TEPZZ 67585¥B_T

(19)

(11) EP 2 675 853 B1

(12) EUROPEAN PATENT SPECIFICATION

(45) Date of publication and mention (51) Int Cl.:

of the grant of the patent: C09D 5/00 (2006.01)
14.09.2016 Bulletin 2016/37
(86) International application number:
(21) Application number: 12707188.4 PCT/US2012/025322

(22) Date of filing: 15.02.2012 (87) International publication number:

WO 2012/112729 (23.08.2012 Gazette 2012/34)

(54) THERMOCHROMIC COATINGS WITH RESIN VEHICLE

THERMOCHROME BESCHICHTUNGEN MIT HARZVEHIKEL
REVÊTEMENTS THERMOCHROMIQUES CONTENANT UN VÉHICULE RÉSINE

(84) Designated Contracting States: (72) Inventors:

AL AT BE BG CH CY CZ DE DK EE ES FI FR GB • OWEN, Timothy, J.
GR HR HU IE IS IT LI LT LU LV MC MK MT NL NO Colorado Springs, CO 80916 (US)
PL PT RO RS SE SI SK SM TR • FLETCHER, Kristin, A.
Colorado Springs, CO 80907 (US)
(30) Priority: 15.02.2011 US 201161443170 P
(74) Representative: Kador & Partner
(43) Date of publication of application: Corneliusstraße 15
25.12.2013 Bulletin 2013/52 80469 München (DE)

(73) Proprietor: Chromatic Technologies, Inc. (56) References cited:

Colorado Springs, CO 80907 (US) EP-A1- 0 357 844 WO-A2-2007/120855
KR-B1- 920 010 717 US-A1- 2003 008 774
US-A1- 2009 143 516
EP 2 675 853 B1

Note: Within nine months of the publication of the mention of the grant of the European patent in the European Patent
Bulletin, any person may give notice to the European Patent Office of opposition to that patent, in accordance with the
Implementing Regulations. Notice of opposition shall not be deemed to have been filed until the opposition fee has been
paid. (Art. 99(1) European Patent Convention).

Printed by Jouve, 75001 PARIS (FR)

 EP 2 675 853 B1

Description

RELATED APPLICATIONS

5 [0001] This application claims benefit of priority to provisional application serial no. 61/443,170 filed February 15, 2011.

BACKGROUND

[0002] Thermochromic encapsulated dyes undergo a color change over a specific temperature range. By way of
10 example, 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. In one example, 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. For those skilled in the art of
thermochromic microcapsule synthesis, the precise control of the temperatures at which color changes occur is easily
15 achievable. For example, the ideal temperature of color change for cool beverages may range from 0°C to 15°C, while
the ideal temperature change for a warm or hot beverage may lie between 40°C and 65°C.
[0003] Thermochromic systems consist of three main components: an electron donating chromophore, an electron-
accepting color developer and a non-polar solvent that facilitates color change over a specified temperature range. The
properties of thermochromic systems have been exploited for more than 35 years. One technique used to produce the
20 thermochromic encapsulated dye is to combine water, dye, developer, oil, with urea-formaldehyde or melamine-formal-
dehyde resin and agitate to create a very fine emulsification. Interfacial tensions are such that the oil, dye and developer
end up on the inside of a urea-formaldehyde or melamine-formaldehyde capsule distributed primarily throughout the
water phase. The urea-formaldehyde or melamine-formaldehyde substance, while very hard and resistant to breakdown
at high temperature, is permeable. Though there has been significant improvement in microencapsulation technology,
25 thermochromic systems still have inherent chemical instability in polar solvent-based systems. For this reason, micro-
encapsulated thermochromic pigments have found limited applicability in solvent-based systems. For example United
States Patent No. 6,139,779 describes how low molecular weight solvents (generally less than 100 g/mol) have been
shown to permeate the relatively thin microcapsule wall and destroy the thermochromic system. A variety of thermo-
chromic inks may be purchased on commercial order, for example, from Chromatic Technologies, Inc. of Colorado
30 Springs, Colorado.
[0004] United States Patents 4,421,560 and 4,425,161 entitled "Thermochromic Materials" both state that thermo-
chromic 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.
[0005] Thermochromic dye is often sold in a slurry of pigment formed of encapsulated dye in a water base. It happens
35 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 lost. This can be an irreversible effect and,
therefore, it is important to adjust the pH prior to adding the thermochromic dye.
[0006] Several types of ingredients are traditionally added to ink formulations. The combination of all the ingredients
in an ink, other than the pigment, is called the vehicle. The vehicle carries the pigment to the substrate and binds the
40 pigment to the substrate. The correct combination of vehicle ingredients will result in the wetting of a pigment. 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
45 the binder and the colorant. These remaining ingredients may include reducers (solvents), waxes, surfactant, thickeners,
driers, and/or UV inhibitors.
[0007] Plain lids of the type used in beverage cans 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
50 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 can ends, tabs, caps
or closures.
55 [0008] Three piece 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

