Patent Application
20090278090
The present invention relates to thermochromic compounds, inks, compositions and methods thereof.
Maintaining proper handling and storage temperature of food products is an important aspect of food safety. At a recent symposium sponsored by the Food Safety and Inspection Service (FSIS) of the U.S. Department of Agriculture it was disclosed that 76 million Americans reported having a food borne illness each year. In addition, 1 in 1000 people are hospitalized each year with food borne illnesses. These health problems result in over $6.5 Billon in medical expenses. Of the over 2,700 cases reported to the Centers for Disease Control (CDC) between 1993 and 1997, 73% were the result of improper holding conditions of the food products. Therefore, there is a need to develop an easily integrated, computer monitored, low-cost, track and trace temperature monitoring system for food products.
Thermochromic material has been used in time-temperature indicators (TTIs). Currently available time-temperature indicators are derived from one of three types of materials: the time-dependent diffusion of dyed fatty esters through porous material; controlled enzymatic hydrolysis of lipids; and solid state polymerization of uncolored acetylenic monomers that produce highly colored polymers. These TTIs are designed as visually retrievable sensors of the shelf life of products, and provide a good correlation to microbial growth. However, the cost of TTIs is high and there is no automated method to track and trace standard TTIs. The colorants currently utilized in TTIs require macro-encapsulation and can not be readily incorporated into standard ink formulations for TTI. Thus, it would be prohibitively expensive and inconvenient to create a TTIs, which may be bar codes or other indicia, using existing technology.
Development of pigments which can be used in TTI (e.g. bar codes) allows for the creation of an inexpensive and computer verified track and trace system that continuously monitors the temperature of food products. At any point during storage, transport, or distribution of food products the TTI can be scanned to determine that proper holding temperatures have been maintained. Improper storage temperatures will be indicated by a change in the TTI allowing the product to be removed from the food chain to protect the consumer.
Currently available low temperature thermochromic inks are reversible thermochromic inks and cannot be used to continuously and reliably monitor food products in the cold chain during transportation and storage. A reversible thermochromic ink will change color from a first color to a second color when the temperature of the ink meets or exceeds a transition temperature. However, when the ink is cooled from a temperature at or above the transition temperature to below the transition temperature, the ink will change from the second color to the first color. A TTI derived from a reversible thermochromic ink can detect a food product that is presently at or above the transition temperature of the reversible thermochromic ink, but cannot detect a food product that has met or exceeded the transition temperature in the past while it is currently below the transition temperature. Therefore, reversible low temperature thermochromic inks cannot be used to continuously and reliably monitor food products in the cold chain, and there is a need for irreversible low temperature thermochromic ink that can be used in a thermally sensitive TTI to monitor individual food packages in the cold chain during transportation and storage.
One embodiment provides a polythiophene compound that has the chemical structure:
including stereoisomers thereof, wherein:
each R1 of each monomer is independently selected from the group consisting of H, alkyl radical and alkoxyl radical; each R2 and R3 of each monomer is independently selected from the group consisting of alkyl radical and alkoxyl radical; each n of each monomer is an integer selected independently; and p is 2-1000.
In certain embodiments, the polythiophene compound is an irreversible upon activation (IUA) thermochromic compound.
In another aspect, a composition comprising a compound having Structure I is an irreversible upon activation (IUA) thermochromic composition.
In certain embodiments, an IUA thermochromic composition has an irreversible thermochromic transition temperature (IRTTT) between about −30° C. to about 60° C.
Another aspect relates to an IUA thermochromic indicator comprising an IUA thermochromic component prepared using an IUA thermochromic composition, wherein the deactivation of the activated IUA thermochromic composition is detectable.
Another aspect relates to a method of preparing an activated IUA thermochromic composition comprising: converting the IUA thermochromic composition to a high temperature state of the IUA thermochromic composition; and cooling the IUA thermochromic composition from the high temperature state to a cooling temperature in a cooling time.
In certain embodiments, an IUA thermochromic composition is converted to a high temperature state by exposure to high radiant energy (e.g. UV light).
An IUA thermochromic composition may also be converted to a high temperature state by being heated to a heating temperature for a time sufficient to display a high temperature color. In certain embodiments, a heating temperature is at or above a RTTT of an IUA thermochromic composition. In certain embodiments, a heating temperature is 20° C. below a RTTT of an IUA thermochromic composition.
In certain embodiments, a cooling temperature is about 5-20° C. below an IRTTT of an IUA thermochromic composition. In certain embodiments, a cooling temperature is more than 20° C. below an IRTTT of an IUA thermochromic composition. In certain embodiments, a cooling temperature is more than 30° C. below an IRTTT of an IUA thermochromic composition. In certain embodiments, a cooling time is in less than about 2 seconds. A cooling time may also be less than about 1 second.
In certain embodiments, an IUA thermochromic indicator may be made by a method comprising an IUA thermochromic component prepared using an IUA thermochromic composition comprising applying the IUA thermochromic composition to an article in a certain pattern and activating the IUA thermochromic composition, wherein the certain pattern is designed to show deactivation of the activated IUA thermochromic composition.
Another aspect relates to monitoring subjects stored in the absence of a pre-determined condition comprising applying an activated IUA thermochromic indicator to the subjects and detecting the deactivated IUA thermochromic indicator of the subjects which are or have been exposed to the pre-determined condition.
In certain embodiments, a pre-determined condition is a temperature-related pre-determined condition. In certain embodiments, a temperature-related pre-determined condition is exposure to a pre-determined temperature for a pre-determined time period.
A novel polythiophene compound has the following Structure I:
including stereoisomers thereof.
As used herein, unless otherwise specified, each R1 of each monomer is independently selected from the group consisting of H, alkyl radical and alkoxyl radical;
each R2 of each monomer is independently selected from the group consisting of alkyl radical and alkoxyl radical;
each R3 of each monomer is independently selected from the group consisting of alkyl radical and alkoxyl radical;
each n of each monomer of a polythiophene is an integer selected independently; and
p is an integer.
