Phase-change nano material, ink composition comprising same, method and application

Abstract

The invention relates to a phase change nano material, which comprises a core based on mesoporous nano particles; a first response indicator, wherein the first response indicator is loaded in the mesopores based on the mesoporous nanoparticles; a shell mechanically constraining the core, the shell comprising a phase change polymer; wherein the first response indicator can be released from the shell when the phase-change nano material is placed in a temperature environment above the phase-change temperature of the phase-change polymer, and compared with a multi-layer structural design of a traditional temperature indicator, the ink composition disclosed by the invention can be used for realizing printing, so that the cost is reduced when the ink composition is used as the temperature indicator. Meanwhile, operation is convenient, the material selection range is wide, and application and popularization are easy.

Description

Technical Field

[0001] The present invention relates to the field of temperature monitoring and application technology, and specifically to a phase change nanomaterial. More specifically, the phase change nanomaterial can be used in an ink composition with temperature indication and monitoring capabilities. The present invention also relates to the preparation of the above-mentioned phase change nanomaterial and ink composition, and products containing the ink composition. Background Art

[0002] Currently, temperature monitoring methods on the market can be divided into electronic and non-electronic technologies. Electronic instruments are generally large and suitable for large products or entire boxes of products. They are costly and have the potential for mid-process failure. Non-electronic temperature monitors generally rely on gas or liquid diffusion. When the monitored substance is heated and melted, specific substances present in it react to produce a color indicator. However, they are relatively expensive and easily damaged, limiting their scope of use.

[0003] Compared to measuring with instruments or based on other indicators, being able to quickly and intuitively distinguish the storage quality of a product with the naked eye can greatly enhance confidence in the product and work efficiency for both merchants and consumers. Patent CN208706144U discloses a temperature-indicating functional label based on temperature-variable ink, which uses a combination of an ordinary ink pattern layer and a reversible temperature-variable ink pattern layer. The reversible temperature-variable ink pattern displays its specific color above the critical temperature of the temperature change and is colorless below the critical temperature of the temperature change. Patent CN220251216U discloses a liquid crystal temperature-variable label, which uses multiple groups of liquid crystal temperature-variable ink layers protruding from the upper surface of the substrate layer to produce a reversible temperature-sensitive color change display effect at different temperatures. These reversible temperature-variable ink labels are not only complex in structure, but also difficult to monitor whether the product is at an excessively dangerous temperature, and it is difficult to judge the storage quality of the product. Patent CN105419485B discloses an anti-counterfeiting water-based irreversible temperature-changing ink and its preparation method. The ink uses a diacetylenic diol-based irreversible color-changing pigment and is produced using a static mixer. The ink irreversibly changes from blue to red within a temperature range of 50°C to 70°C. However, the number of organic compounds capable of such irreversible color changes is limited, the color change is single, and the monitoring temperature range is narrow, making widespread use difficult.

[0004] Therefore, it is of great significance to invent a temperature indicator with simple structure, easy operation and the ability to monitor multiple temperatures simultaneously. Summary of the Invention

[0005] The purpose of this application is to address the above technical problems existing in the prior art and provide a phase change nanomaterial, including its ink composition, method and application.

[0006] According to the first aspect of the present invention, the present application provides a phase change nanomaterial, wherein when the ambient temperature is above the polymer phase transition temperature, the polymer in the shell undergoes a phase transition, and the phase change nanomaterial can release a first response indicator loaded in its mesopores.

[0007] Specifically, a phase-change nanomaterial includes: a core based on mesoporous nanoparticles;

[0008] a first response indicator loaded in the mesopores of the mesoporous nanoparticle-based particles;

[0009] a shell mechanically constraining the core, the shell comprising a phase change polymer;

[0010] Wherein, when the phase-change nanomaterial is placed in a temperature environment above the phase-change temperature of the phase-change polymer, the first response indicator can be released from the shell.

[0011] In certain embodiments, the mesoporous nanoparticles are selected from one or more of mesoporous nano-silica, mesoporous nano-alumina, and mesoporous graphitic carbon nitride, all of which contain amino groups on their surfaces.

[0012] In certain embodiments, the first response indicator is a cryptic dye or a triggering substance.

[0013] In certain embodiments, the cryptic dye is a fluoran dye or a triarylmethane dye.

