# Patent

## Title
Thermochromic micro particles and thermochromic ink composition, writing apparatus and smart window using the same

## Abstract

The present invention relates to thermochromic micro particles capable of stably implementing a high chromogenic property and a decolorization property and having an improved erasing property, thermal resistance, and chemical resistance, and a thermochromic ink composition, a writing apparatus, and a smart window using the same. The thermochromic micro particles comprise a core part including a phase change material, a dye, and a developer, the phase change material including at least one selected from the group consisting of at least one chain hydrocarbon having a carbon number of 8 or more, a hydrated inorganic salt, alcohol having a carbon number of 3 or more, and polyalkyleneglycol; and a shell layer including a polymer resin.

## Background
CROSS-REFERENCE TO RELATED APPLICATION
This application claims the benefit of priority to Korean Patent Application No. 10-2015-0091148 filed in the Korean Intellectual Property Office on Jun. 26, 2015 and Korean Patent Application No. 10-2016-0048338 filed in the Korean Intellectual Property Office on Apr. 20, 2016, the entire contents of which are incorporated herein by reference.
TECHNICAL FIELD OF THE INVENTION
The present invention relates to thermochromic micro particles, and a thermochromic ink composition, a writing apparatus, and a smart window using the same. More specifically, the present invention relates to thermochromic micro particles capable of stably implementing a high chromogenic (color development) property and a decolorization property depending on a temperature change, and having an improved erasing property, thermal resistance, and chemical resistance, and a thermochromic ink composition, a writing apparatus, and a smart window using the same.
BACKGROUND OF THE INVENTION
In general, an ink for writing is divided into a water-based ink and an oil-based ink, and is absorbed or attached to settle onto writing surfaces to maintain a state in which the ink is written for a long period of time. The water-based ink and the oil-based ink for writing are absorbed or attached onto the writing surfaces (for example, a paper, a synthetic resin, etc.), to settle, and are not easily removed.
In a written document employing a writing apparatus using the water-based ink and the oil-based ink for writing, if it happens to require modification of a text or correction of typographical error, the written document needs to be erased, but is not clearly erased with an eraser for general pencil. Further, if it attempts to erase the document with an eraser for a ballpoint pen, a surface settled with the water-based ink and the oil-based ink is ground and ripped off, such that a paper may be torn or deformed.
Accordingly, a technology of manufacturing an ink by using a material having a color-change property in which a colorless compound shows colors, or reversely, a colored compound is changed into colorless by external stimulus, has been recently suggested. The external stimulus may include heat, light, pressure, etc. Particularly, a research into a technology of securing an erasing property of an ink by using a thermochromic compound showing the color-change property in which colorless is implemented from color when applying heat, has been actively conducted.
However, in the thermochromic material in which color-change is performed at a relatively high temperature, there is a limitation in that portability is not satisfied since heating apparatuses such as a hair dryer, hot water, etc., are required to erase the ink.
In addition, in the case of using a material in which thermochromism is possible by body heat, frictional heat due to an eraser, etc., there is a limitation in that a chromogenic property is not sufficiently maintained, for example, color-change is performed even at a summer temperature, etc.
Therefore, development of a thermochromic compound having a color-change temperature range, capable of being rapidly erased by an erasing method with simplicity and portability, while maintaining an excellent chromogenic property has been demanded.
The above information disclosed in this Background section is only for enhancement of understanding of the background of the invention and therefore it may contain information that does not form the prior art that is already known in this country to a person of ordinary skill in the art.
SUMMARY OF THE INVENTION
The present invention has been made in an effort to provide thermochromic micro particles having advantages of stably implementing a high chromogenic property and a decolorization property and having an improved erasing property, thermal resistance, and chemical resistance.
In addition, the present invention has been made in an effort to provide a thermochromic ink composition, a writing apparatus, and a smart window using the thermochromic micro particles.
An exemplary embodiment of the present invention provides thermochromic micro particles including a core part including a phase change material, a dye, and a developer, the phase change material including at least one selected from the group consisting of at least one chain hydrocarbon having a carbon number of 8 or more, a hydrated inorganic salt, alcohol having a carbon number of 3 or more, and polyalkyleneglycol; and a shell layer including a polymer resin.
In addition, another exemplary embodiment of the present invention provides a thermochromic ink composition including the thermochromic micro particles as described above.
Further, still another exemplary embodiment of the present invention provides a thermochromic writing apparatus including an ink storage container filled with the thermochromic ink composition as described above.
In addition, yet another exemplary embodiment of the present invention provides a smart window including a coating layer in which the thermochromic micro particles as described above are dispersed.



BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 shows a phase change characteristic of thermochromic micro particles of Examples.
FIG. 2 shows a SEM image of a surface of the thermochromic micro particles manufactured by Example 1.
FIG. 3 shows a DSC characteristic of particles for a thermoerasable ink manufactured by Example 1.
FIG. 4 shows a thermochromic characteristic of a thermochromic ink composition of Example.
FIG. 5 shows a schematic structure of a cap type writing apparatus or a knock type writing apparatus including the thermochromic ink composition of Example.
FIG. 6 shows a schematic structure of an absorption type marking pen including the thermochromic ink composition of Example.
FIG. 7 shows a schematic structure of a direct liquid type marking pen including the thermochromic ink composition of Example.