In certain embodiments, n is selected from 0 to 100; in certain embodiments, n is selected from 0 to 15; in certain embodiments, n is selected from 0 to 6; in certain embodiments, n is selected from 1 to 15; in certain embodiments, n is selected from 1 to 6. In certain embodiments, p is 1-1000; in certain embodiments, p is 2-1000; in certain embodiments, p is 1-500; in certain embodiments, p is 2-500; in certain embodiments, p is 1-100; in certain embodiments, p is 2-100; in certain embodiments, p is 10-100.
As used herein, the term “alkyl radical” means a branched or unbranched, saturated or unsaturated, monovalent or multivalent hydrocarbon group. Examples of alkyl include, but are not limited to, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, t-butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, ethenyl, propenyl, butenyl, isobutenyl, pentenyl, hexenyl, heptenyl, octenyl, nonenyl, decenyl, undecenyl, dodecenyl, ethynyl, propynyl, butynyl, isobutynyl, pentynyl, hexynyl, heptynyl, octynyl, nonynyl, decynyl, undecynyl, dodecynyl, methylene, ethylene, propylene, isopropylene, butylene, isobutylene, t-butylene, pentylene, hexylene, heptylene, octylene, nonylene, decylene, undecylene and dodecylene. In certain embodiments, the hydrocarbon group contains 1 to 20 carbons. In certain embodiments, the hydrocarbon group contains 1 to 30 carbons. In certain embodiments, the hydrocarbon group contains 3 to 50 carbons.
As used herein, unless specified otherwise, the term “alkoxyl” means an alkyl, cycloalkyl or heterocycloalkyl, which further contains one or more oxygen atoms. Examples of alkoxyl include, but are not limited to, —CH2—OH, —OCH3, —O-alkyl, -alkyl-OH, -alkyl-O-alkyl-, wherein the two alkyls can be the same or different.
As used herein, unless specified otherwise, the term “cycloalkyl” means an alkyl which contains at least one ring and no aromatic rings. Examples of cycloalkyl include, but are not limited to, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclononyl, cyclodecyl, cycloundecyl and cyclododecyl. In certain embodiments, the hydrocarbon chain contains 3 to 20 carbons. In certain embodiments, the hydrocarbon group contains 3 to 30 carbons.
As used herein, unless specified otherwise, the term “heterocycloalkyl” means a cycloalkyl wherein at least one ring atom is a non-carbon atom. Examples of the non-carbon ring atom include, but are not limited to, S, O and N.
In certain embodiments, a polythiophene compound has Structure I, including stereoisomers thereof, wherein R1 is the same for each monomer and R2 is the same for each monomer. In certain embodiments, R1 is an alkyl radical containing 1 to 12 carbons. In certain embodiments, R1 is methyl.
In certain embodiments, a polythiophene compound is a poly(3-methyl-4-polyoxyethylenealkylether)thiophenes (PMOET) having Structure II
including stereoisomers thereof, wherein:
each m of each monomer of the polythiophene compound is an independently selected integer; the average of m of all monomers (“m”) is 7 to 21;
each n of each monomer of the polythiophene compound is an independently selected integer; the average of n of all monomers (“n”) is 0 to 6;
3n+m+1 is 20 to 40; a
p is an independently selected integer.
In certain embodiments, a polythiophene compound has Structure II, including stereoisomers thereof, wherein m is 17 and the average of n is 2 (“PMOE-2-SET”), and the corresponding monomer is MOE-2-SET.
In certain embodiments, a polythiophene compound has Structure II, including stereoisomers thereof, wherein m is 11 and the average of n is 4 (“PMOE-4-LET”), and the corresponding monomer is MOE-4-LET.
In certain embodiments, a polythiophene compound has Structure II, including stereoisomers thereof, wherein the monomers are a mixture of MOE-2-SET (m is 17 and the average of n is 2) and MOE-4-LET (m is 11 and the average of n is 4).
Another aspect of the invention relates to a polythiophene composition comprising a polythiophene compound having Structure I, Structure II, or a plural or a mixture thereof.
In certain embodiments, a polythiophene composition has Structure II, including stereoisomers thereof, wherein the monomers of all polymers contain 50% MOE-2-SET and 50% MOE-4-LET (Copolymer-1). In certain embodiments, a polythiophene composition has Structure II, including stereoisomers thereof, wherein the monomers of all polymers contain 75% MOE-2-SET and 25% MOE-4-LET (Copolymer-2). In certain embodiments, a polythiophene composition has Structure II, including stereoisomers thereof, wherein the monomers of all polymers contain 25% MOE-2-SET and 75% MOE-4-LET (Copolymer-3).
In certain embodiments, a polythiophene composition of the invention comprises a carrier medium and a polythiophene compound having Structure I, Structure II, or a plural or a mixture thereof. A concentration of the polythiophene compound(s) in the polythiophene composition is from about 0.05% to about 99.5% by weight. In certain embodiments, the concentration of polythiophene compound(s) in a polythiophene composition is from 0.05% to 25% by weight. In certain embodiments, the concentration of polythiophene compound(s) in a polythiophene composition is from 0.05% to 5% by weight. In certain embodiments, the concentration of polythiophene compound(s) in a polythiophene composition is 10% by weight.
As used herein, the term “carrier medium” means a material, composition or a formula, such as liquid or solid solvent, diluent. Examples of carrier medium include, without limitation, polyurethanes; elastomers including polysiloxanes and polydienes; polyacrylates, poly(ethylene terephthalate)s (PET), polystyrenes, polyolefins including polyethylenes (HDPE and LDPE) and polypropylene, polycarbonates, polyacrylics, polyacrylic acids, polyacrylamides, polymethacrylics, polyvinyl ethers, polyvinyl halides, poly(vinyl nitrile)s, polyvinyl esters, polyesters, polysofones, polysulfonamides, polyamides, polyimines, polyimides, and carbohydrates.
In certain embodiments, a carrier medium comprises an ink formulation, wherein the ink formulation comprises oils, resins, pigment extenders and additives.
In certain embodiments, a polythiophene composition of the invention is an irreversible upon activation (IUA) thermochromic composition.
As used herein, the term “thermochromic” means the ability of a composition to change color due to a change of temperature.