[0014] In certain embodiments, the leuco dye is blue pigment-8, green pigment-5, red pigment-16, melanin-1, crystal violet lactone, thermosensitive scarlet dye, 3,3-bis(N-octyl-2-methylindole)phthalide, 6'-(diethylamino)-1',3'-dimethylfluoran, 3-diethylamino-6-chlorofluoran, 6-dimethylamino-3,3-bis(4-dimethylaminophenyl)phthalide, leuco crystal violet, 7-[4-(diethylamino)-2-ethoxyphenyl]-7-(2-methyl-1-octyl-1H-indole-3 -yl)3,4-B]pyridin-5(7H)-one, 4,4'-[(9-butyl-9H-carbazol-3-yl)methylene]bis[N-methyl-N-phenylaniline], 2-phenylamino-3-methyl-6-dibutylaminofluoran, 2-phenylamino-3-methyl-6-diethylaminofluoran, 3',6'-dimethoxyfluoran, 3,3-bis(4-diethylamino-2-ethoxyphenyl)-4-azaphthalide, heat (pressure) sensitive green TF-G, and 3-(N-ethyl-4-toluinyl)-6-methyl-7-anilinofluoran.

[0015] In certain embodiments, the initiating species is a Lewis acid donating material, an oxidative metal ion donating material, or a hydrogen ion donating material.

[0016] In certain embodiments, the material providing a Lewis acid is at least one of a diaryliodonium salt, a triarylsulfonium salt, an alkylsulfonium salt, an iron arene salt, a sulfonyloxyketone, and a triarylsiloxyether.

[0017] In certain embodiments, the material providing oxidative metal ions is selected from at least one of salts containing Zn, Fe, Sn, Pb, Cu, Hg, Ag, Pt, and Au metal ions.

[0018] In certain embodiments, the material providing hydrogen ions is selected from one or more of bisphenol A, bisphenol F, bisphenol S, 4-hydroxy-4'-isopropoxydiphenyl sulfone, and DBSP (2,4-diphenylsulfonylphenol).

[0019] In certain embodiments, the phase-change polymer is a phase-changeable polymer having a phase-change temperature of 36°C to 80°C.

[0020] According to the second aspect of the present invention, the present application also provides a method for preparing the above-mentioned phase change nanomaterial, comprising the following steps: S1, dispersing mesoporous nanoparticles in a first response indicator to obtain mesoporous nanoparticles loaded with the first response indicator; S2, adding a shell material monomer to the mesoporous nanoparticles loaded with the first response indicator, and generating the phase change nanomaterial under the action of a free radical initiator.

[0021] In certain embodiments, based on 100 parts by weight of the mesoporous nanoparticles, the amount of the first response indicator is 10-20 parts, the amount of the shell material monomer is 20-40 parts, and the amount of the free radical initiator is 0.04-0.08 parts.

[0022] In certain embodiments, the shell material monomer is one or more of diethylene glycol hexadecyl ether monomethacrylate, diethylene glycol octadecyl ether monomethacrylate, diethylene glycol eicosyl ether monomethacrylate, diethylene glycol behenyl ether monomethacrylate, diethylene glycol hexacosyl ether monomethacrylate, and diethylene glycol triacontyl ether monomethacrylate.

[0023] According to the third aspect of the present invention, the present application also provides an uncured ink composition, which comprises the phase change nanomaterial defined above, and also includes a film-forming resin, a second response indicator, a leveling agent, a defoaming agent and an organic solvent, wherein, when the first response indicator is a recessive dye, the second response indicator is a triggering substance; when the first response indicator is a triggering substance, the second response indicator is a recessive dye.

[0024] In certain embodiments, based on 100 parts by weight of the film-forming resin component, the amount of the phase change nanomaterial is 20-40 parts, the second response indicator is 10-20 parts, the leveling agent is 1-2 parts, the defoaming agent is 1-2 parts, and the organic solvent is 10-20 parts.

[0025] In certain embodiments, the film-forming resin is selected from at least one of acrylic resin, polyurethane, polyester, and epoxy resin.

[0026] In certain embodiments, the cryptic dye is a fluoran dye or a triarylmethane dye.