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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.
[0009] Thermochromic inks have been used successfully as indicators of a preferred usage temperature and as a
5 brand differentiator. Specifically, thermochromic inks have been used as cold indicators on aluminum cans, via metal
decorating inks, to communicate optimum consumption temperature to the consumer. This interactivity through thermo-
chromic color change so far does not extend to coating on can ends, tabs, caps and closures. To date, no such coatings
are commercially available. In part, this is due to significant mechanical forces that are applied to precoated coil stock
to form can ends, tabs, caps and other closures. Because of the stress and sheer during the tooling process the coating
10 must be flexible and resistant to cracking, flaking, and other damage. In addition, the coating must be sufficiently chemically
resistant to be unaffected by pasteurization or other processes. In order to meet the above requirements, the reversible
thermochromic coating described herein must contain a thermochromic pigment, a formulated vehicle system and/or a
commercially-available coating commonly used for can and coil coatings. In order to engineer additional coating prop-
erties, for example, chemical resistance or flexibility, components such as a curing agent, an accelerator or catalyst to
15 enhance curing, or wax may be added. Furthermore, thermochromic microcapsule wetting agents may be incorporated
to aid pigment dispersion, and one or more solvents may be selected. United States patent application 2003/0127415
A1 describes the use of thermochromic inks to apply printable images to metal lids and caps. United States Patent
Application 2011/0226636 A1 describes the use of thermochromic inks as applied in multiple ways to aluminum can
ends, the displaceable tear panel and the non-detachable tab. While these disclosures describe the application of
20 thermochromic inks, they do not teach practical means of achieving the claims described. Conventional thermochromic
inks are generally unsuited for the manufacturing stresses involved in making the can ends and tabs which, practically
speaking, are made from aluminum rolls commonly known as coil stock that must be coated prior to the machining
operations that form the can ends, tabs, caps and other closures. Because of the durability and chemical stability of
epoxy coatings, these are commonly applied to aluminum and metal cans where direct or indirect food contact may
25 occur. The prior art does not, however, provide detailed formulations for a reversible thermochromic epoxy-based, or
other resin systems, for use in can ends, tabs, caps or closures. Reversible thermochromic coating is known, for example,
for use in different applications. US 2009/0143516 A1 describes coating a latex glove, WO 2007/120855 A2 describes
coating a cast, US 2003/0008774 A1 describes coating a laminate and KR 920 010717 B1 describes coating a cloth.
[0010] It is problematic that existing thermochromic coatings fail to withstand the stresses of these manufacturing
30 operations which may, for example, excessively thin or scratch the coatings or crush the microcapsules forming the
thermochromic pigment.

SUMMARY

35 [0011] The presently disclosed instrumentalities overcome the problems outlined above and advance the art by pro-
viding reversible thermochromic can and coil coatings to fabricate can ends, tabs, caps and/or closures using aluminum
or steel alloys. Furthermore, the inventors have discovered processes in the manufacture of the thermochromic micro-
capsule as well as processing conditions when making the coating that enhance the solvent stability of the thermochromic
pigment.
40 [0012] The use of thermochromic systems as a substitute for conventional pigments in resin based coatings creates
an interactive effect which can provide an indicator or purely artistic effect. In addition to the visual appeal of thermochromic
can ends, tabs, caps and closures, they have also a functional purpose indicating the internal temperature of the beverage
within the can as, for example, the pigment changes from colorless to colored or from one color to a different color.
[0013] According to the invention, a thermochromic coating may include a pigment and a vehicle. In one aspect, the
45 pigment is present in an amount ranging from 1% to 40% of the coating by weight, and the vehicle forms the balance
of from 99% to 60% by weight. The pigment may be provided in a slurry form having various liquid content, so for
consistency the weight of pigment is assessed using pigment that is completely dry. For example, pigment that is provided
in a water-based slurry would be assessed after elimination of the water, although it is not strictly necessary to eliminate
the water when mixing all formulations.
50 [0014] The pigment includes thermochromic microcapsules. These are usually urea-formaldehyde or melamine-for-
maldehyde resins encapsulating a core that contains a thermochromic system including a thermochromic dye (such as
a leuco dye), a developer and a solvent that controls the color activation temperature of the dye and developer. Other
thermochromic systems are known to the art. Methods of forming thermochromic capsules with predetermined activation
temperatures are well known in the art. The pigment may also contain dyes or solids that impart color and are not
55 thermochromic in nature.
[0015] The vehicle contains a polymerizable resin that contains the pigment and may be, for example, epoxy, polyester,
urethane, acrylic acid and acrylate. These may incorporate curing agents as are known in the art, such as primary,
secondary, tertiary, and cyclic aliphatic amines, blocked amines (e.g. Hycat), amino resins with a range of alkylation,