In certain embodiments, a polythiophene composition of the invention has a reversible thermochromic transition temperature (RTTT) determined by variable temperature reflection spectra, wherein the center of the sigmoid transition curve of the variable temperature spectra is the RTTT. The thermochromic transition is reversible. The polythiophene composition also has a low reversible thermochromic transition temperature (RTTTL) determined by variable temperature reflection spectra, wherein the temperature at which the reversible thermochromic transition starts is the RTTTL. The composition has a high temperature state and a low temperature state. At a temperature below the RTTTL, the composition shows a low temperature color and is at a low temperature state. When the composition is heated to or above the RTTTL, the composition shows a high temperature color and is at a high temperature state. This temperature-dependent color change is reversible because when the high temperature color composition is cooled to a temperature below the RTTTL, the composition color will change back to the low temperature color.
In certain embodiments, a polythiophene composition has a high temperature color of yellow. In certain embodiments, a polythiophene composition has a low temperature color of burgundy or violet.
In certain embodiments, a RTTTL is about 0.5-40° C. below the RTTT. In certain embodiments, a RTTTL is about 5-20° C. below the RTTT. In certain embodiments, a RTTTL is about 5-10° C. below the RTTT. In certain embodiments, a RTTTL is about 0.5-5° C. below the RTTT.
In certain embodiments, a polythiophene composition of the invention has an irreversible thermochromic transition temperature (IRTTT) determined by variable temperature reflection spectra, wherein the center of a sigmoid transition curve of the variable temperature spectra is the IRTTT. The thermochromic transition is irreversible. The polythiophene composition also has a low irreversible thermochromic transition temperature (IRTTTL) determined by variable temperature reflection spectra, wherein the temperature at which the reversible thermochromic transition starts is the IRTTTL. Such a composition is also referred to as an irreversible upon activation (IUA) thermochromic composition. In certain embodiments, an IRTTTL is about 0.5-40° C. below the IRTTT. In certain embodiments, an IRTTTL is about 5-20° C. below the IRTTT. In certain embodiments, an IRTTTL is about 5-10° C. below the IRTTT. In certain embodiments, an IRTTTL is at about 0.5-5° C. below the IRTTT.
As used herein, an IUA thermochromic composition has a RTTT, a RTTTL, a high temperature state and color, and a low temperature state and color as defined supra. The IUA thermochromic composition further has an IRTTT, an IRTTTL and a metastable state (activated state) and shows an IUA color at the activated state. Both the low temperature state and the high temperature state are referred to as deactivated states, the low temperature state is a deactivated low state and the high temperature state is a deactivated high state. In certain embodiments, an IUA thermochromic composition has a high temperature color of yellow. In certain embodiments, an IUA thermochromic composition has a low temperature color burgundy or violet. In certain embodiments, an IUA thermochromic has an IUA color of pink or orange.
The process by which an IUA thermochromic composition is converted from a deactivated state to an activated state is called “activation.” An IUA thermochromic composition at an activated state is called an “activated” IUA thermochromic composition. In certain embodiments, an IUA thermochromic composition is activated by converting the IUA thermochromic composition to a high temperature state and then cooling the IUA thermochromic composition rapidly enough to an activated state. An activated IUA thermochromic composition will retain an IUA color as long as the composition is kept below an IRTTT.
The process by which an IUA thermochromic composition is converted from an activated state to a deactivated state is called deactivation. An IUA thermochromic composition at a deactivated state is called a “deactivated” IUA thermochromic composition. An activated IUA thermochromic composition will be deactivated and change color from an IUA color to a low temperature color when the IUA thermochromic composition is heated to or above an IRTTTL but below a RTTTL. The deactivated IUA thermochromic composition is now at a deactivated low state. This temperature-dependent color change is irreversible because when the deactivated IUA thermochromic composition is cooled from the deactivated low state to or below the IRTTTL, the IUA thermochromic composition will retain the low temperature color, remain deactivated and will not change back to the IUA color. An activated IUA thermochromic composition will be deactivated and change color from an IUA color to a high temperature color when the composition is heated to or above a RTTTL. The IUA thermochromic composition is now at a deactivated high state. This temperature-dependent color change is also irreversible when the deactivated IUA thermochromic composition is cooled from the deactivated high state to or below the IRTTTL without re-activating the IUA thermochromic composition. The IUA thermochromic composition will change to the low temperature color, remain deactivated and will not change back to the IUA color.
In certain embodiments, an IUA thermochromic composition has an IRTTT between about −30° C. to about 60° C. In certain embodiments, an IUA thermochromic composition has an IRTTT between about −20° C. to about 20° C. In certain embodiments, an IUA thermochromic composition has an IRTTT of −20° C., −18° C., −12° C., −6° C., 5° C. or 18° C. In certain embodiments, an IUA thermochromic composition is a PMOE-4-LET and has an IRTTT of 5° C. In certain embodiments, an IUA thermochromic composition is a PMOE-2-SET and has an IRTTT of 18° C. In certain embodiments, an IUA thermochromic composition is a 50:50 MOE-4-LET:MOE-2-SET Copolymer-1 and has an IRTTT of −18° C. In certain embodiments, an IUA thermochromic composition is a 75:25 MOE-4-LET:MOE-2-SET Copolymer-2 and has an IRTTT of −6° C. In certain embodiments, an IUA thermochromic composition is a 25:75 MOE-4-LET:MOE-2-SET Copolymer-3 and has an IRTTT of −20° C.
In certain embodiments, an IUA thermochromic composition is activated by converting the IUA thermochromic composition to a high temperature state and cooling the composition to a cooling temperature in a cooling time.
In certain embodiments, an IUA thermochromic composition is converted to a high temperature state by exposure to high radiant energy (e.g. UV light). In certain embodiments, an IUA thermochromic composition is converted to a high temperature state by exposure to heat.
In certain embodiments, an IUA thermochromic composition is converted to a high temperature state by heating the IUA thermochromic composition to a heating temperature for a heating time sufficient to display a high temperature color. As used herein, the term “heating temperature” means a temperature to which an IUA thermochromic composition is raised. In certain embodiments, a heating temperature is a temperature at or above a RTTTL. In certain embodiments, a heating temperature is 20° C. below a RTTT of an IUA thermochromic composition. In certain embodiments, a heating temperature is a temperature at which an IUA thermochromic composition exhibits a high temperature color in less than about 1 minute. In certain embodiments, a heating temperature is between 80 and 150° C. In certain embodiments, a heating time is between 0.5 and 4 seconds.