DETAILED DESCRIPTION OF THE INVENTION
Hereinafter, thermochromic micro particles, and a thermochromic ink composition, a writing apparatus, and a smart window using the same according to specific exemplary embodiment of the present invention are described in more detail.
According to an embodiment of the present invention, there may be provided thermochromic micro particles including a core part including a phase change material, a dye, and a developer, the phase change material including at least one selected from the group consisting of at least one chain hydrocarbon having a carbon number of 8 or more, a hydrated inorganic salt, alcohol having a carbon number of 3 or more, and polyalkyleneglycol; and a shell layer including a polymer resin.
The present inventors confirmed through experiments that when the above-described thermochromic micro particles are used, a decolorization property could be implemented depending on a temperature change while exhibiting a high chromogenic property, and a temperature range at which thermochromism is performed by the phase change material could be controlled, such that the decolorization property and the chromogenic property could be easily maintained and the thermochromic micro particles could be rapidly erased by an erasing method with simplicity and portability, and completed the present invention.
In addition, when the above-described thermochromic micro particles are used, deterioration of function may be prevented and heat stability may be secured despite contacting chemical active materials such as acid materials, basic materials, peroxides, etc., or other solvent components.
The thermochromic micro particles according to the exemplary embodiment of the present invention may be utilized in various fields that thermochromism property is required, for example, an ink composition, an ink, a pen, a coating composition, a fiber, a construction material, etc.
In particular, the thermochromic micro particles may include the phase change material. The phase change material is a material absorbing and storing latent heat as the phase is changed from solid to liquid or from liquid to gas depending on a phase change temperature, and may store or release heat through chemical bond.
The phase change material (PCM) may include at least one selected from the group consisting of at least one chain hydrocarbon having a carbon number of 8 or more, a hydrated inorganic salt, alcohol having a carbon number of 3 or more, and polyalkyleneglycol. That is, the phase change material may include at least one chain hydrocarbon having a carbon number of 8 or more, or a carbon number of 10 to 50, or a carbon number of 12 to 40, or a carbon number of 19 to 30, or a carbon number of 21 to 30, a hydrated inorganic salt, alcohol having a carbon number of 3 or more, or a carbon number of 6 to 50, or a carbon number of 8 to 40, or a carbon number of 10 to 30, or a carbon number of 12 to 18, polyalkyleneglycol, or mixtures of two or more thereof.
The mixture may be, for example, a mixture of the chain hydrocarbon having a carbon number of 8 or more and the alcohol having a carbon number of 3 or more, wherein a weight ratio of the chain hydrocarbon having a carbon number of 8 or more and the alcohol having a carbon number of 3 or more may be 1:1.2 to 1:5, or 1:1.3 to 1:3.
The chain hydrocarbon having a carbon number of 8 or more means a compound in which carbon atoms of 8 or more, or 10 or more, or 19 or more are linked in a chain shape. The chain hydrocarbon having a carbon number of 8 or more may be present as at least one kind, i.e., alone or as mixtures, and a mixture of chain hydrocarbon having a carbon number of 8 or more means a mixture of at least two chain hydrocarbons classified on the basis of the number of carbons.
The chain hydrocarbon having a carbon number of 8 or more may include a straight chain saturated hydrocarbon having a carbon number of 10 to 50, or 12 to 40, or 20 to 40. Examples of the straight chain saturated hydrocarbon having a carbon number of 10 to 50 may include n-dodecane, n-tetradecane, n-pentadecane, n-hexadecane, n-heptadecane, n-octadecane, n-eicosane, n-docosane, etc.
The straight chain saturated hydrocarbon having a carbon number of 20 to 40 or a mixture thereof is commonly referred to as paraffin, and when the straight chain saturated hydrocarbon having a carbon number of 20 to 40 or a mixture thereof is present in a solid state, it is referred to as paraffin wax.
The hydrated inorganic salt means a hydrate of inorganic salt, specifically, may include hydrates of inorganic acid metal salts or hydrates of organic acid metal salts. The inorganic acid metal salt may include sulfates, nitrates, carbonates, phosphates, thiosulfates or halides of metals. In addition, the organic acid metal salt may include acetates of metals. The metal may include both of typical metals and transition metals.
Specifically, alkali metals such as lithium, sodium, potassium, etc., alkaline earth metals such as magnesium, calcium, barium, etc., or transition metals such as manganese, iron, nickel, copper, zinc, silver, etc., may be used. Specific examples of the hydrated inorganic salt may include Na2SO4.10H2O, Na2HPO4.12H2O, Zn(NO3)2. 6H2O, Na2S3O3.5H2O and CH3COONa.3H2O, etc.
The alcohol having a carbon number of 3 or more may include aliphatic alcohol having a carbon number of 6 to 50, or 8 to 40, or 14 to 30, or 18 to 25 or aromatic alcohol having a carbon number of 3 to 20, or 3 to 15, or 4 to 10.
The aliphatic alcohol having a carbon number of 6 to 50 may include chain saturated hydrocarbon having a carbon number of 6 to 50 as a main chain, wherein a compound bonded with at least one hydroxy group may be included in the main chain or the end, preferably, a compound bonded with one hydroxy group may be included in the end of the main chain including the straight chain saturated hydrocarbon having a carbon number of 6 to 50.
Examples of the compound bonded with one hydroxy group in the end of the main chain including the chain saturated hydrocarbon having a carbon number of 6 to 50 may include n-octyl alcohol, n-decyl alcohol, n-lauryl alcohol, n-myristyl alcohol, n-cetyl alcohol, n-stearyl alcohol, etc.
The aromatic alcohol having a carbon number of 3 to 50 may include an aromatic hydrocarbon having a carbon number of 3 to 20 or a heteroaromatic compound having a carbon number of 3 to 20; and at least one hydroxy group, preferably, may include a heteroaromatic compound having a carbon number of 3 to 20 and a compound including at least one hydroxy group, wherein at least one hydroxy group may be directly combined with the heteroaromatic compound having a carbon number of 3 to 20.
Examples of the heteroaromatic compound having a carbon number of 3 to 20 are not significantly limited, and for example, may include furan, thiophene, pyrrole, imidazole, pyridine, pyrimidine, indole or derivatives thereof.
The polyalkyleneglycol may include a repeating unit represented by Chemical Formula 1 below:




in Chemical Formula 1 above, R1 is an alkylene group having a carbon number of 1 to 10, and n is an integer from 1 to 1000. Examples of the alkylene group having a carbon number of 1 to 10 may include a methylene group, an ethylene group, a propylene group, a butylene group, etc. In Chemical Formula 1, ‘*’ may mean a direct bond.
The polyalkyleneglycol may include a main chain including polyoxyalkylene and hydroxy groups bonded to both ends of the main chain. The compound bonded with the hydroxy groups in both ends of the main chain including the polyoxyalkylene may be represented by Chemical Formula 2 below:




in Chemical Formula 2 above, R1 is an alkylene group having a carbon number of 1 to 10, and n is an integer from 1 to 1000.
Specific examples of the polyalkyleneglycol are not significantly limited, and for example, may include polyethyleneglycol, polypropyleneglycol, polybutyleneglycol, etc.
In the thermochromic micro particles, a color-change temperature range defined by General Formula 1 below may be 50° C. or more. Accordingly, thermochromism of the dye may be controlled, such that the thermochromic micro particles may be rapidly erased by an erasing method with simplicity, while maintaining an excellent chromogenic property. Specifically, in the thermochromic micro particles, the color-change temperature range defined by General Formula 1 below is 50° C. or more, which is large, such that a phase change zone in which a solid phase and a liquid phase of the phase change material coexist widens, and accordingly, it is easy to maintain a chromogenic state and a decolorization state before and after the color-change, respectively.

Color-change temperature range(ΔT)=an absolute value of a difference between a melting point of the phase change material and a crystallization temperature of the phase change material.  [General Formula 1]

