阅读说明：本技术 聚合物、热致变色剂和/或水凝胶组合物和设备，包括体现它们的产品以及制备它们的方法和工艺 (Polymer, thermochromic and/or hydrogel compositions and devices, including products embodying same, and methods and processes for making same ) 是由 范立涛 尤勇 潘云光 何东甲 R·曼戈 于 2018-03-02 设计创作，主要内容包括：聚合物、水凝胶和热致变色剂,包括体现它们的产品,使用它们的方法以及制备它们的工艺。在某些实施方式中,温度疗法包利用整合到固体、半固体或液体水凝胶中的热致变色剂。在优选的(但任选的)实施方式中,将热致变色剂整合到用作疗法包的温度交换材料的组合物中。在某些其他实施方式中,使用热致变色整合的温度交换材料的方法,或制造这种热致变色整合的温度交换材料的工艺和/或制造或使用体现这种材料的热包的方法或工艺。在某些特别优选的实施方式中,新型聚合物组合物和/或制备聚合物的工艺可以改善产品耐久性或寿命和/或改善使用周期或使用时间。(Polymers, hydrogels, and thermochromic agents, including products embodying them, methods of using them, and processes for making them. In certain embodiments, the temperature therapy package utilizes a thermochromic agent integrated into a solid, semi-solid, or liquid hydrogel. In a preferred (but optional) embodiment, the thermochromic agent is incorporated into a composition that is used as a temperature exchange material for the therapy pack. In certain other embodiments, methods of using thermochromic integrated temperature exchange materials, or processes of making such thermochromic integrated temperature exchange materials and/or methods or processes of making or using heat packs embodying such materials. In certain particularly preferred embodiments, the novel polymer compositions and/or processes for making polymers may improve product durability or longevity and/or improve service cycle or service time.)

1. A reversible thermochromic lining, wherein the lining comprises the following components in mass fraction:

the polymer comprises at least one of a polyacrylic polymer, a natural polymer, and a cellulose derivative.

2. A reversible thermochromic lining according to claim 1, wherein said polymer is a mixture of a polyacrylic polymer and a cellulose derivative.

3. A reversible thermochromic lining according to claim 1, wherein the polyacrylic acid polymer comprises at least one of the following components: polyacrylic acid, sodium polyacrylate, polyacrylamide and acrylamide/sodium acrylate copolymer.

4. A reversible thermochromic lining as claimed in claim 1 or 3, wherein the polymeric raw material substance for the polypropylene-based polymer comprises a monomer and an initiator; the monomers comprise acrylic acid and one or more of related acrylates, acrylamides, and acrylates; the initiator comprises one or more of potassium persulfate, ammonium persulfate, tert-butyl hydroperoxide and dimethylsulfonyl peroxide; the mass ratio of the monomer to the initiator is 50: 1-200: 1.

5. the reversible thermochromic liner of claim 1, wherein the natural polymer is selected from at least one of agar, ammonium alginate, algin, alginic acid, pullulan, tragacanth, calcium alginate, carrageenan, cassia gum, locust bean gum, quinoa starch, guar gum, dehydroxanthan gum, dextrin, carrageenan, gelatin, gellan gum, gum ghatti, magnesium alginate, natto gum, pectin, potassium alginate, potassium carrageenan, peach gum, rhizobia gum, sclerotium gum, sodium carrageenan, karaya gum, tamarind seed gum, tapioca starch, TEA-alginate, welan gum, and xanthan gum.

6. The reversible thermochromic liner of claim 1, wherein the cellulose derivative is selected from the group consisting of hydroxypropyloxycetalhexadecylhydroxyethylcellulose, carboxymethylcellulose calcium, C12-16 alkyl PEG-2 hydroxypropylhydroxyethylethylcellulose, carboxymethylcellulose acetate butyrate, carboxymethylcellulose, cellulase, cellulose acetate propionate, ascorbyl methylsilanol pectin (ascorbyl methyl silanol pectin), calcium octenyl succinate starch, glyceryl alginate, hydrolyzed cellulose gum, hydroxyethylchitosan, hydroxypropyl chitosan, hydroxypropyl guar gum, hydroxypropyl starch phosphate, hydroxypropyl xanthan gum, carboxymethyl chitin, carboxymethyl chitosan, sodium carboxymethyl dextrin, sodium polydextrose, sodium carboxymethyl starch, carboxymethyl dextran, sodium starch octenyl succinate, One or more of starch hydroxypropyltrimethyl ammonium chloride, cetyl hydroxyethylcellulose, croscarmellose, carboxymethyl hydroxypropyl guar gum, ethyl cellulose, sodium carboxymethylcellulose, hydrogenated tallow benzyldimethyl bentonite, hydroxybutyl methylcellulose, hydroxyethyl cellulose, hydroxypropyl methylcellulose, methyl cellulose, methyl ethyl cellulose, methyl hydroxyethyl cellulose, microcrystalline cellulose, nonylphenol polyether hydroxyethyl cellulose, oxidized cellulose, sodium cellulose sulfate, and stearic acid PG-hydroxyethyl cellulose sulfonate.

7. A reversible thermochromic lining according to claim 1, wherein the dispersant comprises at least one of tween-20, tween-40, tween-60, tween-80, tween-85, span-40, span-60 and span-80.

8. The reversible thermochromic interlining of claim 1, wherein the dispersing aid comprises at least one of allyl alcohol, n-propanol, butanetriol, polyethylene glycol, and polyglycerol.

9. A reversible thermochromic lining according to claim 1, wherein the thermochromic powder is selected from at least one of a thermal color development type and a thermal discoloration type.

10. A reversible thermochromic lining according to claim 9, wherein said thermochromic powder has a particle size of 5-20 microns.

11. A reversible thermochromic lining as claimed in claim 1, wherein the solvent comprises at least one of the following components: water, glycerol, ethanol and propylene glycol.

12. A reversible thermochromic lining according to claim 1, wherein the lining is in the form of a gel or microspheres.

13. A method for preparing a reversible thermochromic lining according to claim 1, comprising the steps of: and uniformly mixing the polymer, the dispersing agent, the dispersing aid, the thermochromic powder and the solvent.

14. A method for making a reversible thermochromic lining according to claim 13, wherein the method comprises the steps of: premixing the thermochromic powder with a dispersant, a solvent and a dispersing auxiliary agent to obtain thermochromic color paste, and mixing the thermochromic color paste with a polymer to obtain the gel lining.