As used herein, the term “cooling temperature” means a temperature to which an IUA thermochromic composition is cooled. In certain embodiments, a cooling temperature is a temperature below an IRTTTL of an IUA thermochromic composition. In certain embodiments, a cooling temperature is about 5-20° C. below an IRTTT. In certain embodiments, a cooling temperature is more than 20° C. below an IRTTT. In certain embodiments, a cooling temperature is more than 30° C. below an IRTTT.
As used herein, the term “cooling time” means a time period when an IUA thermochromic composition is cooled from a heating temperature to a cooling temperature. In certain embodiments, a cooling time is less than about 2 seconds. In certain embodiments, a cooling time is less than about 1 second.
In certain embodiments, an IUA thermochromic composition is activated using a thermochromic ink label activator as described in patent application Ser. No. 12/428,323, filed on Apr. 22, 2009, the disclosure of which is herein incorporated by its entirety. The thermochromic ink label activator includes a first stage activation energy source and a second stage rapid label cooling unit. The first stage activation energy source may include a radiant illumination unit, such as a UV or IR lamp. It may also instead include a contact hot plate or hot air source to help cause rapid absorption of energy into the IUA thermochromic composition. The rapid cooling unit may include a cold plate moving into momentary physical contact with the IUA thermochromic composition to cool the high temperature state IUA thermochromic composition to an IUA state.
Another aspect of the invention relates to an IUA thermochromic indicator comprising at least one IUA thermochromic component prepared using an IUA thermochromic composition. The terms relating to the thermochromic properties of an IUA thermochromic composition (e.g. “activation,” “activated,” “deactivation,” “deactivated,” “IUA color,” “RTTT,” “IRTTT,” “RTTTL,” “IRTTTL”) are defined the same as supra when applied to or associated with an IUA thermochromic component and an IUA thermochromic indicator. For example, an IUA thermochromic component has the same RTTT/RTTTL or IRTTT/IRTTTL as that of the IUA thermochromic composition. An IUA thermochromic component is activated/deactivated when the IUA thermochromic composition it is made of is activated/deactivated.
An IUA thermochromic component or indicator is activated before it is put in use. Therefore, the activated IUA thermochromic component or indicator will remain activated in the absence of a pre-determined condition and become deactivated upon exposure to the pre-determined condition. As used herein, the deactivation process of an activated IUA thermochromic component or indicator upon exposure to a pre-determined condition is called “triggering,” and the deactivated IUA thermochromic component or indicator is “triggered.”
In certain embodiments, a pre-determined condition is a temperature-related pre-determined condition. In certain embodiments, a temperature-related pre-determined condition comprises exposure to a pre-determined temperature/temperature range for a pre-determined time period. In certain embodiments, for different pre-determined temperature/temperature range, the pre-determined time period may be different. For example, a temperature-related pre-determined condition may comprise an exposure to 33-39° F. for more than 2 hours. The temperature-related pre-determined condition may further comprise an exposure to 40-75° F. for more than 1 hour. The temperature-related pre-determined condition may further comprise an exposure to a temperature that is at or above 90° F. for more than 5 minutes. Another example of a temperature-related pre-determined condition comprises an exposure to 10° C. for 2 hours, and/or an exposure to 15° C. for less than 1 minute.
In certain embodiments, a pre-determined temperature is +/—O—20° C. of an IRTTT of an IUA thermochromic composition. In certain embodiments, a pre-determined temperature is +/−0-10° C. of an IRTTT of an IUA thermochromic composition. In certain embodiments, a pre-determined temperature is +/—O—5° C. of an IRTTT of an IUA thermochromic composition. In certain embodiments, a pre-determined time is selected from 1 sec to 20 hours.
In certain embodiments, an IUA thermochromic component is designed such that it is invisible or undetectable when it is activated and becomes visible or detectable when it is triggered upon exposure to a pre-determined condition.
As used herein, the term “invisible” means a subject is invisible to a human eye or not recognizable by a scanning or detecting device, wherein the subject can be a pattern; the term “visible” means visible to a human eye or recognizable by a scanning or detecting device. For example, an IUA thermochromic component may remain “visible” to human eyes by always showing a color regardless of the exposure to a pre-determined condition. However, it may not be visible when the IUA thermochromic component is scanned by a pre-determined wavelength. For example, an activated IUA thermochromic component made of an IUA thermochromic POMET (e.g. PMOE-2-SET, PMOE-4-LET or a copolymer thereof) or a composition thereof may be transparent/invisible when scanned under 650 nm. However, the IUA thermochromic component will become visible under 650 nm when it is deactivated. Therefore, the IUA thermochromic component will have a pattern “appear” after it is triggered upon exposure to a pre-determined condition. Based on the same principles, an IUA thermochromic component may be designed to “disappear” after being trigged upon exposure to a pre-determined condition. For example, in the activation process as described supra, instead of activating the whole IUA thermochromic component by rapid cooling from its high temperature state, only part of the IUA thermochromic component can be activated to form a pattern (e.g. a dot in a square, or a word such as “NOT”) which will be invisible or “disappear” when it is triggered. In certain embodiments, a chilling press engraved with a desired pattern can be pressed on an IUA thermochromic component that is in its high temperature state. The part of the IUA thermochromic component that has contact with the chilling press will be cooled rapidly and become activated. The part of the IUA thermochromic component that has no contact with the chilling press will be cooled slowly and remain deactivated. Because of the different visibility or readability of the activated and deactivated IUA thermochromic composition, the pattern is “visible” to human eyes or a scanning or detecting device in the absence of a pre-determined condition. However, after exposure to the pre-determined condition, the activated part of the IUA thermochromic component will be deactivated and can no longer be differentiated from the deactivated part of the IUA thermochromic component. Therefore, the original visible pattern will be “invisible” and “disappear” and become invisible when the IUA thermochromic component is triggered.
In certain embodiments, an IUA thermochromic component is by itself an indicium the readability of which is changed after the IUA thermochromic component is triggered. In certain embodiments, an IUA thermochromic component is by itself an indicium and can form an indicium by associating with other component(s) the readability of which is (are) changed after the IUA thermochromic component is triggered. In certain embodiments, an IUA thermochromic component is not by itself an indicium but by associating with other component(s) forms an indicium the readability of which is changed after the IUA thermochromic component is triggered.