[0027] In certain embodiments, the leuco dye is blue pigment-8, green pigment-5, red pigment-16, melanin-1, crystal violet lactone, thermosensitive scarlet dye, 3,3-bis(N-octyl-2-methylindole)phthalide, 6'-(diethylamino)-1',3'-dimethylfluoran, 3-diethylamino-6-chlorofluoran, 6-dimethylamino-3,3-bis(4-dimethylaminophenyl)phthalide, leuco crystal violet, 7-[4-(diethylamino)-2-ethoxyphenyl]-7-(2-methyl-1-octyl-1H-indole-3 -yl)3,4-B]pyridin-5(7H)-one, 4,4'-[(9-butyl-9H-carbazol-3-yl)methylene]bis[N-methyl-N-phenylaniline], 2-phenylamino-3-methyl-6-dibutylaminofluoran, 2-phenylamino-3-methyl-6-diethylaminofluoran, 3',6'-dimethoxyfluoran, 3,3-bis(4-diethylamino-2-ethoxyphenyl)-4-azaphthalide, heat (pressure) sensitive green TF-G, and 3-(N-ethyl-4-toluinyl)-6-methyl-7-anilinofluoran.

[0028] In certain embodiments, the initiating species is a Lewis acid donating material, an oxidative metal ion donating material, or a hydrogen ion donating material.

[0029] In certain embodiments, the material providing a Lewis acid is at least one of a diaryliodonium salt, a triarylsulfonium salt, an alkylsulfonium salt, an iron arene salt, a sulfonyloxyketone, and a triarylsiloxyether.

[0030] In certain embodiments, the material providing oxidative metal ions is selected from at least one of salts containing Zn, Fe, Sn, Pb, Cu, Hg, Ag, Pt, and Au metal ions.

[0031] In certain embodiments, the material providing hydrogen ions is selected from one or more of bisphenol A, bisphenol F, bisphenol S, 4-hydroxy-4'-isopropoxydiphenyl sulfone, and DBSP (2,4-diphenylsulfonylphenol).

[0032] According to the fourth aspect of the present invention, the present application also provides a method for preparing the above-mentioned ink composition, which comprises uniformly mixing the phase change nanomaterial, the mixed film-forming resin, the second response indicator, the initiator, the leveling agent, the defoaming agent and the organic solvent.

[0033] According to the fifth aspect of the present invention, the present application also provides a coated product, comprising: a substrate; and a cured coating layer located on the substrate, wherein the coating layer is obtained by printing the above-mentioned ink composition and then curing it with ultraviolet light.

[0034] According to a sixth aspect of the present invention, the present application also provides the use of the above-mentioned ink composition as a temperature indicator in the packaging of toys, printed materials, decorations, writing tools, and medical products.

[0035] The beneficial effect of the present application is that it provides a phase-change nanomaterial and an ink composition containing the same, wherein the phase-change nanomaterial is loaded with a first response indicator in the mesopores of its mesoporous nanoparticles, and at the same time, a shell of a phase-change polymer can be grafted around the core of the mesoporous nanoparticles through a RAFT reaction, so that the first response indicator in the mesopores can be released under conditions higher than the phase change temperature of the polymer, and react with the second response indicator in the ink composition, thereby sensitively achieving an irreversible change from colorless to colored. Compared with the multi-layer structure design of traditional temperature indicators, the ink composition of the present invention can be printed when used as a temperature indicator, and is convenient to operate, has a wide range of material selection, and is easy to promote and apply. BRIEF DESCRIPTION OF THE DRAWINGS

[0036] Figure 1 This is a schematic diagram of the structure of the phase change nanomaterial before color change;

[0037] Figure 2 Schematic diagram of the structure of phase-change nanomaterials releasing the first response indicator in an environment above the phase-change temperature of the polymer;

[0038] Reference Number:

[0039] 101-mesoporous nanoparticles;

[0040] 102-mesopore;

[0041] 103-housing;

[0042] 104-First response indicator. DETAILED DESCRIPTION

[0043] To make the purpose, technical solutions and advantages of this application clearer, the technical solutions of this application will be clearly and completely described below in conjunction with the specific embodiments and drawings of this application. Obviously, the described embodiments are only part of the embodiments of this application, not all of them, and are not intended to limit the scope of the invention. Based on the embodiments in this application, all other embodiments obtained by ordinary technicians in this field without making creative work are within the scope of protection of this application.

[0044] In the present invention, unless otherwise specified, the term "temperature environment" has the corresponding meaning commonly used in this field, and refers to the actual temperature environment in which the phase-change nanomaterial, the ink composition, and the coated article are located.

[0045] As described in the prior art, although there are many technical solutions for temperature indicators, it is still desirable to provide a temperature indicator that accurately indicates temperature, is printable, and has a relatively simple structure.