15. A method for making a reversible thermochromic lining according to claim 13, wherein the method comprises the steps of:

s1, mixing a dispersing agent, a dispersing aid, a solvent and thermochromic powder, and then adding the mixture to a polymerization raw material substance of a polypropylene-based polymer or a mixture of a polymerization raw material substance of a polypropylene-based polymer and a cellulose derivative to obtain a mixed liquid;

s2, polymerizing the mixed liquid at 40-88 ℃ to obtain a gel lining or a microsphere lining.

16. The method for producing a reversible thermochromic lining according to claim 15, wherein in step S2, the polymerizing includes a step of directly polymerizing the mixed liquid to obtain a gel lining.

17. The method for producing a reversible thermochromic interlining according to claim 15, wherein in step S2, the polymerizing includes a step of dropping the mixed liquid into an oil phase to perform polymerization to obtain a microsphere interlining.

18. A method for making a reversible thermochromic lining according to claim 17, wherein after polymerization is complete, the method comprises the steps of: cleaning to remove oil phase and drying at low temperature;

the cleaning time is 10-30 minutes, and the cleaning temperature is 0-45 ℃;

the low-temperature drying temperature is 40-80 ℃, and the low-temperature drying time is 1-4 hours.

19. A thermochromic product encapsulated by the reversible thermochromic liner of claim 1.

20. A temperature therapy kit comprising:

a temperature exchange material encapsulated in a temperature therapy pack shell for providing temperature therapy to a user, the temperature exchange material in combination with a thermochromic agent, the combination of the temperature exchange material and the thermochromic agent comprising a reversible thermochromic therapeutic material comprising, in mass fractions:

the amount of polymer is 5-40%;

the amount of the thermochromic powder is 1% -7%;

the amount of the dispersant is 1.5 to 33 percent;

the amount of the dispersing aid is 1.5 to 35 percent;

the amount of the solvent is 5 to 30 percent; and is

Wherein the polymer comprises at least one of the following components: polyacrylic acid polymers, natural polymers, and cellulose derivatives.

21. A temperature therapy kit comprising:

a temperature exchange material encapsulated in a temperature therapy pack shell for providing temperature therapy to a user, the temperature exchange material in combination with a thermochromic agent, the combination of the temperature exchange material and the thermochromic agent comprising a reversible thermochromic therapeutic material comprising, in mass fractions:

the amount of polymer is 5-40%;

the amount of the first thermochromic agent is 1% -3.5%;

the amount of the second thermochromic agent is 1% -3.5%;

the amount of the dispersant is 1.5 to 33 percent;

the amount of the dispersing aid is 1.5 to 35 percent;

the amount of the solvent is 5 to 30 percent; and is

Wherein the polymer comprises at least one of the following components: polyacrylic acid polymers, natural polymers, and cellulose derivatives.

Technical Field

The invention described herein relates to polymers, hydrogels, and thermochromic agents, including products embodying them, methods of using them, and processes for making them. In certain embodiments, the disclosed invention relates to temperature therapy packages utilizing thermochromic agents integrated into solid, semi-solid, or liquid hydrogels. In a preferred (but optional) embodiment, the invention described herein relates to a thermochromic agent incorporated into one or more compositions of a temperature exchange material used as a therapy pack. In certain other embodiments, the invention described herein relates to methods of using thermochromic integrated temperature exchange materials, or processes of making such thermochromic integrated temperature exchange materials and/or methods or processes of making or using heat packs embodying such materials. In certain particularly preferred embodiments, one or more of the inventions described herein relates to novel polymer compositions and/or processes for preparing polymers in which product durability or longevity is improved and/or in which the number of use cycles is improved or in which the time of use is increased.

Background

The term "thermochromic" as used throughout the specification is generally used in the art to refer to pigments or dyes that undergo a color change when exposed to a change in temperature. Similarly, when used to describe such pigments or dyes, the term "reversible" reflects that the color change obtained during a thermal cycle can be reversed. Thermochromic pigments or dyes (or "thermochromic agents" in general) are known in various fields from the novelty product field to the medical industry. Typically, thermochromic agents are used to add or create aesthetic effects, have no practical purpose other than entertainment, or are used as a sort indicator to identify temperature changes in products in which they are embodied or otherwise utilized.

For example, U.S. patent No. 5,219,625 ("Matsunami") discloses the use of thermochromic materials for clothing and toys for recreational purposes. In contrast, for example, international publication No. WO2016/093788 ("Isildak") teaches the application of thermochromic agents to imaging blood vessels to, for example, identify cancerous tumors that include a higher density of blood vessels (according to this publication). U.S. publication No. 2009/0143516 ("MacDonald") also teaches the use of thermochromic agents in the medical field, but applies such agents to gloves to enable a determination of whether a surgical glove has been punctured. Among other uses of thermochromic agents, U.S. publication No. 2014/0291585 ("touuka") teaches introducing a thermochromic agent into an ink of a writing instrument so that if a mistake is made in writing, the writing ink (which includes a thermochromic pigment) can be heated by friction to visually disappear.

In addition to the above-mentioned uses, the technical knowledge of the use of thermochromic agents in the field of temperature therapy is limited. For example, U.S. publication No. 2013/0073018 ("Harwood") teaches the use of applying a thermochromic film to a thermal pack "cover" or "overlay" for notifying a user when the pack is ready for use. The Harwood reference, however, has a number of disadvantages that the applicant of the present application has overcome or addressed by the present application for invention. For example, the thermal pack cover is not an accurate indicator of the temperature of the therapy pack, nor is it a reliable indicator that the therapy pack is ready for therapeutic use. The hot pack cover is exposed to ambient air and also to the skin of the pack user, or to a refrigerator surface, or a table or other surface, with which the cover is in contact when the hot pack is used refrigerated or placed on a surface prior to use. Thus, as opposed to providing an accurate measurement of the "core" temperature of the temperature therapy pack itself, the thermal pack cover taught by Harwood may sometimes change color in response to (or at least be affected by) ambient air or skin (or other surface) temperature. Thus, a user such as the package disclosed in Harwood may be misled by the color change features disclosed therein. This is particularly true of the embodiments disclosed in Harwood, where the thermochromic agent is incorporated into a fabric cover that is wrapped over the disclosed temperature therapy packs to impart a particular aesthetic appearance (see, e.g., Harwood paragraph [0029 ]).