An indicium is a component or structure which may be identified or read by human, conventional scanner, optical scanner, computer or other automated identification and data capture methods, and is associated with a desired message or information. Examples of indicia include those known in the art, for example, Reduced Space Symbology (RSS, see GS1 website at http://www.gs1.org), UPC, JAN, EAN/UPC, GS1-128, ITF-14, Data matrix, Composite Component (CC), RRFID, Auto-ID, RFID, biometrics, magnetic stripes, OCR, smart cards, voice recognition, other identification, standard language system and platform provided locally, nationally, globally, and used by GS-1. Also included are indicia comprising human readable data combined with other readable indicia such as bar code data, RSS, UPC, EAN, UCC-13, GTIN, RFID, GILBAR™, or those comprising a component of the Food Sentinel System™.
In certain embodiments, an indicium can be identified or read due to its optical readability. The term “optical readability” is intended to cover all indicia that can be recognized by a human or optical scanning equipment such as scanners, cameras, and lasers. Examples of optically readable indicia include, without limitation, RSS, UPC, JAN, EAN/UPC, GS1-128, ITF-14, Data matrix and Composite Component (CC).
In certain embodiments, an IUA thermochromic indicator comprises an indicium that is identifiable or remains readable regardless of the presence or absence of a pre-determined condition (“always-readable indicium”). In certain embodiments, an IUA thermochromic indicator comprises an indicium that is readable in the absence of a pre-determined condition and unreadable after exposure to the pre-determined condition (“selectively-unreadable indicium”). In certain embodiments, an IUA thermochromic indicator comprises an indicium that is unreadable in the absence of a pre-determined condition and becomes readable after exposure to the pre-determined condition (“selectively-readable indicium”).
In certain embodiments, an always-readable component or indicium of an IUA thermochromic indicator includes product identifying information, source of manufacturer, source of distributor, or other information that is of use in tracking and tracing an item or is desired. In certain embodiments, an always-readable component or indicium of an IUA thermochromic indicator includes a two-dimensional structure such as a Composite Component structure.
In certain embodiments, a selectively-readable indicium of an IUA thermochromic indicator comprises an initially non-readable component and an IUA thermochromic component designed to identify the absence or presence of exposure to the indicator to a pre-determined condition. Upon exposing the indicator to the pre-determined condition, the IUA thermochromic component is triggered such that the initially non-readable component itself or by associating with the triggered IUA thermochromic component becomes a readable indicium (e.g. a readable bar code) identifying the product as having been exposed to the pre-determined condition. Upon such identification, the product is targeted for removal or culling from the distribution chain. In addition, the location and time of occurrence of presence of such product is marked and archived.
In certain embodiments, a selectively-readable indicium is an IUA thermochromic component, wherein the indicium is not readable in the absence of a pre-determined condition, and is triggered to become readable or identifiable after exposure to the pre-determined condition.
In certain embodiments, a selectively-unreadable indicium may include an initially readable component (e.g. a readable bar code) and an IUA thermochromic component designed to identify the absence or presence of exposure to a pre-determined condition. Upon exposure to the pre-determined condition, the IUA thermochromic component is triggered such that the triggered IUA thermochromic component by itself or by associating with the initially readable component becomes an unreadable indicium and therefore identify the product as having been exposed to the pre-determined condition. Upon such identification, the product is targeted for removal or culling from the distribution chain. In addition, the location and time of occurrence of presence of such product is marked and archived.
In certain embodiments, a selectively-nonreadable indicium is an IUA thermochromic component, wherein the indicium is readable in the absence of a pre-determined condition, and is triggered to become non-readable after exposure to the pre-determined condition.
In certain embodiments, an IUA thermochromic indicator comprises an always-readable indicium and a selectively-readable indicium. In certain embodiments, an IUA thermochromic indicator comprises an always-readable indicium and a selectively-nonreadable indicium. In certain embodiments, an IUA thermochromic indicator comprises a selectively-readable indicium and a selectively-nonreadable indicium. In certain embodiments, an IUA thermochromic indicator comprises an always-readable indicium, a selectively-readable indicium, a selectively-nonreadable indicium, a plurality or a mixture thereof.
In certain embodiments, an IUA thermochromic indicator comprises a paired bar code and printing structure associated with an IUA component wherein when the indicator is or has been exposed to a pre-determined condition the IUA component will change so that only an indicium indicating the exposure to the pre-determined condition will be readable. Such indicium may show or encode “do not sell” or “remove item from distribution.”
In certain embodiments, an IUA thermochromic indicator (
In certain embodiments, an IUA thermochromic indicator comprises two bar codes aligned as bar codes under the trademark GILBAR™ (
In certain embodiments, an IUA thermochromic indicator includes an IUA thermochromic indicia combining human recognized language or code and machine recognized indicia (e.g. bar code) (32,
In certain embodiments, an IUA thermochromic indicator comprises multiple condition indicia, wherein the each condition indicia reflects an absence or presence of different or same pre-determined conditions. In certain embodiments, the predetermined conditions may also include toxin-related pre-determined condition, such as in U.S. patent application Ser. No. 11/838,727, filed on Aug. 14, 2007 and U.S. Pat. No. 5,306,466, issued on Apr. 26, 1994; No. 5,869,341, issued on Feb. 9, 1999; No. 6,190,610, issued on Feb. 20, 2001; No. 6270724, issued on Aug. 7, 2001; No. 6,479,016, issued on Nov. 12, 2002; No. 7156597, issued on Jan. 2, 2007 and No. 7157048, issued on Jan. 2, 2007, the disclosure of which is incorporated by reference herein in their entireties. In certain embodiments, an IUA thermochromic component adopts the same design as the condition indicia disclosed in the US patent application and/or the US patents referred supra.
In certain embodiments, an IUA thermochromic indicator includes a multiple condition indicator such as that marketed under the Food Sentinel System™ (U.S. patent Ser. No. 09/153,565, filed Sep. 15, 1998, the disclosure of which is incorporated by reference herein in its entirety.). (100,
In certain embodiments, an IUA thermochromic indicator (200,
Each condition indicium can be spaced apart from another or be arranged in an overlapping manner, a continuous manner, or any combination thereof. In certain embodiments, an IUA thermochromic indicator incorporates one of RSS formats (e.g. stacked RSS symbology such as RSS-14 stacked and RSS expanded Stacked, RSS Limited, RSS-14 Trunctated, RSS-14 Stacked and others, as described in further detail at htpp://www.gs1.org/) as described in U.S. Patent application 2008/0043804, the disclosure of which is incorporated by reference herein in its entirety.