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aromatic amines, polyamines, polyamides, amidoamines, ketimines, melamine resins, isocyanates or resins that can
be cured using ultraviolet radiation. Surfactants or other dispersing agents may facilitate dispersion of the pigment in
the vehicle. The dispersing agents may suitably include, for example, nonionic, anionic, cationic, or zwitterionic sur-
factants, polymers or copolymers, or reactive diluents such as aliphatic or cycloaliphatic glycidyl ethers. Nonpolar alkane
5 or aromatic solvents, polar, aprotic solvents such as esters, ketones, amides or polar, protic solvents such as alcohols
or acids may be added for rheological control.

In one embodiment, a thermochromic coating formulation includes:

Ingredient Weight Percent of Coating
10
Pigment* 1% to 40%
Vehicle
Polymerizable resin 5% to 30%
15 Dispersing agent 0% to 5%
Solvent 0% to 50%
Curing agent 0% to 25%
Wax 0% to 5%
20
*Assessed by solids content upon complete drying of pigment
capsules, but does not need to be dried and may be mixed as a slurry.

[0016] In one aspect, a reversible thermochromic coating for use in can and coil coatings contains a reversible ther-
25
mochromic pigment in an amount from 1% to 40% by weight of the coating, and a vehicle forming the balance of the
coating. According to the invention, the vehicle includes a resin selected from the group consisting of epoxy, polyester,
urethane, acrylic acid and acrylate resins, and combinations thereof. Commercially available thermochromic pigments
may be readily obtained in a variety of colors demonstrating color transition temperatures from about 5 °C and up to
about 65 °C. A range of color formulations may be made by mixing the pigment to include one or more of the following
30
reversible thermochromic colors: yellow, magenta, cyan, and black. These may be further mixed to include other dyes
or solid pigments that are non-thermochromic in nature. The pigment may change from a colorless state to a colored
state upon cooling to the reactive temperature, or to a colored state upon heating to the reactive temperature. It is
preferred that the microcapsules are formed of urea-formaldehyde or melamine-formaldehyde that is acid catalyzed to
enhance the inherent stability in polar, low molecular weight solvents having a molecular weight of about less than 100
35
g/mol.
[0017] When premised using a nonpolar solvent, the coatings can demonstrate shelf stability exceeding 14 or 45 days
when stored at about 20°C. Some coating formulations demonstrate shelf stability in excess of one year.
[0018] The curing agent is generally compatible with the resin for this purpose and may be, for example, a latent
blocked amine to initiate a polymerization reaction upon heating.
40
[0019] The coating is preferably roller-coated onto coil stock aluminum or steel and the roll stock aluminum is subse-
quently formed into one or more beverage can components. These components may be selected from the group consisting
of beverage can ends, beverage can tabs, bottle caps, and/or beverage container closures. The aluminum is preferably
an alloy that is commonly used in canning operations, such as aluminum alloy 5182-H48. The coating process preferably
occurs in one or more coats to yield a dried film with a thickness ranging from 1 mg/in2 up to 5.5 mg/in2.
45

BRIEF DESCRIPTION OF THE FIGURES

[0020]
50
Figure 1 compares beverage cans with ends that are coated with a thermochromic coating according to the present
disclosure and chilled to different temperatures corresponding to Fig. 1A and Fig. 1B.
Fig. 2 shows a beverage can lid having a pull tab with a thermochromic coating.
Fig. 3 shows a process of applying the coating to make thermochromically functional aluminum that can be used to
fabricate thermochromically functional beverage can components.
55

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 EP 2 675 853 B1

DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0021] Thermochromic ink coatings contain, in combination, a vehicle and a pigment including thermochromic micro-
capsules. The thermochromic microcapsules are, according to the invention, present in an amount ranging from 1% to
5 50% of the coating by weight on a sliding scale. The vehicle contains a solvent that is preferably present in an amount
ranging from 25% to 75% by weight of the coating.