The "temperature exchange material" of the thermal pack is the payload of the thermal pack which stores hot or cold temperatures (heat, lacking heat if a cold pack) for transfer to the skin or body part of the end user. Notably, Harwood does not teach anywhere to incorporate a thermochromic agent into the temperature exchange material of the heat pack itself. Furthermore, Harwood does not teach anywhere how to technically implement such heat exchange materials integrated into a heat pack, or how to manufacture such heat packs. In particular, the applicant has found that there are a number of difficulties and obstacles to doing so.

The applicant of the present invention has also found problems associated with hydrogels of the prior art, including the durability of the hydrogels in semi-solid or solid form. Furthermore, applicants of the invention disclosed herein have discovered that there is a need in the art for hydrogels in the form of solid, semi-solid, and/or fluid gels that permanently incorporate thermochromic agents. More generally, applicants have also discovered that there is a need for polymers that incorporate thermochromic agents that have improved lifetimes (e.g., in storage and otherwise) and/or have increased numbers of usable cycles and/or exhibit improved service times.

In view of the above-mentioned deficiencies in the prior art, applicants have addressed, overcome or overcome (solve), in whole or in part, these deficiencies with one or more of the methods, processes or apparatus described below. In certain embodiments, the methods, processes, or apparatuses described herein are directed to addressing one or more of the above-identified deficiencies or needs of the prior art. It is also an object of the methods, processes or apparatus described herein to address other shortcomings in the prior art and/or other improved needs, whether currently known or not, which will become more readily apparent to those skilled in the art given the present disclosure.

Disclosure of Invention

In some embodiments, the present invention relates to improvements in polymers and/or the use of thermochromic agents (e.g., thermochromic pigments or dyes) in combination with (combined with) or in combination with (in connection with) polymers. In other embodiments, the invention relates to a therapy package for delivering hot/cold temperature therapy to a body part of a user. In a preferred embodiment, a hot/cold temperature therapy pack is provided that includes or employs a thermochromic agent. In certain other embodiments, the invention relates to hydrogels, including semi-solid, and fluid forms of hydrogels that exhibit improved durability and/or incorporate or otherwise contain thermochromic agents. In certain preferred embodiments, these improved hydrogels are used in combination with thermochromic agents as one or more temperature exchange materials for hot/cold temperature therapy packs.

In preferred embodiments, the present application relates to novel thermochromic polymer or hydrogel compositions, and processes for making such polymers or hydrogels having useful thermochromic properties. In these embodiments, processes and methods are provided for usefully (and preferably) persistently integrating thermochromic agents into polymers and hydrogels. In related embodiments, the present application relates to devices (e.g., temperature therapy packs) manufactured using the thermochromic compositions disclosed herein and/or using the novel manufacturing methods and processes described herein. Each and every such embodiment, individually or in combination, is contemplated by the applicants to be one or more aspects of the present invention, whether an apparatus, method or process.

Although applicants of the present invention contemplate that certain embodiments are most preferred, any use of the term "preferred" is not intended to be limiting in any way. Furthermore, the word "embodiment" should be interpreted broadly to reflect examples of the class (genus) or class (species) of the invention described herein. That is, whether described as "preferred" or as "embodiments" (or as "preferred embodiments"), the examples to which these terms refer are still optional, and variations thereof are still considered by the applicants to be within the scope of the invention.

In one such example (i.e., optional) preferred embodiment, a temperature therapy pack is provided that utilizes a hydrogel formed as a plurality of beads (or microspheres) as a filler material to provide temperature exchange properties. In this embodiment, the hydrogel beads are mounted into a preferably transparent therapy enclosure such that the hydrogel beads are visually visible to a user of the therapy enclosure. Further, in this preferred example, the hydrogel beads include or otherwise utilize one or more thermochromic agents (e.g., incorporated into the beads) such that the beads will exhibit a useful color change effect upon exposure to a change in temperature.

As a practical example of this preferred embodiment, a temperature therapy pack filled (partially or completely) with a hydrogel (in the form of beads or a fluid gel) is constructed with a specially selected thermochromic composition (or combination of thermochromic agents) such that the thermochromic agent provides one or more visual indicia to the user. In particular, the thermochromic agent or combination thereof is preferably selected to indicate that the therapy pack is hot or cold enough to provide hot or cold temperature therapy, respectively, to the user. Conversely, if the therapy package is not hot or cold enough for temperature therapy, the package is preferably designed with a different color imparted by the thermochromic agent, or simply a lack of color (due to discoloration of the thermochromic agent) to indicate lack of readiness. For example, in applicants' most preferred embodiment, the temperature therapy pack is comprised of a transparent envelope such that the thermochromic hydrogel beads included in the pack gel are visible to the user. In this most preferred embodiment, the hydrogel beads appear blue when the therapy pack is not ready to provide temperature therapy (e.g., when they are at or near normal room temperature). Conversely, when the hydrogel beads of the therapy pack are displayed as white or transparent, the beads (acting as heat exchange material) have been heated sufficiently to provide heat therapy to the user. In certain preferred embodiments, the packets may be microwaved to heat them prior to use. However, other methods of heating the packet may also be used, such as by placing the packet in hot water. Similarly, when the hydrogel beads of the therapy pack show a purple color, the beads have cooled sufficiently (e.g., in a refrigerator or in a cold water bath) to provide cold therapy to the user. Of course, other color combinations or schemes may be selected and used for providing temperature (or other state) indicia by selecting different thermochromic pigments or by otherwise tailoring the combination or composition of thermochromic agents used.

When applicants of the invention disclosed herein began the process of creating the novel temperature therapy package described herein, a number of unexpected obstacles and problems were encountered during the development process. For example, the thermochromic properties of hydrogel beads impregnated with a thermochromic agent have an insufficient lifetime (e.g., experience fading), and/or the hydrogel beads themselves exhibit poor structural durability. This problem is exacerbated when hydrogel beads are installed in a prototype therapy pack containing a lubricant (e.g., water) and/or antifreeze composition such that the hydrogel beads are free to move between other beads and/or such that the lubricant does not freeze to a solid during cooling in a refrigerator. Other problems encountered relate to the uniform and sufficient distribution of thermochromic pigments in the hydrogel to obtain product uniformity and/or sufficient thermochromic visual effect, respectively, for adequate adjuvant thermotherapy.

