# US 2013/0152848 A1 · Low temperature irreversible thermochromic compositions

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- Number: US 2013/0152848 A1
- Document ID: US20130152848A1
- Status: Published application
- Kind: A1
- Application number: 13/767,300
- Filed: 2013-02-14
- Published: 2013-06-20
- Earliest claimed: 2008-05-07
- Assignees: The Board of Governors for Higher Education, State of Rhode Island and Providence Plantations
- Inventors: Brett L. Lucht; William B. Euler
- Web page: https://patentgrep.com/patent/US20130152848A1

## CPC

- G01N 25/00: Investigating or analyzing materials by the use of thermal means (G01N3/00 - G01N23/00 take precedence)
- B41M 5/284: {Organic thermochromic compounds}
- C08F 28/06: by a heterocyclic ring containing sulfur
- C08G 61/126: {with a five-membered ring containing one sulfur atom in the ring}
- C09D 11/50: Sympathetic, colour changing or similar inks
- C09K 9/02: Organic tenebrescent materials
- C09K 2211/1425: Non-condensed systems
- C09K 2211/1458: containing sulfur as the only heteroatom
- G01N: INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES (measuring or testing apparatus or processes other than immunoassay, involving enzymes or microorganisms C12M, C12Q)
- B41M: PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING, (correction of typographical errors B41J; processes for applying transfer pictures or the like B44C1/16; fluid media for correction of typographical errors by coating C09D10/00; printing textiles D06P)
- C08F: MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08G: MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C09D: COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR (cosmetics A61K; processes for applying liquids or other fluent materials to surfaces, in general, B05D; staining wood B27K5/02; glazes or vitreous enamels C03C; natural resins, French polish, drying-oils, driers, turpentine, per se, C09F; polishing compositions other than French polish, ski waxes C09G; adhesives or use of materials as adhesives C09J; materials for sealing or packing joints or covers C09K3/10; materials for stopping leaks C09K3/12; processes for the electrolytic or electrophoretic production of coatings C25D)
- C09K: MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE

## Abstract

Provided herein are novel polythiophene compounds having polyalkoxyl sidechains and low temperature irreversible upon activation (IUA) thermochromic compounds/compositions thereof. The IUA thermochromic compounds or compositions are activated and exhibit an IUA color by heating to or above a reversible thermochromic transition temperature (RTTT) and cooling to or below an irreversible thermochromic transition temperature (IRTTT) in less than 2 seconds. The activated IUA thermochromic compounds or compositions will retain their IUA color as long as the compounds or compositions are kept at or below about 5° C. below the IRTTT. The activated IUA thermochromic compounds or compositions will be deactivated and show a different color upon exposure to a temperature equal to or higher than about 5° C. below the IRTTT unless the compounds or compositions are activated again. The IUA thermochromic compounds/composition can be used to prepare IUA thermochromic indicators which can monitor subjects stored below a pre-determined temperature and detect the subjects that have been exposed to a temperature above the pre-determined temperature.

## Claims

### Claim 1

A polythiophene compound having the following chemical structure:
including stereoisomers thereof, wherein:
each R1 of each monomer is independently selected from the group consisting of H and alkyl 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 is an independently selected integer; and
p is 2-1000.

### Claim 2 (depends on 1)

The compound according to claim 1, wherein R1 is CH3.

### Claim 3 (depends on 2)

The compound according to claim 2, wherein:
R3 is CmH2m−1, wherein m of each monomer is an independently selected integer;
the average of m of all monomers is 7 to 21;
the average of n of all monomers is 0 to 6; and
3n+m+1 is 20 to 40.

### Claim 4 (depends on 3)

The compound according to claim 3, wherein
R2 is CH2CH2;
m is 17 or 11;
when m is 11, the average of n is 4 (monomer MOE-4-LET); and
when m is 17, the average of n is 2 (monomer MOE-2-SET).

### Claim 5 (depends on 1)

A composition comprising a compound according to claim 1.

### Claim 6 (depends on 5)

The composition according to claim 5, further comprising a carrier medium.

### Claim 7 (depends on 5)

The composition according to claim 5, wherein R1 is CH3.

### Claim 8 (depends on 7)

The composition according to claim 7, wherein:
R3 is CmH2m+1, wherein m of each monomer is an independently selected integer;
the average of m of all monomers for each polythiophene compound is 7 to 21;
The average of n of all monomers for each polythiophene compound is 0 to 6; and
3n+m+1 is 20 to 40.

### Claim 9 (depends on 8)

The composition according to claim 8, wherein R2 is CH2CH2.