Pigment

10 [0022] Careful preparation of encapsulated reversible thermochromic material enhances coating stability in the pres-
ence of low molecular weight polar solvents that are known to adversely affect thermochromic behavior. One skilled in
the art of microencapsulation can utilize well-known processes to enhance the stability of the microcapsule. For example,
it is understood that increasing the cross linking density will reduce the permeability of the capsule wall, and so also
reduces the deleterious effects of low molecular weight polar solvents. It is also commonly understood that, under certain
15 conditions, weak acids with a pKa greater than about 2 may catalyze microcapsule wall polymerization and increase the
resulting cross linking density. It is presently the case that using formic acid as a catalyst enhances solvent stability of
blue thermochromic microcapsules in the presence of low molecular weight ketones, diols, and aldehydes at room
temperature. Further, it is well understood that increasing the diameter of the thermochromic microcapsule can result
in enhanced solvent stability.
20 [0023] The selection of material for use as the nonpolar solvent for the thermochromic dye and color developer that
is encapsulated within the thermochromic pigment determines the temperature at which color change is observed. For
example, changing the solvent from a single component to a two-component solvent system can shift the temperature
at which full color is perceived almost 7°C from just under 19°C to 12°C. The present disclosure shows how to apply
this knowledge in preparing resin-based vehicle coatings for use in can and coil coatings with full color temperatures,
25 i.e., the temperature at which maximum color intensity is observed, as low as -5°C and as high as 65°C. No adverse
effects on the physical properties of the resulting coating were observed as the full color temperature was changed over
the above temperature range by the use of different straight chain alkyl esters, alcohols, ketones or amides.
[0024] Thermochromic materials including encapsulated thermochromic systems with a variety of color properties
may be purchased on commercial order from such companies as Chromatic Technologies, Inc., of Colorado Springs,
30 Colorado.
[0025] Control over observed color intensity is demonstrated in several ways, generally by presenting providing in-
creased amounts of pigment. For a typical coating, material thickness ranges from 1 mg/in2 to 6 mg/in2. Very intense
color is observed for coatings with thickness greater than about 3 mg/in2. Increasing thermochromic pigment solids can
also result in a more intense observed color even when coating thickness is decreased. However, dried film properties
35 such as flexibility and toughness may be compromised if too much thermochromic pigment is incorporated. The optimal
range of thermochromic pigment solids is within 5 to 40% by weight of the coating.

Vehicle

40 [0026] Physical properties of the finished coating can be significantly affected by the selection of resin to be used.
When no resin is used in formulating a reversible thermochromic coating, a matte finish is achieved that is able to be
formed into can ends, tabs, caps and/or other closures. While this result may be desired, the inclusion of a low viscosity,
relatively low molecular weight resin, monomer, oligomer, polymer, or combination thereof, can enhance gloss and affect
other physical film properties such as hardness, flexibility and chemical resistance. The resin is designed to supplement
45 the total solids deposited on the substrate, thus impacting the physical properties of the dried film. Any resin material,
monomer, oligomer, polymer, or combination thereof, that can be polymerized into the commercially-available can and
coil coating material is suitable for inclusion in the formulation of the current reversible thermochromic can and coil
coating. Acceptable classes of resins include, but are not limited to, epoxy, polyester, urethane, acrylic acid and acrylate,
or other types of resin systems with suitably high solids content.
50 [0027] Final coating properties such as chemical resistance, hardness and flexibility can be manipulated by selection
of cross linkers or curing agents. Materials that readily react with and incorporate into the selected resin system is suitable
for inclusion as a cross linker or curing agent. Examples include, but are not limited to, primary, secondary, tertiary, and
cyclic aliphatic amines, blocked amines, amino resins with a range of alkylation, aromatic amines, polyamines, polya-
mides, amidoamines, ketimines, melamine resins, isocyanates or resins that can be cured using ultraviolet radiation.
55 Care should be taken to balance reactivity needs with pot life / shelf life. For example, if the curing agent reacts too
quickly with the resin, the reversible thermochromic coating may cure before the coating can be applied to the aluminum
or steel substrate.
[0028] In order to ensure the reversible thermochromic coating fully cures before the coil is re-wound, accelerators