To address these unforeseeable problems, applicants of the invention described herein unexpectedly discovered that reversible thermochromic properties of sufficient lifetime can be obtained using the novel manufacturing processes and/or compositions described herein, and that improved durability of hydrogel beads can be obtained. These novel compositions and processes include, but are not limited to, the novel hydrogel compositions disclosed herein, as well as methods and processes for making or processing hydrogel beads. These compositions and/or processes allow for the manufacture of reversible thermochromic temperature therapy packs having a suitably long "shelf life" such that they can be successfully commercialized without significant loss of product performance over time as the product is shipped or placed on store shelves prior to use. These uniquely created novel temperature therapy packages (optionally) are also capable of changing color through thermal cycling over a greater number of cycles of use. Furthermore, the duration of the color display is also improved.

One non-limiting example of a reversible thermochromic material developed by the applicant, embodying these improvements in the prior art, comprises the following composition in mass fractions: the amount of polymer is 5-40%; the amount of the thermochromic powder is 1-7; the amount of the dispersant is 1.5 to 33 percent; the amount of the dispersing aid is 1.5 to 35 percent; the amount of solvent is 5-30%. Preferably, in this example, the polymer comprises at least one of the following components: polyacrylic acid polymers, natural polymers, and cellulose derivatives.

In at least one embodiment, the reversible thermochromic materials disclosed above are used as part of a temperature therapy package. In one such embodiment, for example, there is provided a temperature therapy pack comprising: a temperature exchange material encapsulated in a temperature therapy pack shell (enclosure) for providing temperature therapy to a user, the temperature exchange material in combination with a thermochromic agent, the combination of the temperature exchange material and the thermochromic agent comprising a reversible thermochromic therapeutic material comprising, in mass fractions: the amount of polymer is 5-40%; the amount of the thermochromic powder is 1% -7%; the amount of the dispersant is 1.5 to 33 percent; the amount of the dispersing aid is 1.5 to 35 percent; the amount of the solvent is 5 to 30 percent; and wherein the polymer comprises at least one of the following components: polyacrylic acid polymers, natural polymers, and cellulose derivatives.

In certain exemplary embodiments utilizing the above-described reversible thermochromic materials, the polyacrylic acid polymer may optionally include at least one of the following components: polyacrylic acid, sodium polyacrylate, polyacrylamide, acrylamide/sodium acrylate copolymer, acrylate/ethylammonium chloride acrylate copolymer, acrylamide/ethyltrimethyl ammonium chloride acrylate/ethylammonium chloride acrylate copolymer, acrylamide/sodium acryloyldimethyltaurate copolymer, acrylate/acetoacetoxyethyl methacrylate (acetoxy methacrylate) copolymer, acrylate/behenyl polyether-25 methacrylate/HEMA cross-linked polymer-2, acrylate/C5-8 alkyl acrylate copolymer, acrylic acid/ethyl methacrylate/HEMA cross-linked polymer copolymer, acrylic acid/ethyl methacrylate copolymer, acrylic acid/sodium acrylate/ethyl methacrylate copolymer, acrylic acid/ethyl methacrylate copolymer, acrylic acid/ethyl acrylate copolymer, acrylic acid/ethyl acrylate/, acrylate/C10-30 alkyl acrylate crosspolymer, acrylate/C10-3 alkyl methacrylate copolymer, acrylate/ceteareth-20 methacrylic acid crosspolymer, acrylate/ceteareth-20 itaconate copolymer, acrylate/ceteareth-20 methacrylate polymer, acrylate crosspolymer-3, acrylate crosspolymer-4, acrylate/laureth-25 methacrylate copolymer, acrylate/laureth-25 acrylate copolymer, acrylate/laureth-25 itaconate, acrylate/steareth-50 acrylate copolymer, acrylate/laureth-25 acrylate copolymer, acrylate/laureth-3 acrylate copolymer, acrylate/ceteareth-20 acrylate copolymer, acrylate/laureth-25 acrylate copolymer, acrylate/laureth-50, Acrylate/steareth-20 itaconate copolymer, acrylate/steareth-20 methacrylate copolymer, acrylate/steareth-30 methacrylate copolymer, acrylate/stearyl methacrylate copolymer, acrylate/vinyl isodecanoate (vinyl isocyanate) crosspolymer, acrylate/vinyl neodecanoate crosspolymer, acrylic acid/acrylonitrile copolymer, acrylic acid/phosphocholine ethylene glycol acrylate crosspolymer, ammonium acrylate/acrylonitrile copolymer, ammonium acrylate (ammonium acrylate) copolymer, ammonium acryloyl dimethyl taurate/carboxyethyl acrylate (carboxyl ethyl acrylate) crosspolymer, acryloyl dimethyl taurate/steareth-8 methacrylate copolymer, acryloyl dimethyl taurate/stearyl alcohol polyether-8 methacrylate copolymer, and mixtures thereof, C18-22 alkyl PEG-25 methacrylate/2-methacrylic acid diethylaminoethyl ester copolymer, glyceryl acrylate/acrylic acid copolymer, HEA/sodium acryloyldimethyl taurate/steareth-20 methacrylate copolymer, potassium polyacrylate, sodium acrylate/acrolein copolymer, sodium acrylate/acrylonitrile copolymer, sodium acrylate/acryloyldimethyl taurate/dimethylacrylamide crosspolymer, sodium acrylate/beheneth-25 methacrylic acid crosspolymer, sodium acrylate copolymer, sodium acrylate/sodium acrylamidomethylpropanesulfonate copolymer, sodium acrylate/sodium acryloyldimethyl taurate/acrylamide copolymer, sodium acrylate/sodium acryloyldimethyl taurate copolymer, sodium acryloyl, Sodium acrylate/vinyl isodecanoate crosspolymer, sodium acrylate/vinyl acetamide copolymer, sodium acrylate/vinyl alcohol copolymer, sodium acryloyldimethyl taurate/acrylamide/VP copolymer, sodium styrene/acrylate copolymer, sodium polymethacrylate, sodium polyacrylate starch, sodium taurate acrylate/acrylic acid/acrylonitrile copolymer, starch/acrylate/acrylamide copolymer and trimethylamine acrylate/acrylonitrile copolymer.

