding a an alkali substance. The greatest benefit of a neutral or low acid value vehicle is increased shelf life.
  • Buffers may be used to minimize the effects of the fountain solution on pigment particles. This is one possible solution to the potential acidity problem of the varnishes.
  • One ingredient often used as a buffer is cream of tartar. A dispersion of cream of tartar and linseed oil can be incorporated into the ink. The net effect is that the pigments in the ink are protected from the acidic fountain solution.
  • Scented microcapsules i.e., those having a scenting agent with essentially no thermochromic system components, are less sensitive to acid content than are microcapsules that contain a thermochromic system.
  • the component that contains the scented microcapsules preferably should not cause the mixture pH to fall outside the range of 6.5 to 7.5.
  • the pH adjustment may be performed as needed using a proton donor or acceptor, depending on whether the pH must be adjusted up or down. For example, HCl is used to lower the pH. KOH may be used to lower the pH. While pH tolerance sometimes exists in an expanded range between 6.0 and 8.0. A pH below 6.0 and above 8.0 almost always immediately destroys the thermochromic system in an irreversible manner.
  • thermochromic inks are sold in two ways: 1) as a dry powder and 2) in a water based slurry. Conventional mixing systems exists for both slurry and powder that will allow for consistent and well dispersed pigment, and these may be purchased on commercial order.
  • the aqueous slurry can be used to make solvent-based ink formulations by first drying the slurry.
  • traditional ink manufacturing there is a technique known as flushing.
  • Many traditional pigments come in slurry form, similar to that of the thermochromic capsules.
  • “Flushing” in traditional manufacturing means to press most of the water out of the slurry to form what is called a press cake which is then "flushed” into a mixing varnish.
  • the press cake is about 25-40% solids.
  • the pigment Because of the hydrophobic properties of the pigment and the varnish, the pigment is mixed into the varnish and away from the water. The water separates from the varnish and is left behind. Flushing with the thermochromic capsules does not work. All of the water stays in the varnish rather than separating.
  • Microcapsules that have been dried all the way to the consistency of powder are difficult to disperse.
  • the microcapsules tend to aggregate. Too much physical agitation by stirring may damage or denature the dye.
  • the problem may be addressed by adding a solvent to the powder to achieve at least about 50% solids content. Once the solvent and the powder are combined, the container with the mixture is submerged in an ultrasound bath. The vibration breaks up the aggregates and conditions the capsules for addition of the remainder of the vehicle ingredients.
  • the technique is essentially that of adding pigment to different media to attain a desired result; that of mimicking the visual appearance of normal pigments while trying to add the dimension of thermal activity to its properties.
  • the pigment itself is ground into the base. This disperses the pigment throughout the base. The eye cannot see particles that size, so the pigment will give the base a solid color. The addition of more pigment simply intensifies the color. Since the pigment has a very intense color only about 10% of the final ink is made up of normal pigments. Also, the normal pigment itself is relatively impervious to the effects of solvent and pH.
  • thermochromic dyes Although they have used thermochromic dyes, however, these attempts have focused simply on the addition of thermochromic capsules to an ink base at random and observing whether or not the capsules maintain their original color- changing properties.
  • thermochromic dyes in general, the present disclosure teaches the following procedure for making formulations with thermochromic dyes. If in slurry form, and is intended for addition to a water base ink, the water is removed to give slurry between 80% and 95% solids. This is then mixed with an appropriate ink vehicle.
  • a base for an ink is developed using off the shelf ingredients.
  • the ink will incorporate, where possible, and compatible with the ink types, solvents with molecular weights larger than 100 and avoid all aldehydes, diols, and ketones, and aromatic compounds. Selection of the ingredients is critical. The important considerations with respect to the ingredients within the ink vehicle deal with the reactivity of these ingredients with the thermochromic capsule and its contents.
  • Ketones, diols, and aldehyde content is minimized, as well as most mineral spirits, excluding cyclohexane and other chemically similar compounds. Ammonia, and other highly reactive compounds are also avoided. The lower the amounts of these compounds, the better the performance of the thermochromic and the longer the shelf life of the product.
  • Cyclohexane is effective for the purposes of dispersion of the dry thermochromic powder, or for the cleaning of the press in preparation for printing the thermochromic ink. There are however several other possible options for cleaning or as reducers within the ink itself that will also be effective.
  • the pH or acid value of the ink base is adjusted before the pigment is added. This can be done by ensuring that each individual component of the base is at the correct pH or acid value or by simply adding a proton donor or proton acceptor to the base itself prior to adding the pigment.
  • the appropriate specific pH is generally neutral, or 7.0. The pH will vary between 6.0 and 8.0 depending on the ink type and the color and batch of the pigment.
  • the slurry and the base have been properly prepared, they are combined.