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and/or catalysts may be added to the coating formulation. Examples of suitable materials for use as cure accelerators
or catalysts include, but are not limited to, imidazoles, amidoamines, linear phenolics, blocked and unblocked acid
catalysts, isocyanates, dihydrazides or photoinitiators.
[0029] Coating properties can also be manipulated with the inclusion of natural or synthetic waxes. For example,
5 carnuba, polytetrafluoroethylene (PTFE), or a combination thereof may be included to affect physical film properties
such as slip, coefficient of friction and abrasion resistance.
[0030] Adequate dispersion of thermochromic pigment throughout the resin is an aspect of achieving high quality
coatings for commercial use. The inclusion of additional molecular or polymeric dispersing aids, such as nonionic, anionic,
cationic or zwitterionic surfactants, polymers or copolymers, can ensure adequate dispersion. Active diluents, in addition
10 to reacting with the resin selected, may also function as a dispersing aid. Furthermore, active diluents can reduce the
coating viscosity and affect film flexibility and impact resistance. Suitable materials to be included as an active diluent
include, but are not limited to, aliphatic or cycloaliphatic glycidyl ethers, monofunctional and polyfunctional glycidyl ethers.
[0031] Final adjustments to coating rheology may be made by the addition of select reducers, or solvents. A reversible
thermochromic coating can be adjusted to meet rheological criteria established for use in a roller coating application.
15 Many solvents are available for this purpose. Care should be exercised to select solvents most compatible with thermo-
chromic pigment systems. Nonpolar solvents or solvents of low polarity are preferred. However, modifications to ther-
mochromic pigment preparation initiated by the inventors as well as the different coating preparations available to the
inventors increased the solvent options available to include low molecular weight polar solvents such as esters, for
example butyl carbitol acetate, low molecular weight alcohols such as ethanol or butanol, or ketones such as acetone.
20 [0032] The chemical stability and shelf life of the reversible thermochromic coating may be enhanced in various ways.
In one aspect, this involves separating the thermochromic pigment from organic solvents. A two-part coating system
containing thermochromic pigment and resin in Part A and commercially-available coating material and other solvents
in Part B is then mixed immediately prior to coating aluminum or steel alloys. The shelf life of the fully mixed coating
material ranges from several days to many months depending on the identity of the other components selected.
25 [0033] For those situations for which a two-part solution is not preferable, stability can be balanced with convenience
by preparing a one-part reversible thermochromic coating. In this case, careful selection of formulation components is
paramount. The use of water-based commercially-available can and coil coating material enhances the shelf life stability
by minimizing the amount of organic solvents in contact with the thermochromic pigment system. In one example, coating
degradation was observed within 14 days when red thermochromic coatings were prepared using butyl carbitol acetate
30 and stored at room temperature. Enhanced stability was observed when formulation components were modified as well
as when stability enhanced thermochromic pigment systems were used.
[0034] The nonlimiting embodiments that follow teach by way of example and should not be construed as unduly
limiting the scope of this disclosure.

35 EXAMPLE 1-Two Part Coating

[0035]

Part A (30% by weight of coating)

40 Thermochromic pigment (any color)*

Part B (70% by weight of coating)

Clear Coating (an epoxy coating available from Watson Standard of Pittsburgh, Pennsylvania)

45 * This material may be purchased on commercial order from Chromatic Technologies, Inc. of Colorado Springs Colorado,
and may include for example S5BOXX3105W, a blue thermochromic slurry that goes from a colored to colorless state
when the temperature exceeds 31 °C.

EXAMPLE 2 - Two Part Coating

50
[0036]

Part A (60% by weight of coating)

45% Thermochromic Pigment (any color)*
55 50% Epoxy resin (for example Epon 863 available from Lawter of LaVergne, Tennessee)

3.3% Dispersing aid (for example Disperbyk 2025 available from Byk of Wallingford, Connecticut)

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 EP 2 675 853 B1

1.7% Curing agent (for example Ancamine 2458 available from Air Products of Allentown, Pennsylvania)

Part B (40% by weight of coating)

5 85% Clear Coating (an epoxy coating available from Watson Standard of Pittsburgh, Pennsylvania)

15% Solvent to reduce viscosity (for example, butyl carbitol acetate available from Lawter of LaVergne, Ten-
nessee)

10 * This material may be purchased on commercial order from Chromatic Technologies, Inc. of Colorado Springs Colorado,
and may include for example S5BOXX3105W, a blue thermochromic slurry that goes from a colored to colorless state
when the temperature exceeds 31°C.