[0046] Specifically, the present application provides a phase change nanomaterial, combined with Figure 1 and Figure 2 As shown, a phase-change nanomaterial according to a specific embodiment of the present invention comprises: a core based on mesoporous nanoparticles 101; a first response indicator 104, which is loaded within the mesopores 102 of the mesoporous nanoparticles; and a shell 103 mechanically constraining the core, the shell comprising a phase-change polymer. When the phase-change nanomaterial is exposed to a temperature above the phase-change temperature of the phase-change polymer, the first response indicator 104 can be released from the shell. One of the main features of the present invention is that it utilizes the different phase-change temperatures of a given phase-change polymer to achieve the release of the first response indicator at different temperatures, exhibiting irreversible high-temperature transient color change characteristics, thereby achieving the technical effect of thermal indication.

[0047] According to some embodiments of the present invention, the mesoporous nanoparticles are selected from one or more of mesoporous nano-silica, mesoporous nano-alumina, and mesoporous graphitic carbon nitride, all of which contain amino groups on their surfaces.

[0048] According to some embodiments of the present invention, the first response indicator is a recessive dye or an initiating substance, either of which is loaded into the mesopores of the mesoporous nanoparticles. A recessive dye is a dye that develops color upon binding to protons. In a color-changing system, it serves as the electron-donating moiety, and its molecule can adopt two chemical forms, one of which is essentially colorless. The initiating substance is a compound that reversibly releases protons, i.e., an electron-withdrawing compound. The electron-donating moiety binds to the electron-withdrawing compound, resulting in color.

[0049] There is no special restriction on the specific material of the recessive dye, as long as it is a substance that can bind protons and develop color. In some embodiments of the present invention, the recessive dye is a fluoran dye or a triarylmethane dye. In a further preferred embodiment, the recessive dye is blue pigment-8, green pigment-5, red pigment-16, melanin-1, crystal violet lactone, thermosensitive scarlet dye, 3,3-bis(N-octyl-2-methylindole)phthalide, 6'-(diethylamino)-1',3'-dimethylfluoran, 3-diethylamino-6-chlorofluoran, 6-dimethylamino-3,3-bis(4-dimethylaminophenyl)phthalide, leuco crystal violet, 7-[4- At least one of (diethylamino)-2-ethoxyphenyl]-7-(2-methyl-1-octyl1H-indol-3-yl)3,4-B]pyridin-5(7H)-one, 4,4'-[(9-butyl-9H-carbazol-3-yl)methylene]bis[N-methyl-N-phenylaniline], 2-phenylamino-3-methyl-6-dibutylaminofluoran, 2-phenylamino-3-methyl-6-diethylaminofluoran, 3',6'-dimethoxyfluoran, 3,3-bis(4-diethylamino-2-ethoxyphenyl)-4-azaphthalide, heat (pressure) sensitive green TF-G, and 3-(N-ethyl-4-toluinyl)-6-methyl-7-anilinofluoran.

[0050] There are no particular restrictions on the specific material of the initiating substance, as long as it is a compound that can reversibly release protons. In some embodiments of the present invention, the initiating substance is a material that provides a Lewis acid, a material that provides an oxidizing metal ion, or a material that provides a hydrogen ion. In a further preferred embodiment, the material that provides a Lewis acid is at least one of a diaryliodonium salt, a triarylsulfonium salt, an alkylsulfonium salt, an iron arene salt, a sulfonyloxyketone, and a triarylsiloxane. The material that provides an oxidizing metal ion is selected from at least one of salts containing Zn, Fe, Sn, Pb, Cu, Hg, Ag, Pt, and Au metal ions. The material that provides a hydrogen ion is selected from one or more of bisphenol A, bisphenol F, bisphenol S, 4-hydroxy-4'-isopropoxydiphenyl sulfone, and DBSP (2,4-diphenylsulfonylphenol).

[0051] According to some embodiments of the present invention, the phase-change polymer is a phase-changeable polymer having a phase-change temperature of 36°C to 80°C. The phase-change polymer of the present invention is solid at temperatures below the phase-change point and liquid at temperatures above the phase-change point. When the temperature reaches the phase-change temperature, the phase-change material changes from a solid to a liquid state, opening the mesoporous nanoparticles' mesopores and releasing the first response indicator therein.

[0052] The present application also provides a method for preparing the above-mentioned phase change nanomaterial, comprising the following steps: S1, dispersing mesoporous nanoparticles in a first response indicator to obtain mesoporous nanoparticles loaded with the first response indicator; S2, adding a shell material monomer to the mesoporous nanoparticles loaded with the first response indicator, and generating the phase change nanomaterial under the action of a free radical initiator.