  • the method of stirring should be low speed with non-metal stir blades. Other additives may be incorporated to keep the pigment suspended.
  • the ink should be stored at room temperature.
  • thermochromic systems undergo a color change from a specific color to colorless (i.e. clear). Therefore, layers of background colors can be provided under thermochromic layers that will only be seen when the thermochromic layer changes to colorless. If an undercoat of yellow is applied to the substrate and then a layer containing blue thermochromic dye is applied the color will appear to change from green to yellow, when what is really happening is that the blue is changing to colorless. Just about any color may be achieved by these mixtures.
  • All substrates that are made-ready to receive the ink should be approximately neutral in pH, and should not impart any chemicals to the capsule that will have a deleterious effect on it.
  • Many types of paper have relatively low pH that could impact the thermochromic capsules. Low pH could cause serious deterioration in a matter of weeks. If quality control is to be maintained, this aspect of the chemistry should be taken into consideration. Use neutral paper whenever possible.
  • Other substrates may include metal, such as aluminum or steel, glass, plastic, fabric, wood, and other substrates.
  • thermochromic dye formulations are provided below using the principles and techniques taught above. These embodiments teach by way of specific example, and not by limitation.
  • Ink embodiments for may contain, in combination, a conventional vehicle, scented microcapsules, and thermochromic microcapsules.
  • thermochromic microcapsules are preferably present in an amount ranging from 1% to 30% of the coating by weight on a sliding scale. This means that there may be from 1% to 30% if the thermochromic microcapsules and from 30% to 1% of the scented microcapsules.
  • the vehicle contains a solvent is preferably present in an amount ranging from 25% to 75% by weight of the coating, and is most preferably about 50% by weight.
  • the solvent is most preferably xylene.
  • Step A Preparation of encapsulation core material (mixture): A mixture comprising 75% of a mint fragrance (X-7028, manufactured by Takasago International Corporation, this also applies to all subsequent references to mint) and 25% of palmitic acid (melting point: 63° C) is stirred at 70°C, thereby dissolving the palmitic acid in the fragrance.
  • the melting point range (T1-T2) for the resulting mixture is from 5 to 45° C (confirmed visually). The mixture is held at 55°C to prevent it solidifying prior to emulsification.
  • Step B Preparation of emulsion accelerator liquid: 15% of ethylene maleic anhydride resin (Scripset-520, manufactured by Monsanto Company) and 85% of water are mixed together at 60°C, and the mixture is adjusted to pH 4 using acetic acid.
  • ethylene maleic anhydride resin Scripset-520, manufactured by Monsanto Company
  • Step C Preparation of aqueous solution of melamine resin prepolymer: 15% of a melamine-formaldehyde resin (Sumirez Resin 615K, manufactured by Sumitomo Chemical Co., Ltd.) is dissolved in 85% of water at 60° C.
  • a melamine-formaldehyde resin Sudirez Resin 615K, manufactured by Sumitomo Chemical Co., Ltd.
  • Step D Capsulation 100 parts of the above emulsion accelerator liquid from Step B is stirred at 60°C. at 3,000 rpm using a TK Homomixer Mark II 20 (manufactured by Tokushu Kika Kogyo Co., Ltd.), 100 parts of the above
  • encapsulation material from Step A is added and emulsified, the rotational speed is then gradually raised, and stirring is conducted at 7,000 rpm for 30 minutes, yielding an emulsion in which the average particle size of the oil droplets of the encapsulation material is approximately 3 ⁇ (as measured by a laser diffraction particle size analyzer SALD-3100 (manufactured by Shimadzu Corporation). This analyzer is also used to measure all subsequent particle sizes.
  • An encapsulation material (A) is prepared by mixing 75% of the mint fragrance and 25% of behenyl alcohol (melting point: 70° C) at 75° C, thereby dissolving the behenyl alcohol in the fragrance and forming a mixture.
  • the melting point range for the thus obtained mixture is from 10 to 50° C.
  • the mixture is held at 60° C to prevent it FROM solidifying prior to emulsification.
  • An encapsulation material (A) is prepared by mixing 65% of the mint fragrance and 35% of paraffin wax (EMW-0003, manufactured by Nippon Seiro Co., Ltd., melting point: 50° C) at 60°C, thereby dissolving the paraffin wax in the fragrance and forming a mixture.
  • the melting point range for the thus obtained mixture is from 0 to 40° C.
  • the mixture is held at 50°C to prevent it solidifying prior to emulsification.
  • a urea resin monomer (reagent grade, manufactured by Nissan Chemical Industries, Ltd.), 2% of a resorcin resin monomer (reagent grade, manufactured by Mitsui Chemicals, Inc.), and 3% of an ethylene maleic anhydride resin (Scripset-520, manufactured by Monsanto Company) are dissolved in 85% of water, and the solution is adjusted to pH 3 using acetic acid.