EXAMPLE 3 One Part Coating

15
[0037]

20% (w/w) Thermochromic Pigment (any color)*

20 13% Polyester resin (for example, Decotherm 290 available from Lawter of LaVergne, Tennessee)

0.5% (w/w) Dispersing aid (for example, Byk 370 available from Byk of Wallingford, Connecticut)

7% (w/w) Curing agent 1 (for example, Cymel 328 available from Cytec Industries of Woodland Park, New Jersey)
25
1.5% (w/w) Curing agent 2 (for example, imidazole available from Aldrich of St. Louis, Missouri)

2% (w/w) Wax (for example, Fluoron 735 available from Lawter of LaVergne, Tennessee)

30 30% (w/w) Solvent (for example, ethyl-3-ethoxypropionate available from Univar of Redmond, Washington)

26% (w/w) Clear Coating (an epoxy coating available from Watson Standard of Pittsburgh, Pennsylvania)

EXAMPLE 4 One Part Coating

35
[0038]

15% (w/w) Thermochromic Pigment (any color)*

40 10% (w/w) Resin (for example, Epon 896 available from Lawter of LaVergne, Tennessee)

1.5% (w/w) Dispersing aid (for example, Disperbyk 112 available from Byk of Wallingford, Connecticut)

0.5% (w/w) Curing agent 1 (for example, Nacure 2500 available from King Industries of Norwalk, Connecticut)
45
4% (w/w) Curing agent 2 (for example, Cymel 325 available from Cytec Industries of Woodland Park, New Jersey)

1.5% (w/w) Wax - 0.5 wt % (for example, Ultrapoly 211 A available from Lawter of LaVergne, Tennessee)

50 5% (w/w) Solvent 1 (for example, Heloxy Modifier 62 available from Lawter of LaVergne, Tennessee)

21.5% (w/w) solvent 2 (for example, ethyl-3-ethoxypropionate available from Univar of Redmond, Washington)

41% (w/w) Clear Coating (an epoxy coating available from Watson Standard of Pittsburgh, Pennsylvania)
55
[0039] Fig. 1 compares the lids of identical beverage cans 100 (Fig. 1A), and 150 (Fig. 1 B). The cans 100, 150 , differ
in that can 100 is at room temperature and can 150 is chilled to a preferred temperature for human consumption of a
beverage inside can 150. Lids 102, 152 are coated with epoxy-based thermochromic coatings 104, 154. The relative

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 EP 2 675 853 B1

darkness of lid 152 compared to lid 102 indicates that a beverage (not shown) within can 150 is sufficiently chilled to a
recommended temperature for improved palatability. As is known in the art, the lids 102, 152 contain tabs 106, 156 that
may be pulled to open access to space within the interior walls of cans 100, 150, such that liquid or other matter may
be poured into or out of the cans through closures 108, 158 that are scored to rupture when the tabs 106, 156 are lifted.
5 [0040] As opposed to placing thermochromic ink on the entire lid, it is possible to coat selected elements of the can
lid, such as the just the tab, just the closure, or both the lid and the tab without coating the closure. This is shown for
example in Fig. 2 where can 200 has a tab 202 that is covered with a thermochromic coating as described above. The
same coating or one having a different color and/or color transition temperature may be selectively applied to any feature
of lid 201, such as surface 204, closure 206, an indented area 208 surrounding closure 206, and/or rim 210.
10 [0041] Fig. 2 shows a beverage can 200 with a pull tab 202 that has been covered with the coating of any of Examples
1 through 4. The tab 202 is manufactured from coil stock that is precoated with any of the coatings described above
before the tab is formed.
[0042] Fig. 3 is a process diagram that shows sequential processing steps 300 for applying the thermochromic coating
to coil stock of aluminum 302. As the sheet aluminum unwinds 303 from roll 302, a roller coater 304 receives an uncured
15 thermochromic coating material 306, as described above. This places a liquid coating or film 308 on the aluminum. This
film is cured, for example by the application of heat or ultraviolet radiation, at curing station 310, and the sheet 309
including the dried film 309 is coiled 311 onto roll 312. This roll 312 may then be used to make beverage can components
as discussed in context of Figs. 1 and 2. It will be appreciated that additional coating operations (not shown) may be
performed on sheet 309.
20 [0043] Those skilled in the art will appreciate that the various embodiments described herein teach by way of example
and not by limitation. These embodiments may be subjected to insubstantial changes without departing from the true
scope and spirit of the invention. Accordingly, the inventors hereby state their intention to rely upon the Doctrine of
Equivalents in protecting their rights in what is claimed.