The melting temperature (Tm) is a temperature when a state change from solid to liquid is generated, and specifically means the lowest temperature at which the phase change material is capable of being present as a complete liquid state. In addition, the crystallization temperature (Tc) means a temperature at which crystallization is generated, or a heat treatment temperature required for crystallization, and specifically means the highest temperature at which the phase change material is capable of being present as a complete solid state.
The phase change material may have the crystallization temperature of −20° C. to 0° C., or −10° C. to 5° C. In addition, the phase change material may have a melting point of 50° C. or more, 50° C. to 80° C.
Further, the thermochromic micro particle may include a dye. The dye may be a lactone-based dye, wherein the lactone-based dye is leuco dye, and may exhibit thermochromism property. Examples of the lactone-based dye may include a phthalide-based compound or a fluoran-based compound, etc.
The phthalide-based compound may include phthalide compounds or derivative compounds thereof, and the fluoran-based compound may include fluoran compounds or derivative compounds thereof.
Examples of the phthalide-based compound may include diphenylmethane phthalide-based compounds, phenyl indolyl phthalide-based compounds, indolyl phthalide-based compounds, diphenylmethane azaphthalide-based compound, etc.
More specifically, examples of the lactone-based dye may include 3,3-bis(p-dimethylamino phenyl)-6-dimethylamino phthalide, 3-(4-diethylamino phenyl)-3-(1-ethyl-2-methylindol-3-yl)phthalide, 3,3-bis(1-n-butyl-2-methylindol-3-yl)phthalide, 3,3-bis(2-ethoxy-4-diethyl amino phenyl)-4-azaphthalide, 3-[2-ethoxy-4-(N-ethyl anilino)phenyl]-3-(1-ethyl-2-methylindol-3-yl)-4-azaphthalide, 3,6-diphenyl amino fluoran, 3,6-dimethoxy fluoran, 3,6-di-n-butoxy fluoran, 2-methyl-6-(N-ethyl-N-p-tril amino) fluoran, 3-chloro-6-cyclohexylamino fluoran, 2-methyl-6-cyclohexylamino fluoran, 2-(2-chloro anilino)-6-di-n-butyl amino fluoran, 2-(3-trifluoromethyl anilino)-6-diethyl amino fluoran, 2-(N-methylanilino)-6-(N-ethyl-N-p-tril amino) fluoran, 1,3-dimethyl-6-diethyl amino fluoran, 2-chloro-3-methyl-6-diethyl aminofluoran, 2-anilino-3-methyl-6-diethyl amino fluoran, 2-anilino-3-methyl-6-di-n-butyl amino fluoran, 2-xylidino3-methyl-6-diethyl amino fluoran, 1,2-benz-6-diethyl amino fluoran, 1,2-benz-6-(N-ethyl-N-isobutyl amino) fluoran, 1,2-benz-6-(N-ethyl-N-isoamyl amino) fluoran, spiro[5H-(1) benzopyrano(2,3-d) pyrimidine-5,1′(3′H) isobenzofuran]-3-one, 2-(diethyl amino)-8-(diethylamino)-4-methyl-, spiro[5H-(1) benzopyrano(2,3-d) pyrimidine-5,1′(3′H) isobenzofuran]-3-one, 2-(di-n-butylamino)-8-(di-n-butyl amino)-4-methyl-, spiro[5H-(1) benzopyrano(2,3-d) pyrimidine-5,1′(3′H) isobenzofuran]-3-one, 2-(di-n-butyl amino)-8-(diethyl amino)-4-methyl-, spiro[5H-(1) benzopyrano(2,3-d) pyrimidine-5,1′(3′H) isobenzofuran]-3-one, 2-(di-n-butyl amino)-8-(N-ethyl-N-i-amyl amino)-4-methyl-, spiro[5H-(1)benzopyrano(2,3-d) pyrimidine-5,1′(3′H) isobenzofuran]-3′-one, 2-(di-n-butyl amino)-8-(di-n-butyl amino)-4-phenyl, 3-(2-methoxy-4-dimethylamino phenyl)-3-(1-butyl-2-methylindole-3-yl)-4,5,6,7-tetrachlorophthalide, 3-(2-ethoxy-4-diethyl amino phenyl)-3-(1-ethyl-2-methylindole-3-yl)-4,5,6,7-tetrachlorophthalide, 3-(2-ethoxy-4-diethyl amino phenyl)-3-(1-pentyl-2-methylindole-3-yl)-4,5,6,7-tetrachlorophthalide, etc.
Further, the thermochromic micro particle may further include pyridine-based compounds, quinazoline-based compounds, and bisquinazoline-based compounds.
Further, the thermochromic micro particle may include the developer. The developer is a compound that color-develops the lactone-based dye included in the thermochromic micro particle, and examples of the developer are not significantly limited, and for example, may include phenol-based compounds. The phenol-based compound may include phenol compounds or derivative compounds thereof.
Specific examples of the phenol-based compound are not significantly limited, and for example, may include bisphenol-based compounds, gallate compounds, paraben compounds, etc.
More specifically, examples of the developer may include 2,2-bis(4′-hydroxyphenyl) hexafluoropropane, 2,2-bis(4′-hydroxyphenyl) propane, ethyl gallate, methyl p-hydroxybenzoate, phenol, o-cresol, tertiary butylcatechol, nonylphenol, n-octyl phenol, n-dodecylphenol, n-stearyl phenol, p-chlorophenol, p-bromo phenol, o-phenyl phenol, p-hydroxy benzoic acid n-butyl, p-hydroxy benzoic acid n-octyl, resorcinol, 4,4-dihydroxy diphenyl sulfone, 1,1-bis(4′-hydroxyphenyl) ethane, 2,2-bis(4′-hydroxy-3-methyl phenyl) propane, bis(4-hydroxyphenyl) sulfide, 1-phenyl-1,1-bis(4′-hydroxyphenyl)ethane, 1,1-bis(4-hydroxyphenyl)-3-methyl butane, 1,1-bis(4′-hydroxyphenyl)-2-methyl propane, 1,1-bis(4-hydroxyphenyl) n-hexane, 1,1-bis(4-hydroxyphenyl) n-heptane, 1,1-bis(4-hydroxyphenyl) n-octane, 1,1-bis(4-hydroxyphenyl) n-nonane, 1,1-bis(4-hydroxyphenyl) n-decane, 1,1-bis(4-hydroxyphenyl) n-dodecane, 2,2-bis(4′-hydroxyphenyl) butane, 2,2-bis(4′-hydroxyphenyl) ethylpropionate, 2,2-bis(4′-hydroxyphenyl)-4-methyl pentane, 2,2-bis(4′-hydroxyphenyl) hexafluoropropane, 2,2-bis(4′-hydroxyphenyl) n-heptane, 2,2-bis(4′-hydroxyphenyl) n-nonane, 4,4′,4′′-methylidene trisphenol, 2,6-bis[(2-hydroxy-5-methylphenol) methyl]-4-methylphenol, 4,4′-[1-[4-[1-(4-hydroxyphenyl)-1-methyl ethyl]phenyl]ethylidene]bisphenol, 4,4′,4′′-ethylidene tris[2-methylphenol], 4,4′-[(2-hydroxyphenyl) methylene]bis[2,3,6-triphenyl phenol], 2,2-methylenebis[6-[(2-hydroxy-5-methyl phenyl) methyl]-4-methylphenol], 2,4,6-tris(4-hydroxyphenylmethyl) 1,3-benzene diol, 4,4′,4′′-ethylidene trisphenol, 4,4′-[(4-hydroxyphenyl)methylene]bis[2-methylphenol], 4,4′-[(4-hydroxyphenyl) methylene]bis[2,6-dimethylphenol], 4,4′-[(4-hydroxyphenyl) methylene]bis[2-methylphenol], 4,4′-[(4-hydroxyphenyl]methylene]bis[2,6-dimethylphenol], 4,4′-[(4-hydroxy-3-methoxyphenyl) methylene]bis[2,6-dimethylphenol], 2,4-bis[(5-methyl-2-hydroxyphenyl) methyl]-6-cyclohexylphenol, 4,4′-[1-[4-[1-(4-hydroxy-3-methylphenol)-1-methyl ethyl]phenyl]ethylidene]bis[2-methylphenol], 4,4′-[(4-hydroxyphenyl) methylene]bis[2-cyclohexyl-5-methylphenol], 4,6-bis[(4-hydroxyphenyl)methyl]1,3-benzene diol, 4,4′-[(3,4-di-hydroxy phenyl) methylene]bis[2,6-dimethylphenol], 4,4′-(1-phenylethylidene)bisphenol, 5,5′-(1-methylethylidene) bis[1-phenyl-2-ol], 4,4′,4′′-methylidene trisphenol, 4,4′-[1-[4-[1-(4-hydroxyphenyl)-1-methyl ethyl]phenyl]ethylidene]bisphenol, 4,4′-(phenylmethylene) bisphenol, 4,4′-[1,4-phenylenebis(1-methylethylidene)]bis[2-methylphenol], 5,5′-(1,1-cyclohexylidene) bis-[1-biphenyl-2-ol], bis(3,5-dimethyl-4-hydroxyphenyl), bis(3-ethyl-4-hydroxyphenyl) sulfide, bis(3,5-diethyl-4-hydroxyphenyl) sulfide, bis(3-propyl-4-hydroxyphenyl) sulfide, bis(3,5-dipropyl-4-hydroxyphenyl) sulfide, bis(3-t-butyl-4-hydroxyphenyl) sulfide, bis(3,5-t-butyl-4-hydroxyphenyl) sulfide, bis(3-pentyl-4-hydroxyphenyl) sulfide, bis(3-hexyl-4-hydroxyphenyl) sulfide, bis(3-heptyl-4-hydroxy phenyl) sulfide, bis(5-octyl-2-hydroxyphenyl) sulfide, etc. Various materials known to be usable as the developer according to the related art in addition to the above-described developers may be used.