In certain embodiments, an IUA thermochromic indicator incorporates a RSS symbology which includes more than one data. For example, a CC-A code using Composite Component structures (
In certain embodiments, an IUA thermochromic indicator comprises a 2-dimensional code structure (
More information of Composite Component (CC) is available at http://www.aimcilobal.org. Examples of CC structures include, without limitation, CC-A, CC-B and CC-C. CC structures can also be incorporated with other symbologies such as RSS, GS1, EAN, and UPC. Examples of the combined structures include, without limitation, RSS-14 Truncated with CC-A, RSS Limited with CC-B, GS1-12B (SSCC-18) with CC-C, EAN-13 with CC-A, EAN-8 with CC-A, UPC-A with CC-B, UPC-E with CC-A, GS1-128 (SCC-14) with CC-A, and GS1-128 with CC-C.
In certain embodiments, an IUA thermochromic indicator is an article which can be applied to a subject stored in the absence of a pre-determined condition. In certain embodiments, an IUA thermochromic composition is applied to an article and activated to form an IUA thermochromic component/indicator. In certain embodiments, an IUA thermochromic composition is activated and then applied to an article to form an IUA thermochromic component/indicator. An IUA thermochromic indicator will remain activated without exposure to the pre-determined condition. When the IUA thermochromic indicator is exposed to the pre-determined condition, the IUA thermochromic composition is deactivated and such deactivation is detectable.
In certain embodiments, an IUA thermochromic indicator is an indicator on a subject which is stored below a pre-determined temperature, comprising an IUA thermochromic composition wherein the IUA thermochromic composition is activated when the subject is kept below the pre-determined temperature and deactivated when the subject is exposed to a temperature above the pre-determined temperature, and such deactivation is detectable.
In certain embodiments, a thin film of an IUA thermochromic composition is applied to cover a barcode or a portion thereof that can be read by a scanner at a pre-determined wavelength. The IUA thermochromic composition is transparent at the pre-determined wavelength when it is activated. Therefore the barcode can be read by the scanner at the pre-determined wavelength as long as the IUA thermochromic composition remains activated. When the barcode is exposed to a pre-determined condition, the IUA thermochromic composition is deactivated and absorbs at the pre-determined wavelength. The barcode can no longer be read by the scanner at the pre-determined wavelength and will be detected. In certain embodiments, a pre-determined wavelength is 650 nm. In certain embodiments, a pre-determined condition is an exposure to a temperature equal to or higher than about 5° C. below the IRTTT of the IUA thermochromic composition for more than 2 hours. In certain embodiments, a pre-determined condition is an exposure to a temperature equal to or higher than about the IRTTT of the IUA thermochromic composition for more than 15 minutes. In certain embodiments, a pre-determined condition is an exposure to a temperature equal to or higher than about 5° C. above the IRTTT of the IUA thermochromic composition.
In certain embodiments, a barcode or a portion thereof is printed using an IUA thermochromic composition as ink (IUA thermochromic ink). The IUA thermochromic ink is transparent at a pre-determined wavelength when activated therefore the barcode cannot be read by a scanner at the pre-determined wavelength. When the barcode is exposed to a pre-determined condition, the IUA thermochromic ink is deactivated and absorbs at the pre-determined wavelength. The barcode can now be read by the scanner at the pre-determined wavelength. In certain embodiments, the pre-determined wavelength is 650 nm. In certain embodiments, a pre-determined condition is an exposure to a temperature equal to or higher than about 5° C. below the IRTTT of the IUA thermochromic composition for more than 2 hours. In certain embodiments, a pre-determined condition is an exposure to a temperature equal to or higher than about the IRTTT of the IUA thermochromic composition for more than 15 minutes. In certain embodiments, a pre-determined condition is an exposure to a temperature equal to or higher than about 5° C. above the IRTTT of the IUA thermochromic composition.
In certain embodiments, an IUA thermochromic indicator can adopt a similar principles and designs as described supra wherein the IUA thermochromic component will either disappear or appear upon the exposure to a pre-determined condition.
Another aspect of the invention relates to a method of preparing an activated IUA thermochromic composition comprising converting an IUA thermochromic composition to a high temperature state and cooling the composition to a cooling temperature in a cooling time.
In certain embodiments, an IUA thermochromic composition is converted to a high temperature state by exposing the composition to a high radiant energy (e.g. UV light). In certain embodiments, an IUA thermochromic composition is converted to a high temperature state by exposure to heat.
In certain embodiments, an IUA thermochromic composition is converted to a high temperature state by being heated to a heating temperature for a time sufficient to display a high temperature color. In certain embodiments, a heating temperature is at or above a RTTTL. In certain embodiments, a heating temperature is 20° C. below a RTTT of an IUA thermochromic composition. In certain embodiments, a heating temperature is a temperature at which an IUA thermochromic composition exhibits a high temperature color in less than about 1 minute. In certain embodiments, a heating temperature is between 80 and 150° C. In certain embodiments, a heating time is between 0.5 and 4 seconds.
In certain embodiments, a cooling temperature is a temperature below an IRTTTL of an IUA thermochromic composition. In certain embodiments, a cooling temperature is about 5-20° C. below an IRTTT. In certain embodiments, a cooling temperature is more than 20° C. below an IRTTT of an IUA thermochromic composition. In certain embodiments, a cooling temperature is more than 30° C. below an IRTTT.
In certain embodiments, a cooling time is less than about 2 seconds. In certain embodiments, a cooling time is less than 1 second.
In certain embodiments, an IUA thermochromic composition or indicator is activated using a thermochromic ink label activator as described in patent application Ser. No. 12/428,323, filed on Apr. 22, 2009, the disclosure of which is herein incorporated by its entirety, wherein the IUA thermochromic composition or indicator is converted to a high temperature state by exposing to a radiant illumination unit (e.g. a UV or IR lamp) or a heat source (e.g. a contact hot plate or a hot air source).