[0053] According to some embodiments of the present invention, based on 100 parts by weight of the mesoporous nanoparticles, the amount of the first response indicator is 10-20 parts, the shell material monomer is 20-40 parts, and the free radical initiator is 0.04-0.08 parts; in a preferred embodiment, based on 100 parts by weight of the mesoporous nanoparticles, the amount of the first response indicator is 10 parts, the shell material monomer is 20 parts, and the free radical initiator is 0.04 parts.

[0054] According to some embodiments of the present invention, the shell material monomer is one or more of diethylene glycol hexadecyl ether monomethacrylate, diethylene glycol octadecyl ether monomethacrylate, diethylene glycol eicosyl ether monomethacrylate, diethylene glycol behenyl ether monomethacrylate, diethylene glycol hexacosyl ether monomethacrylate, and diethylene glycol triacontyl ether monomethacrylate.

[0055] The present application also provides an uncured ink composition, which comprises the above-mentioned phase change nanomaterial, and also includes a film-forming resin, a second response indicator, a leveling agent, a defoaming agent and an organic solvent, wherein, when the first response indicator is a recessive dye, the second response indicator is an initiating substance; when the first response indicator is an initiating substance, the second response indicator is a recessive dye, and the recessive dye and the initiating substance here are of the same types as described above. This method separates the two response indicators through the special structure of the phase change nanomaterial, and at the same time realizes the separate loading of the first response indicator and the second response indicator in the ink composition.

[0056] According to some embodiments of the present invention, based on 100 parts by weight of the film-forming resin component, the amount of the phase change nanomaterial is 20-40 parts, the second response indicator is 10-20 parts, the leveling agent is 1-2 parts, the defoaming agent is 1-2 parts, and the organic solvent is 10-20 parts; in a preferred embodiment, based on 100 parts by weight of the film-forming resin component, the amount of the phase change nanomaterial is 30 parts, the second response indicator is 10 parts, the leveling agent is 1 part, the defoaming agent is 1 part, and the organic solvent is 10 parts.

[0057] According to some embodiments of the present invention, the film-forming resin is selected from at least one of acrylic resin, polyurethane, polyester, and epoxy resin.

[0058] The present application also provides a method for preparing the uncured ink composition, which comprises uniformly mixing a phase change nanomaterial, a mixed film-forming resin, a second response indicator, an initiator, a leveling agent, a defoaming agent, and an organic solvent.

[0059] The present application also provides a coated product, comprising: a substrate; and a cured coating layer located on the substrate, wherein the coating layer is obtained by UV curing the ink composition after printing.

[0060] The present application also provides use of the ink composition as a temperature indicator in toys, printed materials, decorations, writing instruments, and packaging of medical products.

[0061] The ink composition of the present application utilizes the core mesoporous structure of a phase change nanomaterial, with a first response indicator loaded in the mesopores. The phase change polymer of the outer shell undergoes a phase transition at a specific temperature, releasing the first response indicator, which reacts with the second response indicator to produce a color development reaction, thereby achieving irreversible color change. This allows customers to easily check the temperature changes experienced by the coated product with the naked eye.

[0062] In order to further illustrate the present invention, the present invention will be described in detail with reference to the following examples.

[0063] In the examples, different phase-change nanomaterials and ink compositions were prepared according to the method described in this patent application, and color change tests were performed to evaluate the properties of these ink compositions.

[0064] Color change test

[0065] A sample of the ink composition prepared according to the following examples was printed on an object to be tested and cured with UV light to obtain a printed label. The color change of the ink composition on the object to be tested was then visually inspected.

[0066] Example 1:

[0067] The preparation method of phase change nanomaterials is as follows:

[0068] Take 10g of mesoporous nano-silica with amino groups on the outside of the pores (Ap-MSN) and disperse it in 1g of red pigment-16 recessive dye solution, mix it in a shaker at room temperature for 24h to maximize the dye loading capacity of Ap-MSN, then centrifuge the Ap-MSN mixed with the dye, wash it with deionized water three times, and vacuum dry it at 60℃ for 12h to obtain the dye-loaded Ap-MSN; then react it with amino group and reversible addition fragmentation chain transfer agent (RAFT) to obtain RAFT-MSN; under N2 protection, add 0.004g of free radical initiator 2,2-azoisobutyronitrile (AIBN) and 2g of monomer diethylene glycol hexadecyl ether monomethacrylate, react at 60℃ for 30h, separate, wash and dry, thereby obtaining MSN phase change nanomaterial loaded with recessive dye wrapped by polyethylene glycol hexadecyl ether monomethacrylate phase change polymer, such as Figure 1 shown.