The content of the phase change material included in the thermochromic micro particles may be 10 wt % to 70 wt %, or 30 wt % to 60 wt % on the basis of a weight of the thermochromic micro particles. Accordingly, the thermochromic micro particles allow for the phase change zone in which a solid phase and a liquid phase of the phase change material coexist to widen, such that it is easy to maintain a chromogenic state and a decolorization state before and after the color-change, respectively.
Further, a weight ratio of the developer to the dye may be 1 to 10, or 2 to 5.
A diameter of the thermochromic micro particle may be 0.1 μm to 10 When the diameter of the thermochromic micro particle is excessively increased to be more than 10 dispersion stability at the time of being applied to an ink, etc., may be reduced. On the contrary, when the diameter of the thermochromic micro particle is excessively decreased to be less than 0.1 it may be difficult to exhibit high concentration of chromogenic property.
The core part or the shell layer included in the thermochromic micro particles may further include an expansion agent or a contraction agent. The expansion agent or the contraction agent means a material capable of being expanded or contracted by external specific actions, and may be included in the core part or in the shell layer or in both of the core part and the shell layer to increase or decrease the diameter of the thermochromic micro particles. As described above, the size of the thermochromic micro particles may be modified according to temperature, such that it is easy to reversibly or irreversibly control a chromogenic concentration of the thermochromic micro particles above a specific temperature, thereby implementing excellent chromogenic property.
Examples of the expansion agent are not significantly limited, and for example, may include a low-boiling organic solvent. The low-boiling organic solvent is a solvent of which a boiling point is 90° C. or less, or 80° C. or less, and for example, may include isobutane (boiling point: about −11.7° C.), pentane (boiling point: about 36° C.), petroleum ether (boiling point: about 30° C. to 70° C.), hexane (boiling point: about 69° C.), etc. The low-boiling organic solvent may be easily volatilized when being heated, to generate gas, such that the thermochromic micro particles may be expanded.
Examples of the contraction agent are not significantly limited, and for example, may include a polymer electrolyte (polyelectrolyte). The polyelectrolyte means a polymer having a charge, and includes a repeating unit containing an ionic functional group or an ionizable functional group, and may change a form of the polymer chain by a degree of dissociation of a dissociation group or an ionic strength of a solvent.
The polyelectrolyte includes all of cationic polyelectrolyte and anionic polyelectrolyte. Examples of the cationic polyelectrolyte may include poly(diallyldimethylammonium chloride) (PDADMA-Cl); poly(N,N-dimethyl-3,5-dimethylene piperidinium chloride); poly(ethylenimine) (PEI); poly(vinylamine) (PVAH); poly(N-methyl vinylamine); poly(allylamine) (PAH); poly (4-vinyl-1-methylpyridinium bromide); poly(allylammonium fluoride); poly(dimethylamine-co-epichlorohydrin); poly(lysine); poly(N,N,N′,N′-tetramethyl-N-trimethylenehexamethylenediammonium dibromide); poly (2-(dimethylamino-ethyl)methacrylate); poly (2-methacryloyloxy-ethyl-trimethylammonium chloride); poly (2-hydroxy-3-methacryloxypropyl-trimethylammonium chloride); poly (3-chloro-2-hydroxypropyl-2-methacryloxyethyl-dimethylammonium chloride), (PCHPMEDMAC); poly (N-[3-(dimethylamino)-propyl methacrylamide]); and poly ([3-methacryloylamino-propyl]-trimethylammonium chloride), etc. Examples of the anionic polyelectrolyte may include poly(acrylic acid) (PAA); poly(methacrylic acid) (PMA); poly(itaconic acid); poly (4-styrenesulfonic acid) (PSS); poly(vinylphosphonic acid); poly(vinylsulphonic acid); poly(aspartic acid); poly(glutamic acid); poly(sodium 4-styrenesulfonate) (NaPSS); poly(anetholesulfonic acid); poly (3-sulfopropyl methacrylate); poly (1,4-phenylene ether-sulfone sulfonic acid); or poly (1,4-phenylene ether ketone sulfonic acid), etc.
The thermochromic micro particles may include the core part including the phase change material, the dye, and the developer. In addition, the thermochromic micro particles may include the shell layer including a polymer resin. That is, the thermochromic micro particles may have a core-shell structure, and may have a form in which a mixture of the phase change material, the dye, and the developer is impregnated into the polymer resin.
Examples of the polymer resin are not significantly limited, but various resins that are widely used in fields for manufacturing beads or microcapsules may be used without limitation. For example, melamine resins, urea resins, phenol resins, melamine-urea copolymers, melamine-phenol copolymers, and epoxy resins or mixtures of two or more thereof, etc., may be used.
Examples of a method for manufacturing the thermochromic micro particles are not significantly limited, and for example, an interfacial polymerization method, an in situ polymerization method of melamine-formalin-based, etc., an in-liquid curing coating method, a phase separation method from an aqueous solution, a phase separation method from an organic solvent, a soluble dispersion cooling method, an air suspension coating method, a spray drying method, etc., known in the art, may be used without limitation.
Meanwhile, according to another exemplary embodiment of the present invention, there may be provided a thermochromic ink composition including the thermochromic micro particles according to another exemplary embodiment.
The thermochromic ink composition may be prepared by using the thermochromic micro particles manufactured by the exemplary embodiment above as a pigment, and mixing a solvent, a resin, and other additives that are widely used in fields for preparing the existing ink composition.
Descriptions of the thermochromic micro particles include the contents described with respect to the exemplary embodiment above.
Examples of the solvent may include water, ethanol, propanol, butanol, glycerin, sorbitol, triethanolamine, diethanolamine, monoethanolamine, ethylene glycol, diethylene glycol, thiodiethylene glycol, polyethylene glycol, propylene glycol, butylene glycol, ethyleneglycolmono methylether, ethyleneglycolmono ethylether, ethyleneglycolmono butylether, diethyleneglycolmono methylether, diethyleneglycolmono ethylether, diethyleneglycolmono butylether, propyleneglycol monobutyl ether, ethyleneglycolmono methylether acetate, sulfolane, 2-pyrrolidone, N-methyl-2-pyrrolidone, etc.