### Claim 10 (depends on 4, 9)

The composition according to claim 9, wherein the monomers are selected from the group consisting of MOE-2-SET and MOE-4-LET as defined in claim 4.

### Claim 11 (depends on 6)

The composition according to claim 6, wherein the carrier medium is an ink formulation, poly(ethylene terephthalate)s (PET), polysytrenes, 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.

### Claim 12 (depends on 11)

The composition according to claim 11, wherein the ink formulation comprises oils, resins, pigment extenders and additives.

### Claim 13 (depends on 6)

The composition according to claim 6, wherein the concentration of the compound in the composition is about 0.05% to about 99.5% by weight.

### Claim 14 (depends on 6)

The composition according to claim 6, wherein the concentration of the compound in the composition is about 10% by weight.

### Claim 15 (depends on 5)

An irreversible upon activation (IUA) thermochromic composition comprising a composition according to claim 5, wherein the composition has an irreversible thermochromic transition temperature (IRTTT) and a low irreversible thermochromic transition temperature (IRTTTL).

### Claim 16 (depends on 15)

The IUA thermochromic composition according to claim 15 wherein the IRTTT is between about −30° C. to about 60° C.

### Claim 17 (depends on 15)

The IUA thermochromic composition according to claim 15, wherein the IUA composition is selected from the group consisting of a polymer composition of MOE-4-LET having an IRTTT of 5° C., a polymer composition of MOE-2-SET having an IRTTT of 18° C., a copolymer composition of 50:50 MOE-4-LET:MOE-2-SET having an IRTTT of −18° C., a copolymer composition of 75:50 MOE-4-LET:MOE-2-SET having an IRTTT of −6° C., and a copolymer composition of 25:75 MOE-4-LET:MOE-2-SET having an IRTTT of −20° C.

### Claim 18 (depends on 15)

The IUA thermochromic composition according to claim 15, wherein an activated IUA thermochromic composition has a first set of optical properties, an deactivated IUA thermochromic composition has a second set of optical properties, wherein the two sets of optical properties are not identical, and the difference or differences between the two sets of optical properties can be recognized by a human eye or a detecting device.

### Claim 19 (depends on 18)

The IUA thermochromic composition according to claim 18, wherein the activated IUA thermochromic composition is transparent under a pre-determined wavelength, and the deactivated IUA thermochromic composition is not transparent under the pre-determined wavelength.

### Claim 20 (depends on 15)

An activated IUA thermochromic composition comprising an IUA thermochromic composition according to claim 15, wherein:
the IUA thermochromic composition is activated by heating the IUA thermochromic composition to a heating temperature for a time sufficient to exhibit a high temperature color to convert the IUA thermochromic composition to a high temperature state; and cooling the IUA thermochromic composition to a cooling temperature in less than 2 seconds.

### Claim 21 (depends on 20)

The activated IUA thermochromic composition according to claim 20, wherein the cooling temperature is about 5-20° C. below an IRTTT of the IUA thermochromic composition.

### Claim 22 (depends on 20)

The activated IUA thermochromic composition according to claim 20, wherein the cooling temperature is more than 20° C. below an IRTTT of the IUA thermochromic composition.

### Claim 23 (depends on 20)

The activated IUA thermochromic composition according to claim 20, wherein the IUA thermochromic composition is cooled to the cooling temperature in less than 1 second.

### Claim 24 (depends on 15)

An irreversible upon activation (IUA) thermochromic indicator comprising an IUA thermochromic component prepared using an IUA thermochromic composition according to claim 15.

### Claim 25 (depends on 24)

The IUA thermochromic indicator according to claim 24, wherein the IUA thermochromic component is a selectively-readable indicium by itself, and/or by associating with other component(s) of the IUA thermochromic indicator, the IUA thermochromic component is activated and non-readable in the absence of a pre-determined condition and becomes deactivated and readable upon exposure to the pre-determined condition.

### Claim 26 (depends on 24)

The IUA thermochromic indicator according to claim 24, wherein the IUA thermochromic component is a selectively-non-readable indicium by itself and/or by associating with other component(s) of the IUA thermochromic indicator, the IUA thermochromic component is activated and readable in the absence of a pre-determined condition and becomes deactivated and non-readable upon exposure to the pre-determined condition.

### Claim 27 (depends on 24)

The IUA thermochromic indicator according to claim 24, further comprising one or more indicia that are independently selected from the group consisting of always-readable indicia, selectively-readable indicia, selectively-unreadable indicia, a plurality and a mixture thereof.