[0069] Preparation method of ink composition:

[0070] Take 2g of phase change nanomaterial, 10g of film-forming resin polyester, 1g of diaryliodonium salt, 0.1g of silicone leveling agent, 0.1g of polyether defoaming agent, and 1g of organic solvent ethyl acetate, fully dissolve, mix and stir, and finally formulate into a finished ink composition.

[0071] When the temperature reaches 36°C, near the critical temperature of the phase-change nanomaterial, the phase-change polymer undergoes a phase change, releasing the diaryliodonium salt in the MSN pores, which reacts with red pigment-16, and the printed label undergoes an irreversible change from colorless to red.

[0072] Implementation Case 2:

[0073] The preparation method of phase change nanomaterials is as follows:

[0074] 10g of mesoporous nano-silica with amino groups on the outside of the pores (Ap-MSN) was dispersed in 1g of diaryliodonium salt solution and mixed in a shaker at room temperature for 24h to maximize the initiator loading of Ap-MSN. The Ap-MSN mixed with the initiator was then centrifuged, washed three times with deionized water, and dried in vacuum at 60°C for 12h to obtain Ap-MSN encapsulated with the initiator. RAFT-MSN was then obtained through the reaction of the amino group with a reversible addition-fragmentation chain transfer agent (RAFT). Under N2 protection, 0.004g of 2,2-azoisobutyronitrile (AIBN) and 2g of diethylene glycol hexadecyl ether monomethacrylate were added as a free radical initiator and reacted at 60°C for 30h. After separation, washing, and drying, the initiator-loaded MSN phase change nanomaterial encapsulated by the polyethylene glycol hexadecyl ether monomethacrylate phase change polymer was obtained.

[0075] Preparation method of ink composition:

[0076] Take 2g of phase change nanomaterial, 10g of film-forming resin polyester, 1g of red pigment-16, 0.1g of silicone leveling agent, 0.1g of polyether defoaming agent, and 1g of organic solvent ethyl acetate, fully dissolve, mix and stir, and finally formulate into a finished ink composition.

[0077] When the temperature reaches 36°C, near the critical temperature of the phase-change nanomaterial, the phase-change polymer undergoes a phase change, releasing the diaryliodonium salt in the MSN pores, which reacts with red pigment-16, and the printed label undergoes an irreversible change from colorless to red.

[0078] Example 3

[0079] The preparation method of phase change nanomaterial A is the same as that in Example 1.

[0080] Preparation method of phase change nanomaterial B:

[0081] 10g of mesoporous nano-silica with amino groups on the outside of the pores (Ap-MSN) was dispersed in 1g of green pigment-5 hidden dye solution and mixed in a shaker at room temperature for 24h to maximize the initiator loading of Ap-MSN. The Ap-MSN mixed with the initiator was then centrifuged, washed three times with deionized water, and vacuum dried at 60°C for 12h to obtain Ap-MSN encapsulated with the initiator; then, the amino group reacted with a reversible addition-fragmentation chain transfer agent (RAFT) to obtain RAFT-MSN; under N2 protection, 0.004g of 2,2-azoisobutyronitrile (AIBN) as a free radical initiator and 2g of diethylene glycol octadecyl ether monomethacrylate as a monomer were added, and the reaction was carried out at 60°C for 30h. After separation, washing, and drying, the MSN phase change nanomaterial B loaded with green pigment-5 and encapsulated by the polyethylene glycol octadecyl ether monomethacrylate phase change polymer was obtained.

[0082] Preparation method of ink composition:

[0083] Take 2g of phase change nanomaterial A, 2g of phase change nanomaterial B, 10g of film-forming resin polyester, 1g of diaryliodonium salt, 0.1g of silicone leveling agent, 0.1g of polyether defoaming agent, and 1g of organic solvent ethyl acetate, fully dissolve and mix, stir, and finally formulate into a finished ink composition.