Examples of the resin may include ketone resins, ketone formaldehyde resins, amide resins, alkyd resins, rosin-modified resins, rosin-modified phenol resins, phenol resins, xylene resins, polyvinyl pyrrolidone, α- and β-pinene.phenol polycondensation resins, polyvinyl butyral resins, acrylic resins, styrene-maleic acid copolymers, cellulose derivatives, polyvinyl pyrrolidone, polyvinyl alcohol, dextrin, etc.
In addition, as other additives, moisturizers, thickeners, surfactants, preservatives, or mixtures of two or more thereof, may be used.
Examples of the moisturizer may include oligosaccharides such as urea, glycerin, a non-ionic surfactant, reducing or non-reducing starch hydrolyzate, trehalose, sucrose, cyclodextrin, glucose, dextrin, sorbit, mannite, sodium pyrophosphate, etc.
Examples of the thickener (or shear-thinning tackifier) may include xanthan gum, wellan gum, succinoglycan which is a heteropolysaccharide modified with an organic acid having, as a constituent monosaccharide, glucose and galactose (an average molecular weight of about 100 to 8,000,000), alcagum, guar gum, locust bean gum, and derivatives thereof, hydroxy ethylcellulose, alginic acid alkyl esters, a polymer including alkyl esters of methacrylic acid as a main component and having a molecular weight of 100,000 to 150,000, glucomannan, polysaccharide thickeners having a gelation ability and extracted from seaweeds e.g., agar, carrageenin, etc., benzylidene sorbitol and benzylidene xylitol or derivatives thereof, crosslinking acrylic acid polymers, inorganic particulates, polyglycerin fatty acid esters, polyoxyethylene sorbitan fatty acid esters, polyethylene glycol fatty acid esters, polyoxyethylene castor oil, polyoxyethylene lanolin alcohol beeswax derivatives, polyoxyethylene alkyl ether.polyoxypropylenealkyl ethers, polyoxyethylenealkyl phenyl ethers, non-ionic surfactants having an HLB of 8 to 12, e.g., fatty acid amide, salts of dialkyl- or dialkenyl-sulfosuccinic acid, mixtures of N-alkyl-2-pyrrolidone and an anionic surfactant, and mixtures of polyvinyl alcohol and an acrylic resin.
In addition, examples of the surfactant may include higher fatty acids such as oleic acid, etc., non-ionic surfactants having a long-chain alkyl group, polyether-modified silicone oils, thiophosphite triesters such as tri(alkoxycarbonylmethylester) thiophosphite, tri(alkoxycarbonylethylester) thiophosphite, etc., phosphate monoesters of polyoxyethylenealkyl ether or polyoxyethylenealkyl aryl ether, phosphate diesters of polyoxyethylenealkyl ether or polyoxyethylenealkyl aryl ether, etc.
Examples of the preservative may include carbolic acid, sodium salt of 1,2-benz thiazolin-3-one, sodium benzoate, sodium dehydroacetate, potassium sorbate, propyl paraoxybenzoate, 2,3,5,6-tetrachloro-4-(methylsulfonyl)pyridine, etc.
Meanwhile, according to another exemplary embodiment of the present invention, there may be provided a writing apparatus including an ink storage container filled with the thermochromic ink composition according to another exemplary embodiment above. Examples of the writing apparatus are not significantly limited, and for example, may include, as shown in FIG. 5, a cap type or a knock type writing tool 7 including an ink storage container 2, configured of the ink storage container 2, a ballpoint pen tip 3 installed in a tip end of the ink storage container 2, and a follower unit 4 together with an ink provided in a rear end of the thermochromic ink composition 1.
In addition, as shown in FIG. 6, a marking pen that stores the thermochromic ink composition 1 in an ink absorption body to be marked as a pen line may be used, or as shown in FIG. 7, a direct liquid type marking pen that directly stores the thermochromic ink composition 1 in the ink storage container 2, may also be used.
The thermochromic ink composition may be charged in the ink storage container of the writing apparatus. Examples of a method for filling the thermochromic ink composition in the writing apparatus are not significantly limited, and various methods that are widely used in manufacturing fields of the writing apparatus using an ink may be used without limitation.
In addition, the writing apparatus may further include a friction body or a heating element. The friction body means a material of causing appropriate friction at the time of scraping, to generate friction heat, and may be used to erase handwriting formed by the writing apparatus. Examples of the friction body are not significantly limited, and for example, may include elastic bodies such as elastomers, plastic foams, etc., plastic molded bodies, and metals.
Materials of the friction body may include a silicon resin or a SBS resin (a styrene butadiene styrene block copolymer), wherein the silicon resin is easily attached to a part that is erased by scraping, and has a tendency that the handwriting is bounced when repeatedly writing, such that the SBS resin may be more preferably used.
The heating element means a material that is supplied with power from a battery to generate heat, and may be used to erase the handwriting formed by the writing apparatus. Examples of the heating element are not significantly limited, and for example, may include material capable of generating heat by supply of electricity, such as a nichrome wire, etc.
The heating element may be directly used, but may be used in a form in which the heating element is surrounded with a cover. Examples of the cover are not significantly limited, and for example, may include rubber or various materials having thermal resistance and electrical insulation.
The friction body or the heating element does not significantly limit shapes of the writing apparatus, and may be positioned in a state in which the friction body or the heating element is coupled with the writing apparatus. As the friction body or the heating element is coupled with the writing apparatus, portability may be improved. More specifically, as shown in FIG. 5, the friction body or the heating element 5 may be coupled with a front end of a cap 6 or an end of shaft tube tip of the writing apparatus.
According to still another exemplary embodiment of the present invention, there may be provided a smart window including a coating layer in which the thermochromic micro particles according to the exemplary embodiment of the present invention are dispersed. Accordingly, in the smart window, colors may be changed depending on outside temperatures by the coating layer formed on a glass surface, such that transparency property of the glass may be changed to control an absorption degree of light or heat.
The description of the thermochromic micro particles includes the above-described contents with respect to the exemplary embodiment of the present invention.