Although not in all embodiments, in certain preferred embodiments, the polypropylene polymer described above is (preferably) produced by the reaction of a monomer with an initiator. In at least one such embodiment, the monomer includes acrylic acid and related acrylates, acrylamides, and acrylates, and the initiator includes potassium persulfate, ammonium persulfate, t-butyl hydroperoxide, and dimethyl sulfonyl peroxide. In a particularly preferred (but still optional) embodiment, the mass ratio of monomer to initiator is 50: 1-200: 1. as a further benefit but optional preference, the starting material for the polymerization of the polyacrylic polymer also includes a cross-linking agent comprising N, N' -methylenebisacrylamide. In addition, the preferred mass ratio of the crosslinking agent to monomer is about 1: 100-1: 200.

in preferred, but still optional, embodiments of the reversible thermochromic aspect of the invention described herein, it has been found useful to use a natural polymer comprising at least one of the following components: at least one of agar, ammonium alginate, algin (algin), alginic acid (alginic acid), pullulan, tragacanth gum, calcium alginate, carrageenan (carrageenen), cassia gum, locust bean gum, quinoa starch, Guar gum (Guar gum, Guar bean gum), dehydroxanthan gum (dehydroxanthan gum), alsas gum (alsace gum), carrageenan, gelatin (gelatin), Gellan gum (Gellan gum), Ghatti gum (Ghatti gum), magnesium alginate, natto gum, pectin (pectin ), potassium alginate, potassium carrageenan, peach gum, rhizobium gum, sclerotium gum, sodium carrageenan, gum (gum sterculia), tamarind seed gum (Tamarindus Indica gum), tapioca starch, TEA-alginate, Welan gum (xanthan gum), and xanthan gum. In a most preferred embodiment, the natural polymer is at least one polymer selected from the group comprising agar, algin, carrageenan, gelatin, gellan gum and xanthan gum. The natural polymer has a long-chain macromolecular structure and excellent thickening and gelling effects. They are useful in the novel processes and compositions described herein to effectively encapsulate thermochromic powders without damaging the thermochromic powders, thereby resulting in a stronger structure and longer thermochromic lifetime.

In combination with the optional embodiments described above, or in other embodiments described elsewhere herein, the cellulose derivative utilized in the reversible thermochromic material may optionally comprise: hydroxypropyloxycetalhydroxyethylcellulose, carboxymethylcellulose calcium, C12-16 alkyl PEG-2 hydroxypropylhydroxyethylethylcellulose, carboxymethylcellulose acetate butyrate, carboxymethylcellulose, cellulolytic enzyme, cellulose acetate propionate, octenylcalcium succinate starch, alginic acid glyceride, hydrolyzed cellulose gum, hydroxyethylchitosan, hydroxypropylchitosan, hydroxypropylguar gum, hydroxypropylstarch phosphate, hydroxypropylxanthan gum, carboxymethylchitin (ethylchitin/carboxymethylchitin), carboxymethylchitin, sodium carboxymethylchitin (sodium carboxymethylchitin), sodium carboxydextrin, sodium polyglucoside, sodium carboxymethylstaryl, sodium carboxymethyldextran, sodium starch octenylsuccinate, starch hydroxypropyltrimonium chloride, hexadecylhydroxyethylcellulose, crosslinked carboxymethylcellulose, Carboxymethyl hydroxypropyl guar gum, ethyl cellulose, sodium carboxymethyl cellulose, hydrogenated tallow benzyl dimethyl bentonite, hydroxybutyl methyl cellulose, hydroxyethyl cellulose, hydroxypropyl methyl cellulose, methyl hydroxyethyl cellulose, microcrystalline cellulose, nonylphenol polyether hydroxyethyl cellulose, oxidized cellulose, sodium cellulose sulfate and/or stearic acid PG-hydroxyethyl cellulose sulfonate. Most preferably, the cellulose derivative is one or more materials selected from the group comprising calcium carboxymethylcellulose, carboxymethyl hydroxyethyl cellulose, sodium carboxymethylcellulose, hydroxyethyl cellulose, hydroxypropyl cellulose and hydroxypropyl methyl cellulose. Such cellulose derivatives have excellent thickening effects for use in the compositions and processes described herein. Like the natural polymers specified above in applicants' compositions and processes, they also effectively encapsulate the thermochromic powder without damaging the thermochromic powder. This results in a stronger structure and a longer thermochromic lifetime.

In certain embodiments, the reversible thermochromic materials described herein (preferably) use a dispersant comprising tween-20, tween-40, tween-60, tween-80 and tween-85 and Span (Span) -40, Span-60 and Span-80. In these or other preferred embodiments, the dispersing aid may optionally comprise allyl alcohol, n-propanol, butanetriol, polyethylene glycol and/or polyglycerol. In the most preferred embodiment, the dispersing aid is allyl alcohol, n-propanol or butanetriol. The use of these most preferred dispersing aids unexpectedly results in better dispersing performance, resulting in more uniform color and longer life.

In some embodiments of the present invention, it has been found useful to utilize thermochromic agents in the form of thermochromic powders. In an exemplary embodiment using such thermochromic powders, one (identity) powder may be selected such that the material develops or changes color when heated or cooled (thermochromic type) or loses color when heated or cooled (thermochromic type). In still other embodiments, a blend of powders or other thermochromic agents may be used to achieve multiple thermochromic or color-changing effects in the same product. Preferably, the thermochromic powder has a color development temperature in part in any temperature range from-20 ℃ to 80 ℃. The thermochromic powders are distinguished by characterizing the powder using a temperature color change threshold.

The method disclosed herein for preparing a reversible thermochromic material comprises the following process steps: the polymer, the dispersant, the dispersing aid, the thermochromic powder and the solvent are uniformly mixed. In one particularly effective example, applicants have determined that premixing thermochromic powders in the following process produces particularly desirable compositions and functional results: and premixing the thermochromic powder with a dispersant, a solvent and a dispersing auxiliary agent to obtain the thermochromic color paste. Then, the thermochromic paste is mixed with a polymer to obtain a gel composition. Using this preparation step, described in more detail in the detailed description section of the description, a homogeneous dispersion of the thermochromic agent in the gel composition is more easily obtained.