Another aspect of the invention relates to a method of preparing an activated IUA thermochromic component/indicator.
In certain embodiments, a method comprises applying an activated IUA thermochromic composition to an article to be used as a thermal indicator at a temperature below the IRTTTL of the IUA thermochromic composition.
In certain embodiments, a method comprises:
applying an IUA thermochromic composition to an article to be used as a thermal indicator;
converting the IUA thermochromic composition to a high temperature state; and
cooling the article and/or the IUA thermochromic composition to a cooling temperature in a cooling time.
In certain embodiments, a conversion of an IUA thermochromic composition to a high temperature state is achieved by exposing the IUA thermochromic composition to a high radiant energy (e.g. UV light). In certain embodiments, a conversion of an IUA thermochromic composition to a high temperature state is achieved by heating an article with an IUA thermochromic composition or indicator, or heating the IUA thermochromic composition to a heating temperature for a time sufficient to display a high temperature color. In certain embodiments, a heating temperature is a temperature at or above a RTTTL. In certain embodiments, a heating temperature is 20° C. below a RTTT of an IUA thermochromic composition. In certain embodiments, a heating temperature is a temperature at which an IUA thermochromic composition exhibits a high temperature color in less than about 1 minute. In certain embodiments, a heating temperature is between 80 and 150° C. In certain embodiments, a heating time is between 0.5 and 4 seconds. In certain embodiments, an IUA thermochromic composition or indicator is activated using a thermochromic ink label activator as described in patent application Ser. No. 12/428,323, filed on Apr. 22, 2009, the disclosure of which is herein incorporated by its entirety, wherein the IUA thermochromic composition or indicator is converted to a high temperature state by exposing to a radiant illumination unit (e.g. a UV or IR lamp) or a heat source (e.g. a contact hot plate or a hot air source).
In certain embodiments, a cooling temperature is a temperature below an IRTTTL of an IUA thermochromic composition. In certain embodiments, a cooling temperature is more than 5° C. below an IRTTT of an IUA thermochromic composition. In certain embodiments, a cooling temperature is more than 20° C. below an IRTTT of an IUA thermochromic composition. In certain embodiments, a cooling temperature is more than 30° C. below an IRTTT of an IUA thermochromic composition.
In certain embodiments, a cooling time is less than about 2 seconds. In certain embodiments, a cooling time is less than 1 second.
Another aspect of the invention relates to a method of monitoring a subject stored in the absence of a pre-determined condition. In certain embodiments, a pre-determined condition is defined the same as supra.
In certain embodiments, a method comprises:
applying an activated IUA thermochromic composition, component or indicator on a subject that is to be stored without exposure to a pre-determined condition;
detecting the subject when the subject is or has been exposed to the pre-determined condition by detecting the deactivation of the IUA thermochromic composition, component or indicator.
In certain embodiments, the method comprises:
applying an IUA thermochromic composition, component or indicator on a subject to be stored without exposure to a pre-determined condition;
activating the IUA thermochromic composition, component or indicator;
detecting the subject when the subject has been exposed to the pre-determined condition by detecting the deactivation of the IUA thermochromic composition, component or indicator.
In certain embodiments, a thin film of an IUA thermochromic composition is applied to cover a barcode that can be read by a scanner at a pre-determined wavelength. The IUA thermochromic composition is transparent at the pre-determined wavelength when it is activated. Therefore the barcode can be read by the scanner at the pre-determined wavelength as long as the IUA thermochromic composition is kept activated. When the barcode is exposed to a pre-determined condition, the IUA thermochromic composition is deactivated and absorbs at the pre-determined wavelength. The barcode can no longer be read by the scanner at the pre-determined wavelength and will be detected. In certain embodiments, the pre-determined wavelength is 650 nm. In certain embodiments, a pre-determined condition is an exposure to a temperature equal to or higher than about 5° C. below the IRTTT of the IUA thermochromic composition for more than 2 hours. In certain embodiments, a pre-determined condition is an exposure to a temperature equal to or higher than about an IRTTT of an IUA thermochromic composition for more than 15 minutes. In certain embodiments, a pre-determined condition is an exposure to a temperature equal to or higher than about 5° C. above an IRTTT of an IUA thermochromic composition.
In certain embodiments, a barcode is printed using an IUA thermochromic composition as ink (IUA thermochromic ink). The IUA thermochromic ink is transparent at a pre-determined wavelength when activated therefore the barcode cannot be read by a scanner at the pre-determined wavelength. When the barcode is exposed to a pre-determined condition, the IUA thermochromic ink is deactivated and absorbs at the pre-determined wavelength. The barcode can now be read by the scanner at the pre-determined wavelength. In certain embodiments, the pre-determined wavelength is 650 nm. In certain embodiments, a pre-determined condition is an exposure to a temperature equal to or higher than about 5° C. below the IRTTT of the IUA thermochromic composition for more than 2 hours. In certain embodiments, a pre-determined condition is an exposure to a temperature equal to or higher than about the IRTTTL of the IUA thermochromic composition for more than 15 minutes. In certain embodiments, a pre-determined condition is an exposure to a temperature equal to or higher than about 5° C. above the IRTTT of the IUA thermochromic composition.
The following examples are provided to better illustrate the claimed invention and are not to be interpreted in any way as limiting the scope of the invention. All specific compositions, materials, and methods described below, in whole or in part, fall within the scope of the invention. These specific compositions, materials, and methods are not intended to limit the invention, but merely to illustrate specific embodiments falling within the scope of the invention. One skilled in the art may develop equivalent compositions, materials, and methods without the exercise of inventive capacity and without departing from the scope of the invention. It will be understood that many variations can be made in the procedures herein described while still remaining within the bounds of the invention. It is the intention of the inventors that such variations are included within the scope of the invention.
A compound having Structure I was prepared by polymerization of the thiophene monomers according to the following Scheme 1:
A PMOET was prepared according to Scheme 2.
PMOE-2-SET was prepared according to Scheme 2, wherein the average of m was 17 and the average of n was 2.