The coating layer may further include a binder resin to disperse the thermochromic micro particles and to easily form the coating layer through adhesion. Examples of the binder resin are not significantly limited, and for example, may include polyvinyl alcohol-based resins, polyurethane-based resins, polyester-based resins, acrylic resins, etc. Various polymer resins that are widely used in fields for manufacturing coating layers may be used without limitation, in addition to the above-described examples of the binder resin.
An example of a method for forming the coating layer on the smart window may include a method of applying the binder resin in which the thermochromic micro particles are dispersed on a window surface.
According to the present invention, there may be provided the thermochromic ink composition capable of stably implementing a high chromogenic property and a decolorization property and having an improved erasing property, thermal resistance, and chemical resistance, and particles, an ink, a writing apparatus, and a smart window using the same.
Hereinafter, the present disclosure will be explained in detail with reference to the following examples. However, these examples are only to illustrate the inventive concept, and the scope of the inventive concept is not limited thereto.
Examples 1 to 2: Preparation of Thermochromic Micro Particle and Ink Composition
Example 1
(1) Manufacture of Thermochromic Micro Particle
RT-9HC (Rubitherm Technologies, paraffin wax) and lauryl alcohol as a solvent were mixed with bisphenol A (3 g) as a developer and a lactone-based dye (crystal violet lactone) (1 g). Then, an epoxy compound as a wall film material was subjected to emulsification dispersion in 8% polyvinyl alcohol aqueous solution to form micro water droplets, and diethylenetriamine was added thereto, followed by continuously stirring at 70° C. for about 5 hours to obtain a suspension. Then, the suspension was centrifuged to obtain thermochromic micro particles.
(2) Preparation of Thermochromic Ink Composition
A thermochromic ink composition was obtained by mixing 10 wt % of the thermochromic micro particles, 10 wt % of glycerin as a moisturizer, 0.5 wt % of xanthan gum as a thickener, 1 wt % of phosphoric acid ester-based surfactant (PHOSPHANOL RS-410, Japan, Toho Chemical Industry Co., Ltd), 65 wt % of water, and 0.3 wt % of Proxel XL-2 as a preservative, and dissolving and dispersing the mixture.
Example 2
(1) Manufacture of Thermochromic Micro Particles
ECOJOULE TS 1 (paraffin wax) (10 g) and stearyl alcohol (15 g) as a solvent were mixed with 2,2-bis(4-hydroxyphenyl)-hexafluoropropane (3 g) as a developer, and a lactone-based dye (crystal violet lactone) (1 g). Then, KER 828 (epoxy resin, Kumho P&B Chemicals, INC.) as a wall film material was subjected to emulsification dispersion in 8% polyvinyl alcohol aqueous solution to form micro water droplets, and A-053 (Kukdo Chemical Co, Ltd.) as a curing agent was added thereto, followed by continuously stirring at 70° C. for about 5 hours to obtain a suspension. Then, the suspension was centrifuged to obtain thermochromic micro particles.
(2) Preparation of Thermochromic Ink Composition
A thermochromic ink composition was obtained by mixing 10 wt % of the thermochromic micro particles, 10 wt % of glycerin as a moisturizer, 0.5 wt % of xanthan gum as a thickener, 1 wt % of phosphoric acid ester-based surfactant (PHOSPHANOL RS-410, Japan, Toho Chemical Industry Co., Ltd), 65 wt % of water, and 0.3 wt % of Proxel XL-2 as a preservative, and dissolving and dispersing the mixture.
Comparative Examples 1 to 3: Preparation of Thermochromic Micro Particles and Ink Composition
Comparative Example 1
(1) Manufacture of Thermochromic Micro Particles
Thermochromic micro particles were obtained in the same method as Example 1 above except for using furfuryl alcohol only as a solvent.
(2) Preparation of Thermochromic Ink Composition
Thermochromic ink composition was obtained in the same method as Example 1 above.
Comparative Example 2
(1) Manufacture of Thermochromic Micro Particles
Thermochromic micro particles were obtained in the same method as Example 1 above except for using stearyl stearate only as a solvent.
(2) Preparation of Thermochromic Ink Composition
Thermochromic ink composition was obtained in the same method as Example 1 above.
Comparative Example 3
(1) Manufacture of Thermochromic Micro Particles
Thermochromic micro particles were obtained in the same method as Example 1 above except for using butyl stearate only as a solvent.
(2) Preparation of Thermochromic Ink Composition
Thermochromic ink composition was obtained in the same method as Example 1 above.
Experimental Example
1. Crystallization Temperature and Melting Temperature
With respect to the thermochromic micro particles obtained by Examples and Comparative Examples, a crystallization temperature and a melting temperature thereof were measured through the curved line shown in FIG. 3 by using a differential scanning calorimetry (DSC), and results thereof were shown in Table 1 below.
2. Phase Change Characteristic
With respect to the thermochromic micro particles obtained by Examples 1 and 2, phase composition thereof according to fraction (Xpha) of the phase change material was measured, and results thereof were shown in FIG. 1.
As shown in FIG. 1, the thermochromic micro particles of Example had a crystallization temperature between −10° C. and −5° C., and a melting point of 50° C. or more. Accordingly, it could be confirmed that the chromogenic property of the thermochromic micro particles disappeared above 50° C., and the thermochromic micro particles were colorless. The phase change characteristic was caused by the phase change material included in the thermochromic micro particles, which could be confirmed that the color-change temperature range of the dye was controlled by the phase change material.
In addition, it was confirmed that two phases including a solid phase and a liquid phase coexisted on the basis of a boundary surface shown as the curved line in the graph of FIG. 1, and an interval of the phase change zone was maximum at an inflection point fraction (Xpha), such that an effect of maintaining a chromogenic property and a decolorization property was increased.
3. Surface Shape
The surface shape of the thermochromic micro particles obtained by Example 1 was confirmed through FE-SEM, and results thereof were shown in FIG. 2 below.
As shown in FIG. 2 below, it could be confirmed that the thermochromic micro particles obtained by Example 1 had a spherical particle shape having a diameter of 0.1 μm to 10 μm.
4. Thermochromism Property
The thermochromic ink compositions obtained by Examples and Comparative Examples were used to draw images on a paper at room temperature as shown in FIG. 4 below, followed by heating at a temperature of 50° C., and a change of image was observed. Results thereof were evaluated under the following criteria and shown in Table 1 below.
⊚: The image was completely erased after being heated to a temperature of 50° C.
Δ: The image was partially erased and non-erased parts remained after being heated to a temperature of 50° C.
X: The image was not erased after being heated to a temperature of 50° C.