25
Claims

1. A reversible thermochromic coating comprising,

a reversible thermochromic pigment including thermochromic microcapsules which encapsulate a core that contains
30 a thermochromic system including a thermochromic dye, a developer, and a solvent,
said reversible thermochromic pigment in an amount ranging from 1% to 50% by weight of said reversible thermo-
chromic coating, and
a vehicle forming the balance of the coating,
said vehicle including a resin selected from the group consisting of epoxy, polyester, urethane, acrylic acid and
35 acrylate resins, and combinations thereof,
wherein said reversible thermochromic coating coats coil stock aluminum or steel.

2. The reversible thermochromic coating of claim 1, wherein said reversible thermochromic coating coats said coil
stock aluminum to yield a dried film with a thickness ranging from 1 mg/in2 up to 5.5 mg/in2.
40
3. The reversible thermochromic coating of claim 1, wherein said coil stock aluminum or steel is subsequently formed
into one or more beverage can components.

4. The reversible thermochromic coating of claim 3, wherein said beverage can components are selected from the
45 group consisting of beverage can ends, beverage can tabs, bottle caps, and beverage container closures.

5. The reversible thermochromic coating of claim 3, wherein said beverage can component comprises a beverage can
tab.

50 6. The reversible thermochromic coating of claim 1, wherein said coating is roller-coated onto coil stock aluminum or
steel.

7. The reversible thermochromic coating of claim 1, wherein said thermochromic microcapsules achieve color change
between a temperature of about -5 °C and up to about 65 °C.
55
8. The reversible thermochromic coating of claim 1, wherein said thermochromic microcapsules change from a colorless
state to a colored state upon cooling to a reactive temperature.

8
 EP 2 675 853 B1

9. The reversible thermochromic coating of claim 1, wherein said thermochromic dye comprises a leuco dye.

10. The reversible thermochromic coating of claim 1, further comprising a curing agent which facilitates curing of said
resin.
5
11. The reversible thermochromic coating of claim 1, further comprising a conventional pigment or colored coating
material.

12. The reversible thermochromic coating of claim 1, wherein said resin is epoxy.
10

Patentansprüche

1. Reversible thermochrome Beschichtung, umfassend

15 ein reversibles thermochromes Pigment, das thermochrome Mikrokapseln umfasst, die einen Kern einkapseln, der
ein thermochromes System enthält, welches einen thermochromen Farbstoff, einen Entwickler und ein Lösungsmittel
umfasst,
das reversible thermochrome Pigment mit einer Menge, die von 1 Gew.-% bis 50 Gew.-% der reversiblen thermo-
chromen Beschichtung reicht, und ein Vehikel, das den Ausgleich der Beschichtung bildet,
20 wobei das Vehikel ein Harz umfasst, das aus der Gruppe ausgewählt ist, die aus Epoxy-, Polyester-, Urethan-,
Acrylsäure- und Acrylat-Harzen und Kombinationen davon besteht,
wobei die reversible thermochrome Beschichtung Bandmaterialaluminium oder -stahl beschichtet.

2. Reversible thermochrome Beschichtung nach Anspruch 1, wobei die reversible thermochrome Beschichtung Band-
25 materialaluminium beschichtet, um einen getrockneten Film mit einer Dicke, die von 1 mg/in2 bis 5,5 mg/in2 reicht,
zu ergeben.

3. Reversible thermochrome Beschichtung nach Anspruch 1, wobei das Bandmaterialaluminium oder der Bandmate-
rialstahl anschließend zu einem oder mehreren Getränkedosenbestandteilen geformt wird.
30
4. Reversible thermochrome Beschichtung nach Anspruch 3, wobei die Getränkedosenbestandteile aus der Gruppe
ausgewählt sind, bestehend aus Getränkedosenenden, Getränkedosenlaschen, Flaschenverschlüssen und Ge-
tränkebehälterverschlüssen.

35 5. Reversible thermochrome Beschichtung nach Anspruch 3, wobei der Getränkedosenbestandteil eine Getränkedo-
senlasche umfasst.

6. Reversible thermochrome Beschichtung nach Anspruch 1, wobei die Beschichtung auf das Bandmaterialaluminium
oder den Bandmaterialstahl mittels Walzenbeschichtung geschichtet ist.
40
7. Reversible thermochrome Beschichtung nach Anspruch 1, wobei die thermochromen Mikrokapseln zwischen einer
Temperatur von etwa -5 °C und bis zu etwa 65 °C eine Farbveränderung erreichen.