Under positive nitrogen atmosphere, polyoxyethylene (2) stearyl ether (OE-2-SE, a mixture of compounds having the average molecular structure of C18H37(OCH2CH2)2—OH, Wako Chemicals, 152 g, 0.424 mol) and metal sodium (9.1 g, 0.395 mol) were charged into a 500 mL flask and stirred at about 120° C. until the sodium disappeared (about 2 days) to obtain the sodium salt having the average molecular structure of C18H37(OCH2CH2)2—ONa. Under nitrogen atmosphere, 3-bromo-4-methylthiophene (50 g, 0.28 mol), diglyme (120 mL), copper chloride (0.70 g, 0.007 mol) and 2-aminopyridine (0.56 g, 0.006 mol) were charged into a 250 mL flask and stirred at room temperature for 10 minutes. Then the said mixture was added into C18H37(OCH2CH2)2—ONa and stirred at 100° C. for about 2 days. The reaction was cooled to room temperature, filtered and rinsed with methylene chloride (300 mL) after the reaction was complete. The filtrate was purified on silica gel using ethyl acetate to elute the crude product (500 mL). The eluate was washed by dilute hydrochloric acid (50 mL×3), water (50 mL×2), dilute sodium hydroxide (50 mL×3) and saturated sodium chloride (50 mL). The washed eluate was dried and evaporated to remove unreacted 3-bromo-4-methylthiophene. The purified 3-methyl-4-polyoxyethylene(2) stearyl ether thiophene monomer (MOE-2-SET) was obtained with 50% yield.
Under nitrogen atmosphere, MOE-2-SET monomer (158 g, 0.348 mol, in 250 mL methylene chloride) was transferred into a 2 L flask containing iron trichloride (113 g, 0.696 mol) and methylene chloride (200 mL). The mixture was stirred at room temperature for about 24 hours and precipitated with cold methanol. The resulting polymer was filtered on a Buchner funnel and stirred in methanol with NaOH (300 mL, 1 g). The polymer was recollected, washed with cold methanol and warm methanol and dried to obtain poly(3-methyl-4-dioxyethylenealkylether)thiophenes (PMOE-2-SET) (54 g, yield: 34%).
PMOE-4-LET was prepared according to Scheme 2, wherein the average of m was 11 and the average of n was 4.
Monomers of a copolymer were prepared as described supra. Copolymers were prepared by known polymerization methods. The term “copolymer” and “copolymers” as used herein means polymers that have more than one monomer. For example, a copolymer can be an alternating copolymer (with different monomers arranged in an alternating sequence), a periodic copolymer (with different monomers arranged in a repeating sequence), a random copolymer (with random sequences of different monomers) and a block copolymer (with two or more homopolymer subunits linked by covalent bonds).
MOE-2-SET and MOE-4-LET were prepared as described supra. Copolymer-1 was prepared by polymerizing a monomer mixture containing 50:50 MOE-2-SET: MOE-4-LET as described supra.
MOE-2-SET and MOE-4-LET were prepared as described supra. Copolymer-1 was prepared by polymerizing a monomer mixture containing 25:75 MOE-2-SET: MOE-4-LET as described supra.
MOE-2-SET and MOE-4-LET were prepared as described supra. Copolymer-1 was prepared by polymerizing of a monomer mixture containing 75:25 MOE-2-SET: MOE-4-LET as described supra.
Reflection spectra were measured with an Ocean Optics S2000 instrument using a cylindrical fiber-optic reflection probe containing one source fiber and seven collection fibers. The spectra were referenced against a white standard between 450 and 800 nm and a tungsten-halogen lamp. The samples for variable temperature spectra were prepared by drip-coating a polythiophene composition (saturated in THF) onto a piece of paper and then evaporating the solvent off with a heat gun. The samples were placed on an aluminum block containing a thermometer and placed on a hot plate, which was used to heat the sample at about 2° C./minute. Removal of the heat source gave a similar cooling rate. The surface temperature at the sample site was calibrated by using the reflection change associated with the melting of biphenyl (69° C.) and naphthalene (80° C.). Variable temperature reflection spectra were measured at 600 nm from around −40° C. to around 120° C. Transition temperatures of the sample compounds or compositions were determined by the center of the sigmoid curve. In order for an activated IUA thermochromic composition to remain activated, the composition should be kept below the IRTTTL.
Variable temperature reflection spectra at 600 nm of PMOE-4-LET (
3. IUA thermochromic indicator and detecting of subjects that has been exposed to a temperature exceeds a pre-determined temperature.
Barcodes were coated with a thin film of a composition comprising PMOE-2-SET. When the composition was in the activated phase the pigments were transparent at 650 nm and the bar code was detectable by a scanner. When the activated composition reached or exceeded the IRTTT, the composition reverted to a thermodynamic low temperature phase at which it absorbed at 650 nm, and the bar codes were no longer readable by the scanner.
Barcodes were coated with pure PMOE-2-SET wherein the PMOE-2-SET was activated and stored in a refrigerator at 40° F. for 8 week. Periodic scanning confirmed that the activated phase of the 40° F. pigment was retained during the entire 8 weeks. When the card sock samples (without any cold mass) were removed from the refrigerator, the IUA thermochromic transition occurred in about 20 minutes and the bar codes could no longer be scanned.
Barcodes were coated with a thin film of a composition comprising PMOE-4-LET. When the composition was in the activated phase the pigments were transparent at 650 nm and the bar code was detectable by a scanner. When the activated composition reached or exceeded the IRTTT, the composition reverted to a thermodynamic low temperature phase at which it absorbed at 650 nm, and the bar codes were no longer readable by the scanner.
An IUA thermochromic indicator comprises a complete bar code (such as a purveyor's bar code) and an incomplete bar code (
An IUA thermochromic indicator is prepared adopting a GILBAR™ structure using an ordinary ink (
An IUA thermochromic indicator (32,
An IUA thermochromic indicator includes multiple condition indicia such as that marketed under the Food Sentinel System™ (100,
An IUA thermochromic indicator (200,
The present application claims priority to U.S. Provisional Patent Application No. 61/051,150, filed May 7, 2008, the disclosure of which is incorporated by reference herein in its entirety.
The invention is sponsored by US Army/Natick with Project Number 500-2103-0000-0001326. The U.S. Government has a paid-up license in this invention and the right in limited circumstances to require the patent owner to license others on reasonable terms as provided for by the terms of FY01-PS10 awarded by USDOT.
| Number | Date | Country | |
|---|---|---|---|
| 61051150 | May 2008 | US |