TABLE 1






Crystal-


Color-



lization
Melting
Thermo-
change


Classi-
temperature
temperature
chromism
temperature


fication
(° C.)
(° C.)
property
range



















Example 1
−9
55
⊚
64


Example 2
−29
60
⊚
89


Comparative
—
—
X
—


Example 1


Comparative
50
60
Δ
10


Example 2


Comparative
—
30-35
X
—


Example 3









As shown in Table 1 above, it could be confirmed that the images drawn at room temperature by using the thermochromic ink compositions of Examples were completely erased after being heated to a temperature of 50° C., and had excellent thermochromism property.
On the contrary, it could be confirmed that as to Comparative Examples, the crystallization temperature or the melting temperature was not measured in Comparative Examples 1 to 3, such that the thermochromism property itself was not implemented. Further, the color-change temperature range was below 50° C. in Comparative Example 2, such that sufficient thermochromism property was not implemented.
As described above, it could be confirmed that the thermochromic ink compositions of Examples maintained excellent chromogenic property at room temperature, and had a color-change at between room temperature and 50° C., thereby being rapidly erased by friction heat, etc., with an eraser.

## Claims

1. Thermochromic micro particles comprising:
a core part including a phase change material, a dye, and a developer, the phase change material including at least one selected from the group consisting of at least one chain hydrocarbon having a carbon number of 8 or more, a hydrated inorganic salt, alcohol having a carbon number of 3 or more, and polyalkyleneglycol; and
a shell layer including a polymer resin;
wherein the developer includes 2,2-bis(4′-hydroxyphenyl) hexafluoropropane or 2,2-bis(4′-hydroxyphenyl) propane; and
wherein a weight ratio of the developer to the dye is 2 to 5.

2. The thermochromic micro particles of claim 1, wherein:
a color-change temperature range defined by General Formula 1 below is 50° C. or more:


Color-change temperature range (ΔT)=an absolute value of a difference between a melting point of the phase change material and a crystallization temperature of the phase change material  [General Formula 1].

3. The thermochromic micro particles of claim 2, wherein:
the crystallization temperature of the phase change material is −20° C. to 0° C.

4. The thermochromic micro particles of claim 2, wherein:
the melting point of the phase change material is 50° C. or more.

5. The thermochromic micro particles of claim 1, wherein:
the chain hydrocarbon having a carbon number of 8 or more includes a straight chain saturated hydrocarbon having a carbon number of 10 to 50.

6. The thermochromic micro particles of claim 1, wherein:
the hydrated inorganic salt includes a hydrate of an inorganic acid metal salt or a hydrate of an organic acid metal salt.

7. The thermochromic micro particles of claim 6, wherein:
the inorganic acid metal salt includes sulfates, nitrates, carbonates, phosphates, thiosulfates, or halides of metals.

8. The thermochromic micro particles of claim 6, wherein:
the organic acid metal salt includes acetates of metals.

9. The thermochromic micro particles of claim 1, wherein:
the alcohol having a carbon number of 3 or more includes aliphatic alcohols having a carbon number of 6 to 50 or aromatic alcohols having a carbon number of 3 to 20.

10. The thermochromic micro particles of claim 1, wherein:
a content of the phase change material on the basis of a weight of the thermochromic micro particles is 10 wt % to 70 wt %.

11. The thermochromic micro particles of claim 1, wherein:
the dye is a lactone-based dye.

12. The thermochromic micro particles of claim 11, wherein:
the lactone-based dye includes a phthalide-based compound or a fluoran-based compound.

13. The thermochromic micro particles of claim 1, wherein:
a diameter of the thermochromic micro particle is 0.1 μm to 10 μm.

14. The thermochromic micro particles of claim 1, wherein:
the core part or the shell layer included in the thermochromic micro particles further includes an expansion agent or a contraction agent.

15. A thermochromic ink composition comprising the thermochromic micro particles of claim 1.

16. A writing apparatus comprising
an ink storage container filled with the thermochromic ink composition of claim 15.

17. The writing apparatus of claim 16, further comprising:
a friction body.

18. A window comprising a coating layer in which the thermochromic micro particles of claim 1 are dispersed.