8. Reversible thermochrome Beschichtung nach Anspruch 1, wobei sich die thermochromen Mikrokapseln nach einem
45 Abkühlen auf eine reaktive Temperatur von einem farblosen Zustand zu einem farbigen Zustand verändern.

9. Reversible thermochrome Beschichtung nach Anspruch 1, wobei der thermochrome Farbstoff einen Leukofarbstoff
umfasst.

50 10. Reversible thermochrome Beschichtung nach Anspruch 1, die ferner ein Härtemittel umfasst, das das Aushärten
von dem Harz fördert.

11. Reversible thermochrome Beschichtung nach Anspruch 1, die ferner ein herkömmliches Pigment oder farbiges
Beschichtungsmaterial umfasst.
55
12. Reversible thermochrome Beschichtung nach Anspruch 1, wobei das Harz Epoxy ist.

9
 EP 2 675 853 B1

Revendications

1. Revêtement thermochromique réversible comprenant,

5 un pigment thermochromique réversible incluant des microcapsules thermochromiques qui encapsulent un

coeur qui contient un système thermochromique incluant un colorant thermochromique, un révélateur et un
solvant,
ledit pigment thermochromique réversible étant en une quantité située dans la plage de 1 % à 50 % en poids
dudit revêtement thermochromique réversible, et
10 un véhicule formant le reste du revêtement,
ledit véhicule incluant une résine choisie dans le groupe constitué des résines époxyde, polyester, uréthane,
acide acrylique et acrylate, et des combinaisons de celles-ci,
ledit revêtement thermochromique réversible recouvrant un aluminium ou un acier en rouleaux.

15 2. Revêtement thermochromique réversible selon la revendication 1, ledit revêtement thermochromique réversible

recouvrant ledit aluminium en rouleaux pour donner un film séché ayant une épaisseur située dans la plage de 1
mg/pouce2 à 5,5 mg/pouce2.

3. Revêtement thermochromique réversible selon la revendication 1, dans lequel ledit aluminium ou acier en rouleaux
20 est ensuite mis sous la forme d’un ou plusieurs composants de canette.

4. Revêtement thermochromique réversible selon la revendication 3, dans lequel lesdits composants de canette sont
choisis dans le groupe constitué des couvercles de canette, des anneaux de canette, des capsules pour bouteille
et des fermetures de récipient de boisson.
25
5. Revêtement thermochromique réversible selon la revendication 3, dans lequel ledit composant de canette comprend
un anneau de canette.

6. Revêtement thermochromique réversible selon la revendication 1, dans lequel ledit revêtement est appliqué au
30 rouleau sur l’aluminium ou l’acier en rouleaux.

7. Revêtement thermochromique réversible selon la revendication 1, dans lequel lesdites microcapsules thermochro-
miques présentent un changement de coloration entre une température d’environ -5 °C et une température maximale
d’environ 65 °C.
35
8. Revêtement thermochromique réversible selon la revendication 1, dans lequel lesdites microcapsules thermochro-
miques passent d’un état incolore à un état coloré en refroidissant à une température réactive.

9. Revêtement thermochromique réversible selon la revendication 1, dans lequel ledit colorant thermochromique com-
40 prend un colorant leuco.

10. Revêtement thermochromique réversible selon la revendication 1, comprenant en outre un agent de durcissement
qui facilite le durcissement de ladite résine.

45 11. Revêtement thermochromique réversible selon la revendication 1, comprenant en outre un pigment classique ou
un matériau de revêtement coloré.

12. Revêtement thermochromique réversible selon la revendication 1, dans lequel ladite résine est une résine époxyde.

50

55

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EP 2 675 853 B1

11
EP 2 675 853 B1

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 EP 2 675 853 B1

REFERENCES CITED IN THE DESCRIPTION

This list of references cited by the applicant is for the reader’s convenience only. It does not form part of the European
patent document. Even though great care has been taken in compiling the references, errors or omissions cannot be
excluded and the EPO disclaims all liability in this regard.

Patent documents cited in the description

• WO 61443170 A [0001] • US 20110226636 A1 [0009]

• US 6139779 A [0003] • US 20090143516 A1 [0009]
• US 4421560 A [0004] • WO 2007120855 A2 [0009]
• US 4425161 A [0004] • US 20030008774 A1 [0009]
• US 20030127415 A1 [0009] • KR 920010717 B1 [0009]

13