  • a urea resin monomer (reagent grade, manufactured by Nissan Chemical Industries, Ltd.)
  • a resorcin resin monomer (reagent grade, manufactured by Mitsui Chemicals, Inc.)
  • an ethylene maleic anhydride resin (Scripset-520, manufactured by Monsanto Company)
  • Offset Ink Base is combined with other ink components to produce a Quick-Set lithographic ink as follows:
  • This material is produced in any one of Examples 1, 2, 3 or 4.
  • a finely divided microcrystalline wax, polyethylene wax, Fisher- Tropsch wax, either alone or in combination with a finely divided polytetrafluorethylene polymer is added to the ink to improve the dry rub resistance of the dried ink film.
  • Additions of dry wax may be made from 0.5% to 3.0%.
  • Additions of compounded waxes may be from 1.5% to 10%, depending on the wax compound used should not exceed 15.
  • Offset Ink Base is combined with other ink components to produce a hard drying, high solids ink as follows:
  • An ink or coating may be applied to aluminum to make a beverage can with both scent and thermochromic attributes.
  • the coating may be applied using conventional metal decorating equipment.
  • the coating can be applied to any part of a can including the base or bottom, the side walls, neck, top surface, and the pull tab.
  • the vehicle can be waterbased, solvent based, ultraviolet or radiation curable, heatset, two part epoxy, or one part epoxy but is not limited to these examples.
  • the coating may also be prepared by using one epoxy coating for metal decorating, such as those sold by companies like Valspar or Watson Coatings.
  • Thermochromic pigment loading is preferably between 1% and 30%, and most preferably is about 15%.
  • the aluminum stock may be roller coated, dipped, spray coated, or printed.
  • the coating is prepared by adding a thermochromic to the vehicle or to a component in the finished vehicle.
  • the thermochromic pigment may be dry or may contain between 0-50% moisture.
  • the coating may be ready to use or be mixed with solvent, known by those skilled in the art, to a specific viscosity prior to use. It is preferable that the thermochromic microencapsulated pigment have adequate solvent resistance.
  • the thermochromic microencapsulated pigment may be introduced to the vehicle using any mixer known to the art.
  • the coating may be made in a batch process or in a continuous process.
  • FIG. 2 compares identical beverage cans 200, 300, which differ in that can 200 is a room temperature and can 300 is chilled. Lids 202, 302 are coated with epoxy-based thermochromic coatings 204, 304. As shown in FIG. 2, the relative darkness of lid 302 indicates that the beverage is sufficiently chilled to a
  • the lid 302 may optionally contain scented microcapsules to complement the beverage by imparting, for example, a cherry scent or a citrus scent.
  • the lids 202, 302 contain tabs that may be pulled to open access to space within the interior walls of cans 200, 300, such that liquid or other matter may be poured into or out of the cans 200, 300.
  • thermochromic ink it is possible to coat just the tab 206, 306s, or both the lids 202, 302 and the tabs 206, 306.
  • thermochromic pigment may be as prepared in any of Examples 1, 2, 3 or 4. If scent is not desired, this material may be eliminated and the thermochromic pigment increased to 30%.
  • thermochromic pigment may be as prepared in any of Examples 1, 2, 3 or 4. . If scent is not desired, this material may be eliminated and the thermochromic pigment increased to 30%. [0083] This coating may be cut with xylene (1 : 1) to a desired viscosity, applied using a roller coater, and baked for 5-18 seconds at 400°F.
  • FIG. 3 shows a beverage can 300 that contains an image 308 of a glass that is partially- full of beer.
  • the image 308 is for example printed with a thermochromic ink, as described above, to provide a color change interface zone 310 corresponding to the approximate level of beer inside can 300.
  • the image 308 is optionally but preferably provided with lime-scented microcapsules, such that the scent complements the organoleptic qualities of the beverage.
  • the image 308 is provided with a number of features that sense and inform a beverage drinker of the thermal quality of the beverage.
  • the coating in region 312 has, for example, a yellow color phase (or any other color) when chilled to less than a full color point.
  • This full color point may be associated by design with an intended temperature for the beverage. This may be, for example, a temperature according to a manufacturer's recommendation or a temperature of an average refrigerator. This may be any temperature ranging from 32° F to 55° F (0° C to 13°C) or any other temperature that is perceptibly cooler than normal room temperature in the intended environment of use.
  • region 310 resides above a liquid level 311 and is warmed by ambient room temperature to an activation temperature that causes the color of image 308 to fade on a gradient from the interface level 311 towards region 314.
  • Region 344 has transitioned upon warming to a clearing point temperature.
  • the entire image 308 may be printed over a contrasting color background, such as a white background or a contrasting background of any other color, indicating that no beer is present.