[0084] When the temperature reaches 36°C, near the critical temperature of phase-change nanomaterial A, the phase-changeable polymer undergoes a phase transition, releasing the red pigment-16 from the MSN pores. This reacts with the initiator diaryliodonium salt, causing the printed label to irreversibly change from colorless to red. When the temperature reaches 44°C, near the critical temperature of phase-change nanomaterial B, the phase-changeable polymer undergoes a phase transition, releasing the green pigment-5 from the MSN pores. This reacts with the initiator diaryliodonium salt, causing the printed label to irreversibly change from red to green.

[0085] Although this specification is described according to implementation methods, not every implementation method contains only one independent technical solution. This narrative method of the specification is only for the sake of clarity. Those skilled in the art should regard the specification as a whole. The technical solutions in each implementation method can also be appropriately combined to form other implementation methods that can be understood by those skilled in the art.

[0086] The series of detailed descriptions listed above are only specific descriptions of feasible implementation methods of the present invention. They are not intended to limit the scope of protection of the present invention. Any equivalent implementation methods or changes that do not deviate from the technical spirit of the present invention should be included in the scope of protection of the present invention.

Claims

1. A phase change nanomaterial, characterized in that: include: mesoporous nanoparticle-based core; a first response indicator loaded in the mesopores of the mesoporous nanoparticle-based particles; a shell mechanically constraining the core, the shell comprising a phase change polymer; Wherein, when the phase-change nanomaterial is placed in a temperature environment above the phase-change temperature of the phase-change polymer, the first response indicator can be released from the shell.

2. The phase change nanomaterial according to claim 1, characterized in that: The mesoporous nanoparticles are selected from one or more of mesoporous nano-silica, mesoporous nano-alumina, and mesoporous graphite carbon nitride, all of which contain amino groups on their surfaces.

3. The phase change nanomaterial according to claim 1, characterized in that: The first response indicator is a hidden dye or a triggering substance.

4. The phase-change nanomaterial according to claim 3, characterized in that: The recessive dye is a fluorane dye or a triarylmethane dye.

5. The phase change nanomaterial according to claim 4, characterized in that: The recessive dyes are blue pigment-8, green pigment-5, red pigment-16, melanin-1, crystal violet lactone, thermosensitive scarlet dye, 3,3-bis(N-octyl-2-methylindole)phthalide, 6'-(diethylamino)-1',3'-dimethylfluoran, 3-diethylamino-6-chlorofluoran, 6-dimethylamino-3,3-bis(4-dimethylaminophenyl)phthalide, leuco crystal violet, 7-[4-(diethylamino)-2-ethoxyphenyl]-7-(2-methyl-1-octyl-1H-indol-3-yl)3, 4-B]pyridin-5(7H)-one, 4,4'-[(9-butyl-9H-carbazol-3-yl)methylene]bis[N-methyl-N-phenylaniline], 2-phenylamino-3-methyl-6-dibutylaminofluoran, 2-phenylamino-3-methyl-6-diethylaminofluoran, 3',6'-dimethoxyfluoran, 3,3-bis(4-diethylamino-2-ethoxyphenyl)-4-azaphthalide, heat (pressure) sensitive green TF-G, and 3-(N-ethyl-4-toluinyl)-6-methyl-7-anilinofluoran.

6. The phase-change nanomaterial according to claim 3, characterized in that: The initiating substance is a material that provides a Lewis acid, a material that provides an oxidizing metal ion, or a material that provides a hydrogen ion.

7. The phase-change nanomaterial according to claim 6, characterized in that: The material providing the Lewis acid is at least one of diaryl iodonium salt, triaryl sulfonium salt, alkyl sulfonium salt, iron arene salt, sulfonyloxy ketone and triaryl siloxane ether.

8. The phase-change nanomaterial according to claim 6, characterized in that: The material providing oxidizing metal ions is selected from at least one of salts containing Zn, Fe, Sn, Pb, Cu, Hg, Ag, Pt, and Au metal ions.

9. The phase-change nanomaterial according to claim 6, characterized in that: The material providing hydrogen ions is selected from one or more of bisphenol A, bisphenol F, bisphenol S, 4-hydroxy-4'-isopropoxydiphenyl sulfone, and DBSP (2,4-diphenylsulfonylphenol).

10. The phase-change nanomaterial according to claim 1, characterized in that: The phase-change polymer is a phase-changeable polymer with a phase-change temperature of 36° C. to 80° C.

11. A method for preparing the phase change nanomaterial according to any one of claims 1 to 10, characterized in that: The steps include: S1, dispersing mesoporous nanoparticles in a first response indicator to obtain mesoporous nanoparticles loaded with the first response indicator; S2. Adding shell material monomers to the mesoporous nanoparticles loaded with the first response indicator, and generating the phase change nanomaterial under the action of a free radical initiator.