In an alternative embodiment, the thermochromic gel composition may be prepared as follows: mixing the dispersing agent, the dispersing assistant, the solvent and the thermochromic powder. The resulting mixture is then added to a solution containing monomers and an initiator for preparing the polymer to obtain a mixed liquid. The liquid was then added dropwise to the oil to effect polymerization. Then, after the polymerization reaction is completed, the resultant product is washed and dried to form a thermochromic material.

In certain preferred embodiments, the solvent used to make the reversible thermochromic material may comprise at least one of the following components: water, glycerol, ethanol and propylene glycol.

When developing the products and processes described herein, applicants of the invention disclosed herein have discovered that pigment particle size is an important factor in achieving suitable product performance and durability. More specifically, applicants have unexpectedly found that if the particle size is too large, the particles cannot be effectively dispersed in the polymers and gels described herein, which can result in gel structure disruption (e.g., particularly where the polymer forms a semi-solid form, such as beads). Further, if the particle size is too small, the displayed color is weak and/or the thermochromic life is short due to a small amount of the thermochromic material applied. Furthermore, the use of small particle size thermochromic powders requires more stringent process preparation parameters and yields are obtained in lower yields. In addition, it has been found that the use of too small a particle size is an obstacle to obtaining a sufficiently long shelf life in the final product. Thus, applicants have discovered that heretofore unknown useful ranges of particle sizes for beneficial thermochromic pigments are typically between 5 and 20 microns, which unexpectedly provides the advantages described elsewhere herein. Therefore, it is most preferable to use a thermochromic powder having a fine particle (or grain) size of between 5 and 20 μm. However, the fines can also be between about 3-25 microns or between about 1-30 microns in size.

Thermochromic colorants can be made from a variety of molecules including, for example, spiropyrans, spirooxazines, lactones, spirolactones, diazahydrorhodamine lactones (diazahydrorhodamine lactone), fulgides, chromenes, azobenzenes, quinones, styrylquinolines, fluorans, dianthrones, polythiophenes, polysilanes, polydiacetylenes, phenolphthalein, merocyanines, anilides, diphenylamines, diphenylmethanephthalides, phenylindolphthalides, indolphthalides, diphenylmethaneazaphthalides, phenylindole-azaphthalides, dihydroazulenes, vinyl heptafulvenes (vinylheptafulvene), quinazolines, bisquinazolines, trisubstituted pyridines, liquid crystals, and combinations thereof. More specific examples may include 6-nitro-1 ',3',3 '-trimethylspiro- [ 2H-1-benzofuran-2, 2' -indoline ] (6-nitro-1 ',3',3 '-trimethllpiro- [ 2H-1-benzopyran-2, 2' -indoline ]); (E) -2- [1- (2, 5-dimethyl-3-furanyl) ] ethylene- (Z) -3-ethylene-succinic anhydride; 1, 2-dicyano-1, 2-bis- (2,4, 5-trimethyl-3-thienyl) ethane; 2, 3-bis (2,4, 5-trimethyl-3-thienyl) maleic anhydride; 3, 3-bis (p-dimethylaminophenyl) -6-dimethylaminophthalide (phthalide); 3- (4-diethylaminophenyl) -3- (1-ethyl-2-methylindol-3-yl) phthalide; 3, 3-bis (1-n-butyl-1-2-methylindol-3-yl) phthalide; 3, 3-bis (2-ethoxy-4-diethylaminophenyl) -4-azaphthalide; 3- [ 2-ethoxy-4- (N-ethylanilino) phenyl ] -3- (1-ethyl-2-methylindol-3-yl) -4-azaphthalide; 3,6-dimethoxyfluoran (3, 6-dimethoxyfluoran); 3, 6-di-n-butoxy fluorane; 2-methyl-1-6- (N-ethyl-N-p-tolylamino) fluoran (2-methyl-1-6- (N-ethyl-N-tolylamino) fluoran); 3-chloro-6-cyclohexylaminofluoran; 2-methyl-6-cyclohexylaminofluoran; 2- (2-chloroanilino) -6-di-n-butylaminofluoran; 2- (3-trifluoromethylanilino) -6-diethylaminofluoran; 2- (N-methylanilino) -6- (N-ethyl-N-p-tolylamino) fluoran, 1, 3-dimethyl-6-diethylaminofluoran; 2-chloro-3-methyl-6-diethylaminofluoran; 2-anilino-3-methyl-6-diethylaminofluoran; 2-anilino-3-methyl-6-di-n-butylaminofluoran; 2-dimethylamino-3-methyl-6-diethylaminofluoran; 1, 2-benzo-6-diethylaminofluoran; 1,2-benzo-6- (N-ethyl-N-isobutylamino) fluoran; 1,2-benzo-6- (N-ethyl-N-isopentyl-amino) fluoran (1, 2-benzol-6- (N-ethyl-N-isoamyl-amino) fluoran); 2- (3-methoxy-4-dodecyloxystyryl) quinoline (2- (3-methoxy-4-dodecoxystyryl) quinoline); spiro [5H- (1) benzopyran (2,3-d) pyrimidine-5,1'(3' H) -isobenzofuran ] -3'-one (spiro [5H- (1) benzopyrano (2,3-d) pyrimidine-5,1' (3'H) isobenzofuran ] -3' -one); 2- (diethylamino) -8- (diethylamino) -4-methyl-spiro [5H- (1) benzopyranyl (2,3-d) pyrimidine-5,1' (3' H) isobenzofuran ] -3' -one; 2- (di-n-butylamino) -8- (di-n-butylamino) -4-methyl-spiro [5H- (1) benzopyranyl (2,3-d) pyrimidine-5,1' (3' H) isobenzofuran ] -3' -one; 2- (di-n-butylamino) -8- (diethylamino) -4-methyl-spiro [5H- (1) benzopyranyl (2,3-d) pyrimidine-5,1' (3' H) isobenzofuran ] -3' -one; 2- (di-N-butylamino) -8 (N-ethyl-N-isopentylamino) -4-methyl-spiro [5H- (1) benzopyranyl (2,3-d) pyrimidine-5,1' (3' H) isobenzofuran ] -3' -one; 2- (di-n-butylamino) -8- (di-n-butylamino) -4-benzene (2- (di-n-butyllamino) -8- (di-n-butyllamino) -4-phenyl) and combinations thereof.