  • thermochromic pigments may be adjusted by expert formulation upon commercial order to decrease the length or span of region 310 from the interface 311 towards region 314. This may be done, for example, by reducing the separate with across the hysteresis window, as well as by making a sharper (more vertical) warming curve, such that the span reflects a total temperature change of less than two or three degrees centigrade.
  • a "BEER ME!” message 316 is printed from two different inks each having approximately the same color transition temperature, which here is referred to as the second color transition temperature.
  • the message 316 is normally hidden from view, matching the color of a background 318.
  • a predetermined value such as 10°C above the manufacturer's recommended serving temperature
  • the message 316 becomes visible to indicate that the beverage has warmed to a temperature where the organoleptic qualities of the beverage are less than optimal or may even begin to degrade.
  • This predetermined value preferably differs from the clearing point of the image 308 by having a higher value.
  • the sensed level indicator of interface 311 may more accurately depict a true liquid level with less regard for the organoleptic qualities of the beverage itself, while the message 316 is indicates poor thermal quality of the beverage.
  • thermochromic level indicator may be expanded to encompass any container or package (collectively a housing) that holds a liquid or other matter that may be sensed by a thermal difference, such as ice.
  • the concept extends also to a label that is placed on such containers or packages.
  • the level indicator may be placed on a bottle, jug, keg, bag, box, glass, aluminum two piece can, three piece can, pressure sensitive label, destructible label, or any other item that may bear a label indicator.
  • Package contents for such items may include, for example: liquid beverages including water, soda, or alcohol; or functional fluids such as hydraulic fluids, lubricants, paints, or fire suppressants.
  • the level indicator may be applied using ink that is adapted to particular processes, such as offset ink, metal decorating ink, flood coating, screen print, sheetfed ink, paint, gravure, inkjet, or spray paint.
  • the ink may be applied to a label that is adhered to a container or package, or the ink may be applied directly onto the container or package.
  • the ink for these processes may be formulated as heatset ink, solvent based ink, uv curable ink, epoxy ink, waterbased ink, or any other form of thermochromic ink.
  • the thermochromic microcapsules may be formulated as urea- formaldehyde, melamine formaldehyde, protein, gelatin, or any other type of microcapsule. Specially formulated thermochromic inks having selected color transition temperatures across a wide range of color transition temperatures may be purchased on commercial order from Chromatic Technologies, Inc. of Colorado Springs, Colorado.
  • the indicator may assume any form of artwork.
  • the level indicator may be as simple as a vertical line.
  • the level indicator may also assume a representation of a particular object, such as a thermometer, the image of a glass as described above, a rainbow, or the entire outer coating of the can 300.
  • the level indicator may be printed directly onto the housing or a label that adheres to the housing.
  • the level indicator may be used by filling the can or other housing with the matter to the first level, chilling the can to a temperature exceeding a color transition temperature of the thermochromic ink, and removing matter from the can to arrive at the second level in an environment such that the environmental temperature warms a portion of the thermochromic ink above the second level to a level above the color transition temperature. The color change may then be observed to assess an approximate level of the matter within the can.
  • the foregoing embodiments may be altered in various ways.
  • the pigment may be entirely eliminated to make an overprint varnish.
  • thermochromic inks may be provided with a color transition temperature such that they change color when scratched.

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  • Physics & Mathematics (AREA)
  • Fluid Mechanics (AREA)
  • General Physics & Mathematics (AREA)
  • Thermal Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Mechanical Engineering (AREA)
  • Inks, Pencil-Leads, Or Crayons (AREA)

Abstract

L'invention concerne un boîtier (300) pourvu d'un indicateur thermochromique de niveau (308). Le boîtier peut être, par exemple, une canette ou une bouteille. Le boîtier possède une cloison présentant un espace intérieur susceptible de retenir la matière à un premier niveau dans la cloison. Le boîtier possède également une ouverture ou un couvercle qui peut être ouvert de manière à permettre à la matière de sortir de l'intérieur de la cloison ou de pénétrer à l'intérieur de la cloison de manière à ce que la matière atteigne un second niveau (311). La cloison supporte un indicateur de niveau (308), qui est formé d'encre thermochromique. L'encre thermochromique présente une température de transition de couleur susceptible d'agir comme un indicateur de niveau en détectant la température de la matière retenue à l'intérieur de la cloison dans l'environnement d'utilisation prévu lorsque la matière effectue la transition entre le premier niveau et le second niveau. Par exemple, la matière peut être une boisson et la cloison forme au moins une partie d'un contenant de boisson.
PCT/US2013/047108 2012-06-22 2013-06-21 Indicateur thermochromique de niveau WO2013192549A1 (fr)

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US61/663,089 2012-06-22

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