12. The method according to claim 11, wherein Based on 100 parts by weight of the mesoporous nanoparticles, the usage of the first response indicator is 10-20 parts, the usage of the shell material monomer is 20-40 parts, and the usage of the free radical initiator is 0.04-0.08 parts.

13. The method according to claim 11, wherein The shell material monomer is one or more of diethylene glycol hexadecyl ether monomethacrylate, diethylene glycol octadecyl ether monomethacrylate, diethylene glycol eicosyl ether monomethacrylate, diethylene glycol behenyl ether monomethacrylate, diethylene glycol hexacosyl ether monomethacrylate, and diethylene glycol triacontyl ether monomethacrylate.

14. An uncured ink composition, characterized in that It comprises the phase change nanomaterial as defined in any one of claims 1 to 10, and further comprises a film-forming resin, a second response indicator, a leveling agent, a defoaming agent and an organic solvent, wherein, when the first response indicator is a recessive dye, the second response indicator is a triggering substance; when the first response indicator is a triggering substance, the second response indicator is a recessive dye.

15. The ink composition according to claim 14, wherein Based on 100 parts by weight of the film-forming resin component, the amount of the phase change nanomaterial is 20-40 parts, the second response indicator is 10-20 parts, the leveling agent is 1-2 parts, the defoaming agent is 1-2 parts, and the organic solvent is 10-20 parts.

16. The ink composition according to claim 14, wherein The film-forming resin is selected from at least one of acrylic resin, polyurethane, polyester and epoxy resin.

17. The ink composition according to claim 14, wherein The recessive dye is a fluorane dye or a triarylmethane dye.

18. The ink composition according to claim 17, wherein The recessive dyes are blue pigment-8, green pigment-5, red pigment-16, melanin-1, crystal violet lactone, thermosensitive scarlet dye, 3,3-bis(N-octyl-2-methylindole)phthalide, 6'-(diethylamino)-1',3'-dimethylfluoran, 3-diethylamino-6-chlorofluoran, 6-dimethylamino-3,3-bis(4-dimethylaminophenyl)phthalide, leuco crystal violet, 7-[4-(diethylamino)-2-ethoxyphenyl]-7-(2-methyl-1-octyl-1H-indol-3-yl)3, 4-B]pyridin-5(7H)-one, 4,4'-[(9-butyl-9H-carbazol-3-yl)methylene]bis[N-methyl-N-phenylaniline], 2-phenylamino-3-methyl-6-dibutylaminofluoran, 2-phenylamino-3-methyl-6-diethylaminofluoran, 3',6'-dimethoxyfluoran, 3,3-bis(4-diethylamino-2-ethoxyphenyl)-4-azaphthalide, heat (pressure) sensitive green TF-G, and 3-(N-ethyl-4-toluinyl)-6-methyl-7-anilinofluoran.

19. The ink composition according to claim 14, wherein The initiating substance is a material that provides a Lewis acid, a material that provides an oxidizing metal ion, or a material that provides a hydrogen ion.

20. The ink composition according to claim 19, wherein The material providing the Lewis acid is at least one of diaryl iodonium salt, triaryl sulfonium salt, alkyl sulfonium salt, iron arene salt, sulfonyloxy ketone and triaryl siloxane ether.

21. The ink composition according to claim 19, wherein The material providing oxidizing metal ions is selected from at least one of salts containing Zn, Fe, Sn, Pb, Cu, Hg, Ag, Pt, and Au metal ions.

22. The ink composition according to claim 19, wherein The material providing hydrogen ions is selected from one or more of bisphenol A, bisphenol F, bisphenol S, 4-hydroxy-4'-isopropoxydiphenyl sulfone, and DBSP (2,4-diphenylsulfonylphenol).

23. A method for preparing the ink composition according to any one of claims 14 to 22, characterized in that: The method comprises the steps of uniformly mixing a phase-change nano material, a mixed film-forming resin, a second response indicator, an initiator, a leveling agent, a defoaming agent and an organic solvent.

24. A coated article comprising: a substrate; and a cured coating layer on the substrate, wherein the coating layer is obtained by printing the ink composition according to any one of claims 14 to 22 and then curing it with ultraviolet light.

25. Use of the ink composition according to any one of claims 14 to 22 as a temperature indicator in the packaging of toys, printed materials, decorations, writing instruments, and medical products.

Images