In addition to organic molecules, inorganic compounds can also produce thermochromic reactions, such as: ag2Hg2I4, Cu2HgI4, SrCO3 and MnO 2. In some cases, the use of solutions of inorganic compounds such as CoCl2 can be used to synthesize thermochromic materials in the presence of unsaturated esters, peroxides, and promoters.

As an additional optional feature of the embodiments described herein, applicants have found that uv light negatively impacts product durability and performance. Thus, in some preferred (but still optional) embodiments, a uv coating or filter layer is utilized, such as applied over a clear heat jacket (or elsewhere).

Drawings

Certain examples of the invention are now described below, for certain non-limiting embodiments thereof, as shown in the following figures.

The accompanying drawings, which are filed herewith and form a part of this patent application, each illustrate a non-limiting example embodiment or one or more components of an embodiment of applicants' invention. While these drawings depict certain preferred embodiments of applicants 'invention and certain features thereof that are particularly desirable, they are intended to be illustrative only and should not be construed as limiting the scope of applicants' invention.

FIG. 1A shows one non-limiting embodiment of a temperature therapy pack according to the present invention.

FIG. 1B illustrates another perspective of the embodiment of the temperature therapy pack shown in FIG. 1A.

Fig. 2 shows an alternative embodiment of a temperature therapy pack according to the present invention.

Fig. 3 shows an alternative embodiment of a temperature therapy pack according to the present invention.

Fig. 4 shows an alternative embodiment of a temperature therapy pack according to the present invention.

Fig. 5 shows an alternative embodiment of a temperature therapy pack according to the present invention.

Fig. 6 shows an alternative embodiment of a temperature therapy pack according to the present invention.

Detailed Description

For a more complete understanding of the present invention, reference is now made to the following descriptions of various illustrative and non-limiting embodiments thereof, taken in conjunction with the accompanying drawings, in which like reference numbers indicate like features. These exemplary embodiments, disclosed and discussed below, will aid in a further understanding of the invention described and claimed herein, but are not intended to limit the scope of the invention in any way.

Referring initially to fig. 1, one exemplary embodiment of a heat pack is illustrated in which the novel compositions described herein have utility. As shown, the thermal pack 1 is a therapy pack consisting of a bag or envelope 3 filled with a plurality of spherical elements 5, said spherical elements 5 collectively containing a temperature exchange material that can be heated or cooled to provide a hot or cold temperature therapy to the user. More specifically, in the illustrated embodiment, the shell (or bag) of the thermal pack is a polyvinyl chloride ("PVC") (front) sheet 3a formed into a desired shape, such as the semi-circular pack structure depicted in fig. 1 (e.g., for treating mastitis), which is joined along the perimeter of each respective sheet to a second (rear) sheet 3b of similar shape. Preferably this is done by heat or infrared welding, or using other suitable techniques (e.g. adhesives) to form the sealing edge 9 as shown. Of course, the manner in which the sheets are connected to form the pack is not important to the invention, and different methods of connection or construction may be used to assemble the pack. Similarly, the enclosure may be constructed of other materials, such as, for example, polyethylene ("PE"), or any other suitable material or combination of materials. Preferably, suitable materials include one or more of flexibility, durability when exposed to heat or cold (and/or thermal cycling), and the ability to exhibit transparent or translucent characteristics (i.e., visual transparency). Similarly, the bag need not be made of separate sheets, but may be extruded or prepared using a single sheet fold (sealing the edges), for example.

As shown, by joining only the edges or peripheries of the pieces, a sealed edge 9 is obtained, while having the interior of the shell or bag with a defined volume, which is filled with a plurality of spherical elements 5. As described in further detail in connection with the examples provided below, preferably, the spherical elements 5 are semi-solid gel beads that are formed from a polymer hydrogel impregnated with a thermochromic agent 7 (see fig. 1B) in a novel process to achieve improved bead durability and improved thermochromic properties, including increased color change functional lifetime and increased number of color change cycles (i.e., the product can change color more than prior art products).

As will be readily appreciated, because thermochromic hydrogel beads are utilized (in this embodiment), package 1 is preferably constructed using an envelope that is transparent or at least includes a transparent portion so that the color changing characteristics of the beads within package 1 can be observed by the package user. Thus, for example, the entire enclosure may be transparent, or alternatively, one side may be transparent and the other side formed of an opaque fabric to provide comfort. Further alternatively, a transparent window may be provided in the envelope which is otherwise opaque, so that the thermochromic bead may be observed by the user.

As noted above, preferred embodiments of the invention described herein utilize thermochromic pigments incorporated into the temperature therapy pack so that the (approximate) temperature of the therapy pack can be readily determined by simply observing the color of the pack itself. By thus incorporating the thermochromic properties, it can be readily determined whether the pack has been heated or cooled, and is therefore ready to provide temperature therapy, by simply observing the color of the therapy pack. Furthermore, it can be determined which type of therapy the pack is ready to deliver by simply observing the pack. Nevertheless, it is always recommended to measure the temperature of the heated or cooled therapy pack (to confirm that it is not too hot or too cold) prior to use to prevent burns or frostbite.

For the thermal treatment to be therapeutic, the temperature of the hot/cold pack should be at least a few degrees celsius higher than the skin temperature of the user. Similarly, for cold treatment to be therapeutic, the temperature of the hot/cold pack should be at least a few degrees celsius lower than the skin temperature of the user. Thus, for effective cold therapy, the temperature exchange material of the therapy pack (e.g., element 5 of pack 1) should be cooled to a suitable cold temperature, for example, by cooling the pack in a refrigerator (or using a cold water bath or other suitable method). Instead, for effective thermal therapy, the temperature exchange material of the therapy pack should be heated to a suitable thermal temperature, which can be achieved by microwaving (or using hot water or other suitable methods) the pack. For safety reasons, excessively high or excessively low temperatures should always be avoided. Therefore, the temperature of the pack should always be tested before use.

Recognizing that certain temperature ranges are desirable, preferred embodiments of the heat packs described herein are configured such that color indicia are displayed when the temperature exchange material falls within such temperature ranges, and also such that separate color indicia are displayed when the temperature exchange material falls outside of those temperature ranges. For example, in one particularly preferred embodiment, the package is configured to include a temperature exchange material composition that includes a thermochromic agent specifically selected such that the exemplary thermal package appears blue at room temperature (non-therapeutic temperature), purple when cooled to a temperature range suitable for physician-recommended cold therapy, and white or transparent when heated to a temperature range suitable for physician-recommended hot therapy. Of course, any temperature ranges described herein are not intended to be limiting, and the heat packs described herein may be customized to display such colors in different temperature ranges (or, in another example, different colors in the same range).