### Claim 28 (depends on 27)

The IUA thermochromic indicator according to claim 27, wherein each component can be triggered upon exposure to the same or different pre-determined conditions, wherein the pre-determined condition that triggers the IUA thermochromic component is exposure to a pre-determined temperature for a pre-determined period of time.

### Claim 29 (depends on 28)

The IUA thermochromic indicator according to claim 28, wherein the pre-determined temperature is +/−0-10° C. of an IRTTT of the IUA thermochromic composition used to prepare the IUA thermochromic component; and the pre-determined period of time is selected from 1 second to 20 hours.

### Claim 30 (depends on 29)

The method according to claim 29, wherein the IRTTT of the IUA thermochromic composition is between about −30° C. to about 60° C.

### Claim 31 (depends on 29)

The method according to claim 29, wherein the IRTTT of the IUA thermochromic composition is about −20° C., −18° C., −12° C., −6° C., 5° C. or 18° C.

### Claim 32 (depends on 24, 25)

The IUA thermochromic indicator according to claim 25, comprising an indicium printed by an activated IUA thermochromic composition according to claim 24, wherein the indicium is non-readable in the absence of a pre-determined condition and becomes readable upon exposure to the pre-determined condition.

### Claim 33 (depends on 24, 26)

The IUA thermochromic indicator according to claim 26, comprising an readable indicium, wherein part or the whole of the indicium is coated with an activated IUA thermochromic composition according to claim 24, wherein the indicium is readable in the absence of a pre-determined condition and becomes non-readable upon exposure to the pre-determined condition.

### Claim 34 (depends on 15)

A method of preparing an activated IUA thermochromic composition comprising:
heating an IUA thermochromic composition according to claim 15 to a heating temperature for a time sufficient to exhibit a high temperature color to convert the IUA thermochromic composition to a high temperature state; and
cooling the IUA thermochromic composition to a cooling temperature in less than 2 seconds.

### Claim 35 (depends on 34)

The method according to claim 34, wherein the cooling temperature is about 5-20° C. below an IRTTT of the IUA thermochromic composition.

### Claim 36 (depends on 34)

The method according to claim 34, wherein the cooling temperature is more than 20° C. below an IRTTT of the IUA thermochromic composition.

### Claim 37 (depends on 34)

The method according to claim 34, wherein the IUA thermochromic composition is cooled to the cooling temperature in less than 1 second.

### Claim 38 (depends on 20)

A method of preparing an IUA thermochromic indicator comprising applying an activated IUA thermochromic composition according to claim 20 to an article under a condition that the activated IUA thermochromic composition remains activated.

### Claim 39 (depends on 20)

A method of preparing an IUA thermochromic indicator comprising applying an IUA thermochromic composition according to claim 20 to an article, and then activating the IUA thermochromic composition.

### Claim 40 (depends on 39)

The method according to claim 39, wherein the activating step comprises:
heating the IUA thermochromic composition to a heating temperature for a time sufficient to exhibit a high temperature color to convert the IUA thermochromic composition to a high temperature state; and
cooling the article or the IUA thermochromic composition to a cooling temperature in less than 2 seconds.

### Claim 41 (depends on 40)

The method according to claim 40, wherein the cooling temperature is about 5-20° C. below an IRTTT of the IUA thermochromic composition.

### Claim 42 (depends on 40)

The method according to claim 40, wherein the cooling temperature is more than 20° C. below an IRTTT of the IUA thermochromic composition.

### Claim 43 (depends on 40)

The method according to claim 40, wherein the article or the IUA thermochromic composition is cooled to the cooling temperature in less than 1 second.

### Claim 44 (depends on 24)

A method of monitoring a subject which is to be stored without exposure to a pre-determined condition comprising:
applying an IUA thermochromic indicator according to claim 24 on the subject, wherein the IUA thermochromic indicator is already activated or will be activated without spoiling the subject;
the activated IUA thermochromic indicator will be deactivated upon exposure to the pre-determined condition; detecting the deactivated IUA thermochromic indicator.

### Claim 45 (depends on 44)

The method according to claim 44 wherein the pre-determined condition is exposure to a pre-determined temperature for a pre-determined time.

### Claim 46 (depends on 45)

The method according to claim 45, wherein the pre-determined temperature is +/−0-10° C. of an IRTTT of an IUA thermochromic composition used to prepare the IUA thermochromic indicator; and the pre-determined period of time is selected from 1 second to 20 hours.

### Claim 47 (depends on 46)

The method according to claim 46, wherein the IRTTT is between about −30° C. to about 60° C.

### Claim 48 (depends on 46)

The method according to claim 46, wherein the IRTTT is about −20° C., −18° C., −12° C., −6° C., 5° C. or 18° C.