Generally, thermochromic colorants act by selectively absorbing a portion of the visible spectrum, causing the remainder of the spectrum to be reflected and thus observed. Thus, when a thermochromic colorant is incorporated into a heat exchange material (e.g., a solid, semi-solid, or continuous gel), the apparent color of the gel at a given temperature will depend on the color reflected (i.e., unabsorbed) at the respective temperature. In this same regard, it is important to note that the thermochromic material can be designed (or selected) such that it displays a color above or below a threshold temperature (i.e., develop or turn on), or decolours above or below a threshold temperature (i.e., turn off). For example, a red discolored thermochromic powder may exhibit red color at temperatures below 0 ℃ but not exhibit color (i.e., colorless) at temperatures above 0 ℃. In contrast, the red-developed thermochromic powder may show no color (i.e., show no color) at temperatures below 50 ℃, but show red color at temperatures above 50 ℃.

As described herein, as one aspect of many improvements to the prior art, the applicant has discovered a composition and process that results in a heat pack product that visually indicates three temperature ranges using only two thermochromic agents, thereby saving the cost of using a third thermochromic agent, while also resulting in a heat exchange material in gel form that is more stable and exhibits improved reversible thermochromic properties. As an example of such an improved heat exchange gel, the gel is formed from a composition specifically selected such that the gel exhibits a blue color at room temperature (between about 0 and 38 degrees celsius), a colorless/white color above 38 degrees celsius (e.g., at a temperature effective for heat therapy), and a purple color below 0 degrees celsius (e.g., at a temperature effective for cold therapy). As described in more detail below, such products synergistically utilize two thermochromic agents to produce a third color by simultaneously reflecting two colors (within a preselected temperature range) such that the spectra of the reflected two colors are visually blended to appear as the third color. In this particular embodiment, for example, the thermochromic pigment is selected such that the first-in this case blue-thermochromic agent discolors above 38 degrees celsius (absorbs all wavelengths to appear transparent or white) and otherwise appears blue at any temperature below 38 degrees celsius. The second thermochromic agent-in this case red-typically appears white or transparent at any temperature above 0 degrees celsius, but develops red below this temperature. Thus, in the temperature range where the blue thermochromic pigment is not discolored (and thus shows a blue color) and the red thermochromic pigment develops to show a red color-in this case, the temperature range is below 0 degrees celsius-the reflected blue and red spectra combine and show a purple color visually to the human eye.

As noted above, in the exemplary embodiment shown, the exemplary product exhibits three colors-white/colorless, blue, and purple over three different temperature ranges, but only two thermochromic pigments are used. In this case, eliminating the use of a third thermochromic pigment (to obtain the third color) not only saves costs (i.e., the thermochromic pigment is expensive), but also results in a more structurally stable, better performing color product, particularly when the thermochromic pigment used is blended into a powder having a fine particle size selected between about 5 and about 20 microns. In this case, the fine particle size contributes to this better performance, such as using less thermochromic pigment (lower amount of pigment, thereby replacing less polymer, thereby producing a stronger gel product).

In the embodiment just described above, two thermochromic powders are blended with a polymer mixture, which is further processed to form a continuous gel or a plurality of semi-solid (or solid) hydrogel beads. In an exemplary embodiment employing beads, the resulting gel bead product is then mounted in a (preferably) transparent heat pack shell, as a plurality of spherical elements 5, and then functions as the temperature exchange material of the heat pack depicted in fig. 1. Thus, because the thermochromic pigment is integrated into the temperature exchange material itself, the pack 1 more accurately represents the true temperature of the therapy pack (the temperature of the outer envelope is sensitive to the surrounding air, surfaces in contact therewith, etc.), among other advantages described herein, as compared to mounting the thermochromic pigment in the outer envelope.

As shown in fig. 1, the pack 1 is designed and intended to be heated (e.g. in microwaves) and cooled (e.g. to a freezing temperature) through multiple heating and cooling cycles, so that both heat therapy and cold therapy (in replacement therapy treatment or alternating therapy treatment) can be delivered using the same therapy pack. Thus, the novel thermochromic hydrogels described herein are composed of the compositions described herein using the methods described herein such that they can be repeatedly heated and cooled without losing the structural integrity of the hydrogel. Thus, in the embodiments of hydrogel-forming (preferably, deformable semi-solid) spherical beads described herein, the heating and cooling cycles do not degrade the bead structure (i.e., the beads will retain a bead shape). Similarly, in embodiments employing a continuous gel, the continuous gel is not adversely affected by the heating and cooling cycle. As such, the thermochromic agents used in the various embodiments described herein are impregnated within hydrogels using compositions and methods that result in long-lasting integration and improved thermochromic (i.e., color change) properties.

General procedure：

In general, a method of preparing a thermochromic polymer for use as a heat exchange material is carried out using the following steps:

step 1: mixing the dispersing agent, the dispersing assistant, the solvent and the thermochromic powder. The premixed thermochromic composition is combined with the original polymeric raw material substance obtained from the polypropylene-based polymer (and/or cellulose derivative) to obtain a mixed liquid. Preferably, the pH of the mixed liquor is maintained between about 3 and 10.

Step 2: polymerization of the mixed liquid was started at 40-88 ℃ to obtain a thermochromic hydrogel (used in the form of continuous gel or microspheres). High reaction temperatures are avoided, which can damage or destroy the thermochromic powder (or its properties) or lead to colloidal implosion. Too low a reaction temperature is avoided, which can lead to failure of the polymerization.

In step 2, if the microspheres are being prepared, the mixed liquid is dropped into an oil solution (e.g., silicone oil) in which beads are formed during polymerization. The microspheres (or beads) are then washed to remove the oil. The washing time is preferably about 10 to 30 minutes, and the washing temperature is preferably about 0 to 45 ℃. The microspheres are then dried at low temperature, preferably between 40-80 c, for about 1-4 hours. Applicants have found that it is desirable to avoid higher drying temperature ranges because such higher drying temperatures can damage thermochromic pigments, resulting in shortened pigment lifetimes and reduced usable color change periods. In contrast, applicants have found that drying at lower temperatures reduces process efficiency.

Non-limiting example embodiments: