JP2023110331A - reversible thermochromic mask - Google Patents

Abstract

To provide a reversible thermochromic mask that allows both the mask user and the observer to ascertain fever caused by cold or illness.SOLUTION: In a reversible thermochromic mask 1, a mask body 2 comprises: a reversible thermochromic body 3 including a first reversible thermochromic material and a reversible thermochromic body 4 including a second reversible thermochromic material. The reversible thermochromic material exhibits a hysteresis property where: in a process that temperature increases from a colored state, discoloring starts when a temperature reaches a discoloring start temperature t3, and the reversible thermochromic material comes completely into a discolored state in a temperature range of a complete discolored temperature t4 or higher; and in a process that the temperature decreases from the discolored state, coloring starts when the temperature reaches the coloring start temperature t2 and the reversible thermochromic material comes completely into the colored state in a temperature range of a complete colored temperature of t1 or lower. The first reversible thermochromic material has the temperature t3 of 37 to 42°C and exhibits a hysteresis range of 3°C or less, and the second reversible thermochromic material has the temperature t4 of 37 to 42°C and exhibits a hysteresis width of 10°C or over.SELECTED DRAWING: Figure 3

Description

The present invention relates to a reversible thermochromic mask. More particularly, it relates to a reversible thermochromic mask that changes color with temperature change.

Conventionally, a thermochromic mask has been disclosed in which a thermochromic image that changes color with a change in temperature is provided on the outer surface of the mask, and the thermochromic image changes color depending on exhalation, body heat, and environmental temperature (for example, Patent Documents 1 and 2). reference).
Although the thermochromic mask can add interest and unexpectedness in that the image changes color due to temperature changes, the user himself/herself can check the fever due to a cold or illness by the color change of the mask, and the mask can be used by a third party. It was difficult to properly grasp the user's heat generation due to the discoloration of the product.

Microfilm of Japanese Utility Model Application No. 60-200850 (Japanese Utility Model Application No. 62-107849) Microfilm of Japanese Utility Model Application No. 2-127200 (Japanese Utility Model Application No. 4-83262)

The present invention is intended to solve the above-mentioned conventional problems, that is, a reversible thermochromic mask that allows both the user and the observer of the mask to appropriately grasp the fever caused by a cold or illness. I am trying to provide a mask.

The present invention comprises a mask comprising a reversible thermochromic body containing a first reversible thermochromic material and a reversible thermochromic body containing a second reversible thermochromic material, wherein the reversible thermochromic material comprises ( A reversible thermochromic composition comprising (a) an electron-donating color-forming organic compound, (b) an electron-accepting compound, and (c) a reaction medium for controlling the color reaction of (a) and (b). A reversible thermochromic microcapsule pigment encapsulating a substance, or a reversible thermochromic resin particle in which the reversible thermochromic composition is dispersed in a thermoplastic or thermosetting resin, and has a hysteresis characteristic with respect to the color density-temperature curve In the process of increasing the temperature from the colored state, the color begins to fade when the temperature reaches the temperature t ₃ , and the complete color disappears at a temperature t ₄ higher than the temperature t ₃ . In the above temperature range, the color is completely decolored, and in the process of decreasing the temperature from the decolored state, the color starts to develop when the color development start temperature _t2 is reached, and in the temperature range below the complete color development temperature _t1 , which is lower than the temperature _t2 . The _first reversible thermochromic material exhibits a hysteresis characteristic that completely develops a color. The second reversible thermochromic material has a complete decoloring temperature _t4 of 37 to 42 ° C. and a hysteresis width (ΔH) of 10 ° C. or more with respect to the color density-temperature curve. Requires a discoloration mask.
Furthermore, one surface of the mask is provided with a reversible thermochromic body containing a first reversible thermochromic material, and the other surface is provided with a reversible thermochromic body containing a second reversible thermochromic material, The mask itself is either a reversible thermochromic body containing a first reversible thermochromic material or a reversible thermochromic body containing a second reversible thermochromic material, and the other reversible thermochromic body is formed on the surface of the mask. wherein the first reversible thermochromic material has a discoloration start temperature t ₃ of 37.5 to 40° C., and the second reversible thermochromic material has a complete discoloration temperature t ₄ of 37.5° C. The temperature is 5 to 40° C., and the second reversible thermochromic material is a material exhibiting a hysteresis width (ΔH) of 20° C. or more with respect to the color density-temperature curve.

INDUSTRIAL APPLICABILITY The present invention can provide a highly convenient reversible thermochromic mask that allows both the mask user and the observer to appropriately grasp fever due to a cold or illness.

FIG. 2 is an explanatory diagram showing the discoloration behavior of a heat-erasable reversible thermochromic microcapsule pigment. FIG. 2 is an explanatory diagram showing the color change behavior of a heat-erasable reversible thermochromic microcapsule pigment having color memory properties. BRIEF DESCRIPTION OF THE DRAWINGS It is longitudinal cross-sectional explanatory drawing which shows one Example of the reversible thermochromic mask of this invention. FIG. 4 is a longitudinal cross-sectional explanatory view showing another embodiment of the reversible thermochromic mask of the present invention; FIG. 4 is a longitudinal cross-sectional explanatory view showing another embodiment of the reversible thermochromic mask of the present invention;

The mask includes a reversible thermochromic body containing a first reversible thermochromic material (hereinafter referred to as a first reversible thermochromic body) and a reversible thermochromic body containing a second reversible thermochromic material (hereinafter referred to as a second reversible thermochromic body). (referred to as a reversible thermochromic body).
The mask consists of a mask body having a filter function and, if necessary, ear straps for attaching the mask body.
The material of the mask body is not particularly limited, and fabrics such as woven fabrics, nonwoven fabrics, and knitted fabrics can be used, and nonwoven fabrics are preferably used.

The reversible color-changing material includes (a) an electron-donating color-forming organic compound, (b) an electron-accepting compound, and (c) the three essential components of a reaction medium that determine the temperature at which the color reaction occurs between the two. A reversible thermochromic microcapsule pigment is used in which a reversible thermochromic composition containing at least a reversible thermochromic composition whose color is erased by heating is encapsulated in microcapsules.
The reversible thermochromic microcapsule pigment is described in JP-A-61-9488, etc., which changes color before and after a predetermined temperature (color change point) as a boundary, and in a temperature range above the high temperature side color change point. Exhibits a colorless state and a colored state in a temperature range below the low-temperature side color change point. It is maintained while the heat or cold heat applied is applied, but returns to the state exhibited in the normal temperature range when the heat or cold heat is no longer applied. A reversible thermochromic microcapsule pigment encapsulating a reversible thermochromic composition (which disappears and develops color upon cooling) can be applied (see FIG. 1).

In addition, when the hysteresis width (ΔH) described in JP-A-60-264285, JP-A-7-179777, JP-A-8-39936, and International Publication No. 2014/200053 is 10° C. or higher, Yes, the shape of the curve plotting the change in color density due to temperature change differs greatly between when the temperature is raised from the lower temperature side than the discoloration temperature range and when the temperature is lowered from the higher temperature side than the discoloration temperature range. The color changes along the path, and the color development state in a low temperature range below the complete color development temperature (t ₁ ), or the color disappearance state in a high temperature range above the complete color development temperature (t ₄ ), is a specific temperature range [t ₂ to A reversible thermochromic composition of a heat decoloring type (discolored by heating and developing color by cooling) having color memory in the temperature range between _t3 (substantially two-phase retention temperature range)] Thermochromic microcapsule pigments can also be applied (see Figure 2).

The hysteresis characteristic in the color density-temperature curve of the reversible thermochromic composition will be described.
In FIG. 2, the vertical axis represents color density, and the horizontal axis represents temperature. Changes in color density due to temperature changes progress along the arrows. Here, A is a point that indicates the density at a temperature t ₄ (hereinafter referred to as a complete decoloring temperature) at which a completely decolored state is reached, and B is a temperature t ₃ at which decoloring starts (hereinafter referred to as a decoloring start temperature). C is the point indicating the concentration at the temperature t ₂ at which color development starts (hereinafter referred to as the color development start temperature), and D is the temperature t ₁ at which the color develops completely (hereinafter referred to as the complete It is a point that indicates the density at a color development temperature).
The discoloration temperature range is the temperature range between _t1 and _t4 , and can exhibit either a colored state or a decolored state, and is between _t2 and _t3 , which is a range with a large difference in color density. is the substantial two-phase holding temperature range.
Further, the length of the line segment EF is a measure of the color change contrast, and the length of the line segment HG passing through the midpoint of the line segment EF is the temperature width (hereinafter referred to as hysteresis width ΔH) indicating the degree of hysteresis. If the ΔH value is small, only one of the states before and after discoloration can exist in the room temperature range. Also, when the ΔH value is large, it becomes easy to maintain each state before and after discoloration.
The reversible thermochromic composition exhibits a discoloration behavior that returns to the original color in the process of increasing the temperature from temperature t3 to less than temperature t4 and then decreasing the temperature.
That is, when the body temperature reaches temperature t3, the reversible thermochromic composition begins to lose color, continues to lose color as heating continues, and returns to the colored state when heating is stopped below temperature t4.
Further, when the temperature reaches t3 due to body temperature, the color starts to disappear, and when the heating continues, the color disappears further, and when the temperature exceeds the temperature t4, the color disappears.
Therefore, the reversible thermochromic material in the first reversible thermochromic body has a decoloring start temperature _t3 of 37 to 42°C, so that a third party can The state in which the mask repeats decoloring and color development can be visually confirmed, and the reversible thermochromic material in the second reversible thermochromic body has a complete decoloring temperature _t4 of 37 to 42 ° C. A person can visually confirm the presence or absence of heat generation by removing the mask and confirming that the discoloration is maintained.

The reversible thermochromic material in the first reversible thermochromic body has a discoloration start temperature t ₃ of 37 to 42° C., preferably 37.5 to 40° C., which is the temperature generated by heat generation, and has a color density-temperature curve of 3 C. or less, preferably 2.degree. C. or less, more preferably 1.degree. C. or less.
The reversible thermochromic material exhibits a narrow hysteresis width (ΔH) _of 3° C. or less with respect to the color density-temperature curve and undergoes a sharp thermal color change. By setting the exothermic temperature at 37-42° C., the reversible thermochromic material changes color from color to colorless with the exhaled breath of a mask user having a body temperature above normal. After that, when the exhalation is stopped, the reversible thermochromic material changes color from colorless to colored, so that a third party can visually confirm the state of the user's mask repeatedly decoloring and coloring.
In order to heat discolor more sharply, the temperature difference between the decoloring start temperature _t3 and the complete decoloring temperature _t4 is preferably 5°C or less, more preferably 4°C or less, and still more preferably 3°C. ℃ or less.

The reversible thermochromic material in the second reversible thermochromic body has a complete decoloring temperature _t4 of 37 to 42°C, preferably 37.5 to 40°C, and a color density-temperature curve of 10°C or higher, preferably 20°C. ° C. or higher, more preferably 40 ° C. or higher. Therefore, it has color memory. Therefore, by setting the temperature _t4 at which the color is completely erased to 37 to 42°C, which is the temperature at which humans develop a fever due to a cold (cold) or illness, the exhaled breath and face of the mask user, who has a body temperature higher than normal, is exposed to the mask. As a result, the reversible thermochromic material changes color from colored to colorless, and this state is maintained, so that the user can visually confirm the presence or absence of heat generation after removing the mask.
The reversible thermochromic material in the first reversible thermochromic body has a small temperature difference between the discoloration start temperature _t3 and the reversible thermochromic material in the second reversible thermochromic material completely discolored temperature _t4 . It is preferably 1°C or less, more preferably 0.5°C or less.

Specific examples of compounds for each of the components (a), (b), and (c) are shown below.
Component (a), ie, an electron-donating color-forming organic compound, is a component that determines color, and is a compound that provides electrons to component (b), which is a color developer, to develop color.
Electron-donating color-developing organic compounds include phthalide compounds, fluorane compounds, stilinoquinoline compounds, diazarhodamine lactone compounds, pyridine compounds, quinazoline compounds, bisquinazoline compounds, and the like.
Examples of phthalide compounds include diphenylmethanephthalide compounds, phenylindolylphthalide compounds, indolylphthalide compounds, diphenylmethaneazaphthalide compounds, phenylindolylazaphthalide compounds, and derivatives thereof. Among them, phenylindolylazaphthalide compounds and derivatives thereof are preferred.
Further, examples of fluoran compounds include aminofluoran compounds, alkoxyfluoran compounds, and derivatives thereof.
Compounds that can be used as the component (a) are exemplified below.
3,3-bis(4-dimethylaminophenyl)-6-dimethylaminophthalide,
3-(4-diethylaminophenyl)-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-diethylaminophenyl)-4-azaphthalide,
3-(2-ethoxy-4-diethylaminophenyl)-3-(1-ethyl-2-methylindol-3-yl)-4-azaphthalide,
3-(2-n-hexyloxy-4-diethylaminophenyl)-3-(1-ethyl-2-methylindol-3-yl)-4-azaphthalide,
3-[2-ethoxy-4-(N-ethylanilino)phenyl]-3-(1-ethyl-2-methylindol-3-yl)-4-azaphthalide,
3-(2-acetamido-4-diethylaminophenyl)-3-(1-propyl-2-methylindol-3-yl)-4-azaphthalide,
3,6-bis(diphenylamino)fluorane,
3,6-bis(N-phenyl-Np-tolylamino)fluorane,
3,6-dimethoxyfluorane,
3,6-di-n-butoxyfluorane,
2-methyl-6-(N-ethyl-Np-tolylamino)fluorane,
3-chloro-6-cyclohexylaminofluorane,
2-methyl-6-cyclohexylaminofluorane,
2-chloroamino-6-di-n-butylaminofluorane,
2-(2-chloroanilino)-6-di-n-butylaminofluorane,
2-dibenzylamino-6-diethylaminofluorane,
2-N-methylanilino-6-(N-ethyl-Np-tolylamino)fluorane,
1,3-dimethyl-6-diethylaminofluorane,
2-chloro-3-methyl-6-diethylaminofluorane,
2-anilino-3-methyl-6-diethylaminofluorane,
2-anilino-3-methoxy-6-diethylaminofluorane,
2-anilino-3-methyl-6-di-n-butylaminofluorane,
2-anilino-3-methoxy-6-di-n-butylaminofluorane,
2-xylidino-3-methyl-6-diethylaminofluorane,
2-anilino-3-methyl-6-(N-ethyl-Np-tolylamino)fluorane,
6-diethylamino-1,2-benzofluorane,
6-(N-ethyl-N-isobutylamino)-1,2-benzofluorane,
6-(N-ethyl-N-isopentylamino)-1,2-benzofluorane,
2-(3-methoxy-4-dodecoxystyryl)quinoline,
2-diethylamino-8-diethylamino-4-methylspiro[5H-[1]benzopyrano[2,3-d]pyrimidine-5,1′(3′H)-isobenzofuran]-3′-one,
2-di-n-butylamino-8-di-n-butylamino-4-methylspiro[5H-[1]benzopyrano[2,3-d]pyrimidine-5,1′(3′H)-isobenzofuran] -3′-on,
2-di-n-butylamino-8-diethylamino-4-methylspiro[5H-[1]benzopyrano[2,3-d]pyrimidine-5,1′(3′H)-isobenzofuran]-3′-one ,
2-di-n-butylamino-8-(N-ethyl-N-isoamylamino)-4-methylspiro[5H-[1]benzopyrano[2,3-d]pyrimidine-5,1′(3′H) -isobenzofuran]-3'-one,
2-di-n-butylamino-8-di-n-pentylamino-4-methylspiro[5H-[1]benzopyrano[2,3-d]pyrimidine-5,1′(3′H)-isobenzofuran] -3′-on,
4,5,6,7-tetrachloro-3-(4-dimethylamino-2-methoxyphenyl)-3-(1-n-butyl-2-methylindol-3-yl)-1(3H)-iso benzofuranone,
4,5,6,7-tetrachloro-3-(4-diethylamino-2-ethoxyphenyl)-3-(1-ethyl-2-methylindol-3-yl)-1(3H)-isobenzofuranone,
4,5,6,7-tetrachloro-3-(4-diethylamino-2-ethoxyphenyl)-3-(1-n-pentyl-2-methylindol-3-yl)-1(3H)-isobenzo Furanones,
4,5,6,7-tetrachloro-3-(4-diethylamino-2-methylphenyl)-3-(1-ethyl-2-methylindol-3-yl)-1(3H)-isobenzofuranone,
3′,6′-bis[phenyl(2-methylphenyl)amino]spiro[isobenzofuran-1(3H),9′-[9H]xanthen]-3-one,
3′,6′-bis[phenyl(3-methylphenyl)amino]spiro[isobenzofuran-1(3H),9′-[9H]xanthen]-3-one,
3′,6′-bis[phenyl(3-ethylphenyl)amino]spiro[isobenzofuran-1(3H),9′-[9H]xanthen]-3-one,
2,6-bis(2'-ethoxyphenyl)-4-(4'-dimethylaminophenyl)pyridine,
2,6-bis(2′,4′-diethoxyphenyl)-4-(4′-dimethylaminophenyl)pyridine,
2-(4′-dimethylaminophenyl)-4-methoxyquinazoline,
4,4'-ethylenedioxy-bis[2-(4-diethylaminophenyl)quinazoline]
As the fluoranes, in addition to compounds having a substituent on the phenyl group forming the xanthene ring, a substituent on the phenyl group forming the lactone ring as well as having a substituent on the phenyl group forming the xanthene ring (for example, A compound having a blue or black color having an alkyl group such as a methyl group, a halogen atom such as a chlorine atom, etc.) may also be used.

The component (b), that is, the electron-accepting compound, is a compound that receives electrons from the component (a) and functions as a color developer for the component (a).
Examples of the electron-accepting compounds include a group of compounds having an active proton and derivatives thereof, a group of pseudo-acidic compounds (a group of compounds that are not acids but act as acids in the composition to develop the color of component (a)), electron vacancies. There are compounds selected from the group of compounds having pores, etc. Among these, compounds selected from the group of compounds having active protons are preferred.
Examples of compounds having an active proton and derivatives thereof include compounds having a phenolic hydroxyl group and metal salts thereof, carboxylic acids and metal salts thereof, preferably aromatic carboxylic acids, aliphatic carboxylic acids having 2 to 5 carbon atoms and their metal salts, acidic phosphate esters and metal salts thereof, azole compounds and derivatives thereof, 1,2,3-triazole and derivatives thereof, and among these, effective heat discoloration properties can be expressed. A compound having a phenolic hydroxyl group is preferred because it is possible to
The compounds having a phenolic hydroxyl group are widely included from monophenol compounds to polyphenol compounds, and further include bis-type, tris-type phenols, etc., and phenol-aldehyde condensed resins. Among compounds having a phenolic hydroxyl group, those having at least two benzene rings are preferred. In addition, these compounds may have a substituent, and examples of the substituent include an alkyl group, an aryl group, an acyl group, an alkoxycarbonyl group, a carboxy group and its ester or amide group, and a halogen group.
Examples of the metal contained in the metal salt of the compound having an active proton include sodium, potassium, calcium, zinc, zirconium, aluminum, magnesium, nickel, cobalt, tin, copper, iron, vanadium, titanium, lead and molybdenum. be done.

Specific examples are given below.
Phenol, o-cresol, tert-butyl catechol, nonylphenol, n-octylphenol, n-dodecylphenol, n-stearylphenol, p-chlorophenol, p-bromophenol, o-phenylphenol, n-butyl p-hydroxybenzoate , n-octyl p-hydroxybenzoate, resorcinol, dodecyl gallate, 4,4-dihydroxydiphenylsulfone, bis(4-hydroxyphenyl)sulfide, 1,1-bis(4-hydroxyphenyl)ethane, 1,1- Bis(4-hydroxyphenyl)propane, 1,1-bis(4-hydroxyphenyl)n-butane, 1,1-bis(4-hydroxyphenyl)n-pentane, 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, 1,1-bis(4-hydroxyphenyl)-2-methylpropane, 1,1- bis(4-hydroxyphenyl)-3-methylbutane, 1,1-bis(4-hydroxyphenyl)-3-methylpentane, 1,1-bis(4-hydroxyphenyl)-2,3-dimethylpentane, 1, 1-bis(4-hydroxyphenyl)-2-ethylbutane, 1,1-bis(4-hydroxyphenyl)-2-ethylhexane, 1,1-bis(4-hydroxyphenyl)-3,7-dimethyloctane, 1,1-bis(4-hydroxyphenyl)cyclohexane, 1,1-bis(4-hydroxyphenyl)-3,3,5-trimethylcyclohexane, 1-phenyl-1,1-bis(4-hydroxyphenyl)ethane , 2,2-bis(4-hydroxyphenyl)propane, 2,2-bis(4-hydroxyphenyl)n-butane, 2,2-bis(4-hydroxyphenyl)n-pentane, 2,2-bis( 4-hydroxyphenyl)n-hexane, 2,2-bis(4-hydroxyphenyl)n-heptane, 2,2-bis(4-hydroxyphenyl)n-octane, 2,2-bis(4-hydroxyphenyl) ) n-nonane, 2,2-bis(4-hydroxyphenyl)n-decane, 2,2-bis(4-hydroxyphenyl)n-dodecane, 2,2-bis(4-hydroxyphenyl)ethylpropionate , 2,2-bis(4-hydroxyphenyl)-4-methylpentane, 2,2-bis(4-hydroxyphenyl)-4-methylhexane, 2,2-bis(4-hydroxyphenyl)hexafluoropropane, 2,2-bis(4-hydroxy-3-methylphenyl)propane, 9,9-bis(4-hydroxy-3-methylphenyl)fluorene, 1,1-bis[2-(4-hydroxyphenyl)-2 -propyl]benzene, bis(2-hydroxyphenyl)methane, 1,1,1-tris(4-hydroxyphenyl)ethane, 3,3-bis(3-methyl-4-hydroxyphenyl)butane and the like.
A compound having a phenolic hydroxyl group can exhibit the most effective thermochromic properties, but aromatic carboxylic acids, aliphatic carboxylic acids having 2 to 5 carbon atoms, carboxylic acid metal salts, acidic phosphate esters and their It may be a compound selected from metal salts, 1,2,3-triazoles and derivatives thereof, and the like.

The component (c) of the reaction medium for causing the electron transfer reaction by the components (a) and (b) to occur reversibly within a specific temperature range will now be described. Examples of the component (c) include alcohols, esters, ketones, ethers, and acid amides.
The compounds are exemplified below.
As alcohols, aliphatic monohydric saturated alcohols having 10 or more carbon atoms are effective, and specific examples include decyl alcohol, undecyl alcohol, dodecyl alcohol, tridecyl alcohol, tetradecyl alcohol, pentadecyl alcohol, and hexadecyl. alcohol, heptadecyl alcohol, octadecyl alcohol, eicosyl alcohol, docosyl alcohol and the like.

As esters, esters having 10 or more carbon atoms are effective, and any combination of monohydric carboxylic acid having aliphatic and alicyclic or aromatic ring and monohydric alcohol having aliphatic and alicyclic or aromatic ring Esters obtained from any combination of polycarboxylic acids having aliphatic and alicyclic or aromatic rings and monohydric alcohols having aliphatic and alicyclic or aromatic rings, aliphatic and alicyclic Alternatively, esters obtained from any combination of a monovalent carboxylic acid having an aromatic ring and a polyhydric alcohol having an aliphatic, alicyclic or aromatic ring can be mentioned, specifically ethyl caprylate, octyl caprylate, capryl Stearyl acid, myristyl caprate, docosyl caprate, 2-ethylhexyl laurate, n-decyl laurate, 3-methylbutyl myristate, cetyl myristate, isopropyl palmitate, neopentyl palmitate, nonyl palmitate, cyclohexyl palmitate, stearin n-butyl acid, 2-methylbutyl stearate, 3,5,5-trimethylhexyl stearate, n-undecyl stearate, pentadecyl stearate, stearyl stearate, cyclohexylmethyl stearate, isopropyl behenate, hexyl behenate, behene Lauryl acid, behenyl behenate, cetyl benzoate, p-tert-butyl stearyl benzoate, dimyristyl phthalate, distearyl phthalate, dimyristyl oxalate, dicetyl oxalate, dicetyl malonate, dilauryl succinate, dilauryl glutarate, adipine diundecyl acid, dilauryl azelate, di-(n-nonyl) sebacate, dineopentyl 1,18-octadecylmethylenedicarboxylate, ethylene glycol dimyristate, propylene glycol dilaurate, propylene glycol distearate, hexylene glycol dipalmitate, 1,5-pentanediol distearate, 1,2,6-hexanetriol trimyristate, 1,4-cyclohexanediol didecyl, 1,4-cyclohexanedimethanol dimyristate, xylene glycol dicaprinate, xylene glycol distearate and the like.
Also, esters of saturated fatty acids and branched fatty alcohols, esters of unsaturated fatty acids or branched or substituted saturated fatty acids and branched or branched fatty alcohols having 16 or more carbon atoms, cetyl butyrate, stearyl butyrate and Ester compounds selected from behenyl butyrate are also effective.
Specifically, 2-ethylhexyl butyrate, 2-ethylhexyl behenate, 2-ethylhexyl myristate, 2-ethylhexyl caprate, 3,5,5-trimethylhexyl laurate, 3,5,5-trimethylhexyl palmitate, 3,5,5-trimethylhexyl stearate, 2-methylbutyl caproate, 2-methylbutyl caprylate, 2-methylbutyl caprate, 1-ethylpropyl palmitate, 1-ethylpropyl stearate, 1-ethylpropyl behenate, 1-Ethylhexyl Laurate, 1-Ethylhexyl Myristate, 1-Ethylhexyl Palmitate, 2-Methylpentyl Caproate, 2-Methylpentyl Caprylate, 2-Methylpentyl Caprate, 2-Methylpentyl Laurate, 2-Stearate Methylbutyl, 2-methylbutyl stearate, 3-methylbutyl stearate, 1-methylheptyl stearate, 2-methylbutyl behenate, 3-methylbutyl behenate, 1-methylheptyl stearate, 1-methylheptyl behenate, 1 caproic acid -ethylpentyl, 1-ethylpentyl palmitate, 1-methylpropyl stearate, 1-methyloctyl stearate, 1-methylhexyl stearate, 1,1-dimethylpropyl laurate, 1-methylpentyl caprate, palmitic acid 2-methylhexyl, 2-methylhexyl stearate, 2-methylhexyl behenate, 3,7-dimethyloctyl laurate, 3,7-dimethyloctyl myristate, 3,7-dimethyloctyl palmitate, stearic acid 3, 7-dimethyloctyl, 3,7-dimethyloctyl behenate, stearyl oleate, behenyl oleate, stearyl linoleate, behenyl linoleate, 3,7-dimethyloctyl erucate, stearyl erucate, isostearyl erucate, isostearic acid Cetyl, stearyl isostearate, 2-methylpentyl 12-hydroxystearate, 2-ethylhexyl 18-bromostearate, isostearyl 2-ketomyristate, 2-ethylhexyl 2-fluoromyristate, cetyl butyrate, stearyl butyrate, behenyl butyrate etc.

Further, as the component (c) for obtaining a reversible thermochromic composition having color memory, a carboxylic acid ester compound exhibiting a ΔT value (melting point - cloud point) of 5°C or higher and lower than 50°C, such as A carboxylic acid ester containing a substituted aromatic ring, an ester of a carboxylic acid containing an unsubstituted aromatic ring and an aliphatic alcohol having 10 or more carbon atoms, a carboxylic acid ester containing a cyclohexyl group in the molecule, a fatty acid having 6 or more carbon atoms and Esters of unsubstituted aromatic alcohols or phenols, fatty acids with 8 or more carbon atoms and branched aliphatic alcohols or esters, esters of dicarboxylic acids and aromatic alcohols or branched aliphatic alcohols, dibenzyl cinnamate, heptyl stearate, didecyl adipate , dilauryl adipate, dimyristyl adipate, dicetyl adipate, distearyl adipate, trilaurin, trimyristin, tristearin, dimyristin, distearin, and the like.

In addition, a fatty acid ester compound obtained from an odd aliphatic monohydric alcohol having 9 or more carbon atoms and an even aliphatic carboxylic acid having an even number of carbon atoms, n-pentyl alcohol or n-heptyl alcohol and an even fat having 10 to 16 carbon atoms Fatty acid ester compounds having 17 to 23 total carbon atoms obtained from group carboxylic acids are also effective.
Specifically, n-pentadecyl acetate, n-tridecyl butyrate, n-pentadecyl butyrate, n-undecyl caproate, n-tridecyl caproate, n-pentadecyl caproate, n-nonyl caprylate, n-undecyl caprylate, n-tridecyl caprylate, n-pentadecyl caprylate, n-heptyl caprate, n-nonyl caprate, n-undecyl caprate, n-tridecyl caprate, n-pentadecyl caprate, n-pentyl laurate, lauric acid n-heptyl, n-nonyl laurate, n-undecyl laurate, n-tridecyl laurate, n-pentadecyl laurate, n-pentyl myristate, n-heptyl myristate, n-nonyl myristate, n-myristate undecyl, n-tridecyl myristate, n-pentadecyl myristate, n-pentyl palmitate, n-heptyl palmitate, n-nonyl palmitate, n-undecyl palmitate, n-tridecyl palmitate, n-pentadecyl palmitate, n-nonyl stearate, n-undecyl stearate, n-tridecyl stearate, n-pentadecyl stearate, n-nonyl eicosanoate, n-undecyl eicosanoate, n-tridecyl eicosanoate, n-pentadecyl eicosanoate, behenic acid Examples include n-nonyl, n-undecyl behenate, n-tridecyl behenate, n-pentadecyl behenate and the like.

As ketones, aliphatic ketones having a total carbon number of 10 or more are effective. -dodecanone, 3-dodecanone, 4-dodecanone, 5-dodecanone, 2-tridecanone, 3-tridecanone, 2-tetradecanone, 2-pentadecanone, 8-pentadecanone, 2-hexadecanone, 3-hexadecanone, 9-heptadecanone, 2-pentadecanone , 2-octadecanone, 2-nonadecanone, 10-nonadecanone, 2-eicosanone, 11-eicosanone, 2-heneicosanone, 2-docosanone, laurone, stearone and the like.
In addition, arylalkyl ketones having a total carbon number of 12 to 24, such as n-octadecanophenone, n-heptadecanophenone, n-hexadecanophenone, n-pentadecanophenone, n-tetradecano phenone, 4-n-dodecaacetophenone, n-tridecanophenone, 4-n-undecanoacetophenone, n-laurophenone, 4-n-decanoacetophenone, n-undecanophenone, 4-n-nonylacetophenone, n -decanophenone, 4-n-octylacetophenone, n-nonanophenone, 4-n-heptylacetophenone, n-octanophenone, 4-n-hexylacetophenone, 4-n-cyclohexylacetophenone, 4-tert-butylpropiophenone, n-heptaphenone, 4-n-pentylacetophenone, cyclohexylphenyl ketone, benzyl-n-butyl ketone, 4-n-butylacetophenone, n-hexanophenone, 4-isobutylacetophenone, 1-acetonaphtone, 2-acenaphthone, cyclopentylphenyl ketone etc. can be mentioned.

As ethers, aliphatic ethers having a total carbon number of 10 or more are effective, and dipentyl ether, dihexyl ether, diheptyl ether, dioctyl ether, dinonyl ether, didecyl ether, diundecyl ether, didodecyl ether, ditri Decyl ether, ditetradecyl ether, dipentadecyl ether, dihexadecyl ether, dioctadecyl ether, decanediol dimethyl ether, undecanediol dimethyl ether, dodecanediol dimethyl ether, tridecanediol dimethyl ether, decanediol diethyl ether, undecanediol diethyl ether, etc. can be mentioned.

Acid amides include hexanoic acid amide, heptanoic acid amide, octanoic acid amide, nonanoic acid amide, decanoic acid amide, undecanoic acid amide, lauric acid amide, tridecanoic acid amide, myristic acid amide, palmitic acid amide, stearic acid amide, Docosanoic acid amide and the like can be mentioned.

〔式中、Ｒ_１は水素原子又はメチル基を示し、ｍは０～２の整数を示し、Ｘ_１、Ｘ_２のいずれか一方は－（ＣＨ_２）_ｎＯＣＯＲ_２又は－（ＣＨ_２）_ｎＣＯＯＲ_２、他方は水素原子を示し、ｎは０～２の整数を示し、Ｒ_２は炭素数４以上のアルキル基又はアルケニル基を示し、Ｙ_１及びＹ_２は水素原子、炭素数１～４のアルキル基、メトキシ基、又は、ハロゲンを示し、ｒ及びｐは１～３の整数を示す。〕
前記式（１）で示される化合物のうち、Ｒ_１が水素原子の場合、より広いヒステリシス幅を有する可逆熱変色性組成物が得られるため好適であり、更にＲ_１が水素原子であり、且つ、ｍが０の場合がより好適である。
なお、式（１）で示される化合物のうち、より好ましくは下記一般式（２）で示される化合物が用いられる。

式中のＲは炭素数８以上のアルキル基又はアルケニル基を示すが、好ましくは炭素数１０～２４のアルキル基、更に好ましくは炭素数１２～２２のアルキル基である。
前記化合物として具体的には、オクタン酸－４－ベンジルオキシフェニルエチル、ノナン酸－４－ベンジルオキシフェニルエチル、デカン酸－４－ベンジルオキシフェニルエチル、ウンデカン酸－４－ベンジルオキシフェニルエチル、ドデカン酸－４－ベンジルオキシフェニルエチル、トリデカン酸－４－ベンジルオキシフェニルエチル、テトラデカン酸－４－ベンジルオキシフェニルエチル、ペンタデカン酸－４－ベンジルオキシフェニルエチル、ヘキサデカン酸－４－ベンジルオキシフェニルエチル、ヘプタデカン酸－４－ベンジルオキシフェニルエチル、オクタデカン酸－４－ベンジルオキシフェニルエチルを例示できる。 A compound represented by the following general formula (1) can also be used as the component (c).

[In the formula, R ₁ represents a hydrogen atom or a methyl group, m represents an integer of 0 to 2, and one of X ₁ and X ₂ is -(CH ₂ ) _n OCOR ₂ or -(CH ₂ ) _n COOR ₂ and the other represent a hydrogen atom, n represents an integer of 0 to 2, R ₂ represents an alkyl group or alkenyl group having 4 or more carbon atoms, Y ₁ and Y ₂ represent a hydrogen atom, and have 1 to 4 carbon atoms. is an alkyl group, a methoxy group, or a halogen, and r and p are integers of 1-3. ]
Among the compounds represented by the formula (1), when R ₁ is a hydrogen atom, it is preferable because a reversible thermochromic composition having a wider hysteresis width can be obtained, and R ₁ is a hydrogen atom, and , m are more preferably 0.
Among the compounds represented by the formula (1), the compounds represented by the following general formula (2) are more preferably used.

In the formula, R represents an alkyl group or alkenyl group having 8 or more carbon atoms, preferably an alkyl group having 10 to 24 carbon atoms, more preferably an alkyl group having 12 to 22 carbon atoms.
Specific examples of the compounds include 4-benzyloxyphenylethyl octanoate, 4-benzyloxyphenylethyl nonanoate, 4-benzyloxyphenylethyl decanoate, 4-benzyloxyphenylethyl undecanoate, and dodecanoic acid. -4-benzyloxyphenylethyl, -4-benzyloxyphenylethyl tridecanoate, -4-benzyloxyphenylethyl tetradecanoate, -4-benzyloxyphenylethyl pentadecanoate, -4-benzyloxyphenylethyl hexadecanoate, heptadecanoic acid -4-benzyloxyphenylethyl and 4-benzyloxyphenylethyl octadecanoate can be exemplified.

（式中、Ｒは炭素数８以上のアルキル基又はアルケニル基を示し、ｍ及びｎはそれぞれ１～３の整数を示し、Ｘ及びＹはそれぞれ水素原子、炭素数１～４のアルキル基、炭素数１～４のアルコキシ基、ハロゲンを示す。）
前記化合物として具体的には、オクタン酸１,１－ジフェニルメチル、ノナン酸１,１－ジフェニルメチル、デカン酸１,１－ジフェニルメチル、ウンデカン酸１,１－ジフェニルメチル、ドデカン酸１,１－ジフェニルメチル、トリデカン酸１,１－ジフェニルメチル、テトラデカン酸１,１－ジフェニルメチル、ペンタデカン酸１,１－ジフェニルメチル、ヘキサデカン酸１,１－ジフェニルメチル、ヘプタデカン酸１,１－ジフェニルメチル、オクタデカン酸１,１－ジフェニルメチルを例示できる。 Furthermore, a compound represented by the following general formula (3) can also be used as the component (c).

(Wherein, R represents an alkyl group or alkenyl group having 8 or more carbon atoms, m and n each represent an integer of 1 to 3, X and Y are each a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, a carbon Alkoxy groups of numbers 1 to 4, halogen.)
Specific examples of the compounds include 1,1-diphenylmethyl octanoate, 1,1-diphenylmethyl nonanoate, 1,1-diphenylmethyl decanoate, 1,1-diphenylmethyl undecanoate, and 1,1-dodecanoate. Diphenylmethyl, 1,1-diphenylmethyl tridecanoate, 1,1-diphenylmethyl tetradecanoate, 1,1-diphenylmethyl pentadecanoate, 1,1-diphenylmethyl hexadecanoate, 1,1-diphenylmethyl heptadecanoate, octadecanoic acid 1,1-diphenylmethyl can be exemplified.

（式中、Ｘは水素原子、炭素数１乃至４のアルキル基、メトキシ基、ハロゲン原子のいずれかを示し、ｍは１乃至３の整数を示し、ｎは１乃至２０の整数を示す。）
前記化合物としては、マロン酸と２－〔４－(４－クロロベンジルオキシ）フェニル）〕エタノールとのジエステル、こはく酸と２－（４－ベンジルオキシフェニル）エタノールとのジエステル、こはく酸と２－〔４－(３－メチルベンジルオキシ）フェニル）〕エタノールとのジエステル、グルタル酸と２－（４－ベンジルオキシフェニル）エタノールとのジエステル、グルタル酸と２－〔４－(４－クロロベンジルオキシ）フェニル）〕エタノールとのジエステル、アジピン酸と２－（４－ベンジルオキシフェニル）エタノールとのジエステル、ピメリン酸と２－（４－ベンジルオキシフェニル）エタノールとのジエステル、スベリン酸と２－（４－ベンジルオキシフェニル）エタノールとのジエステル、スベリン酸と２－〔４－(３－メチルベンジルオキシ）フェニル）〕エタノールとのジエステル、スベリン酸と２－〔４－(４－クロロベンジルオキシ）フェニル）〕エタノールとのジエステル、スベリン酸と２－〔４－(２，４－ジクロロベンジルオキシ）フェニル）〕エタノールとのジエステル、アゼライン酸と２－（４－ベンジルオキシフェニル）エタノールとのジエステル、セバシン酸と２－（４－ベンジルオキシフェニル）エタノールとのジエステル、１，１０－デカンジカルボン酸と２－（４－ベンジルオキシフェニル）エタノールとのジエステル、１，１８-オクタデカンジカルボン酸と２－（４－ベンジルオキシフェニル）エタノールとのジエステル、１，１８-オクタデカンジカルボン酸と２－〔４－(２－メチルベンジルオキシ）フェニル）〕エタノールとのジエステルを例示できる。 Furthermore, a compound represented by the following general formula (4) can also be used as the component (c).

(Wherein, X represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, a methoxy group, or a halogen atom, m represents an integer of 1 to 3, and n represents an integer of 1 to 20.)
Examples of the compounds include a diester of malonic acid and 2-[4-(4-chlorobenzyloxy)phenyl)]ethanol, a diester of succinic acid and 2-(4-benzyloxyphenyl)ethanol, a diester of succinic acid and 2- [4-(3-methylbenzyloxy)phenyl)]ethanol diester, glutaric acid and 2-(4-benzyloxyphenyl)ethanol diester, glutaric acid and 2-[4-(4-chlorobenzyloxy) phenyl)]ethanol, adipic acid with 2-(4-benzyloxyphenyl)ethanol, pimelic acid with 2-(4-benzyloxyphenyl)ethanol, suberic acid with 2-(4- benzyloxyphenyl)ethanol, diester of suberic acid with 2-[4-(3-methylbenzyloxy)phenyl)]ethanol, suberic acid with 2-[4-(4-chlorobenzyloxy)phenyl)] Diesters of ethanol, diesters of suberic acid and 2-[4-(2,4-dichlorobenzyloxy)phenyl)]ethanol, diesters of azelaic acid and 2-(4-benzyloxyphenyl)ethanol, sebacic acid and 2-(4-benzyloxyphenyl)ethanol diester, 1,10-decanedicarboxylic acid and 2-(4-benzyloxyphenyl)ethanol diester, 1,18-octadecanedicarboxylic acid and 2-(4-benzyl) Examples include diesters with oxyphenyl)ethanol and diesters with 1,18-octadecanedicarboxylic acid and 2-[4-(2-methylbenzyloxy)phenyl)]ethanol.

（式中、Ｒは炭素数１乃至２１のアルキル基又はアルケニル基を示し、ｎは１乃至３の整数を示す。）
前記化合物としては、１，３－ビス（２－ヒドロキシエトキシ）ベンゼンとカプリン酸とのジエステル、１，３－ビス（２－ヒドロキシエトキシ）ベンゼンとウンデカン酸とのジエステル、１，３－ビス（２－ヒドロキシエトキシ）ベンゼンとラウリン酸とのジエステル、１，３－ビス（２－ヒドロキシエトキシ）ベンゼンとミリスチン酸とのジエステル、１，４－ビス（ヒドロキシメトキシ）ベンゼンと酪酸とのジエステル、１，４－ビス（ヒドロキシメトキシ）ベンゼンとイソ吉草酸とのジエステル、１，４－ビス（２－ヒドロキシエトキシ）ベンゼンと酢酸とのジエステル、１，４－ビス（２－ヒドロキシエトキシ）ベンゼンとプロピオン酸とのジエステル、１，４－ビス（２－ヒドロキシエトキシ）ベンゼンと吉草酸とのジエステル、１，４－ビス（２－ヒドロキシエトキシ）ベンゼンとカプロン酸とのジエステル、１，４－ビス（２－ヒドロキシエトキシ）ベンゼンとカプリル酸とのジエステル、１，４－ビス（２－ヒドロキシエトキシ）ベンゼンとカプリン酸とのジエステル、１，４－ビス（２－ヒドロキシエトキシ）ベンゼンとラウリン酸とのジエステル、１，４－ビス（２－ヒドロキシエトキシ）ベンゼンとミリスチン酸とのジエステルを例示できる。 Furthermore, a compound represented by the following general formula (5) can also be used as the component (c).

(Wherein, R represents an alkyl or alkenyl group having 1 to 21 carbon atoms, and n represents an integer of 1 to 3.)
Examples of the compounds include diesters of 1,3-bis(2-hydroxyethoxy)benzene and capric acid, diesters of 1,3-bis(2-hydroxyethoxy)benzene and undecanoic acid, 1,3-bis(2 -hydroxyethoxy)benzene with lauric acid, 1,3-bis(2-hydroxyethoxy)benzene with myristic acid, 1,4-bis(hydroxymethoxy)benzene with butyric acid, 1,4 - the diester of bis(hydroxymethoxy)benzene with isovaleric acid, the diester of 1,4-bis(2-hydroxyethoxy)benzene with acetic acid, the diester of 1,4-bis(2-hydroxyethoxy)benzene with propionic acid Diesters, diesters of 1,4-bis(2-hydroxyethoxy)benzene and valeric acid, diesters of 1,4-bis(2-hydroxyethoxy)benzene and caproic acid, 1,4-bis(2-hydroxyethoxy) ) diesters of benzene and caprylic acid, diesters of 1,4-bis(2-hydroxyethoxy)benzene and capric acid, diesters of 1,4-bis(2-hydroxyethoxy)benzene and lauric acid, 1,4 -Diesters of bis(2-hydroxyethoxy)benzene and myristic acid can be exemplified.

（式中、Ｘは水素原子、炭素数１乃至４のアルキル基、炭素数１乃至４のアルコキシ基、ハロゲン原子のいずれかを示し、ｍは１乃至３の整数を示し、ｎは１乃至２０の整数を示す。）
前記化合物としては、こはく酸と２－フェノキシエタノールとのジエステル、スベリン酸と２－フェノキシエタノールとのジエステル、セバシン酸と２－フェノキシエタノールとのジエステル、１，１０-デカンジカルボン酸と２－フェノキシエタノールとのジエステル、１，１８-オクタデカンジカルボン酸と２－フェノキシエタノールとのジエステルを例示できる。 Furthermore, a compound represented by the following general formula (6) can also be used as the component (c).

(Wherein, X represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, or a halogen atom, m represents an integer of 1 to 3, and n represents 1 to 20 indicates an integer of
Examples of the compounds include diesters of succinic acid and 2-phenoxyethanol, diesters of suberic acid and 2-phenoxyethanol, diesters of sebacic acid and 2-phenoxyethanol, diesters of 1,10-decanedicarboxylic acid and 2-phenoxyethanol, A diester of 1,18-octadecanedicarboxylic acid and 2-phenoxyethanol can be exemplified.

（式中、Ｒは炭素数４乃至２２のアルキル基、シクロアルキルアルキル基、シクロアルキル基、炭素数４乃至２２のアルケニル基のいずれかを示し、Ｘは水素原子、炭素数１乃至４のアルキル基、炭素数１乃至４のアルコキシ基、ハロゲン原子のいずれかを示し、ｎは０又は１を示す。）
前記化合物としては、４－フェニル安息香酸デシル、４－フェニル安息香酸ラウリル、４－フェニル安息香酸ミリスチル、４－フェニル安息香酸シクロヘキシルエチル、４－ビフェニル酢酸オクチル、４－ビフェニル酢酸ノニル、４－ビフェニル酢酸デシル、４－ビフェニル酢酸ラウリル、４－ビフェニル酢酸ミリスチル、４－ビフェニル酢酸トリデシル、４－ビフェニル酢酸ペンタデシル、４－ビフェニル酢酸セチル、４－ビフェニル酢酸シクロペンチル、４－ビフェニル酢酸シクロヘキシルメチル、４－ビフェニル酢酸ヘキシル、４－ビフェニル酢酸シクロヘキシルメチルを例示できる。 Furthermore, a compound represented by the following general formula (7) can also be used as the component (c).

(Wherein, R is an alkyl group having 4 to 22 carbon atoms, a cycloalkylalkyl group, a cycloalkyl group, or an alkenyl group having 4 to 22 carbon atoms, X is a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, group, an alkoxy group having 1 to 4 carbon atoms, or a halogen atom, and n is 0 or 1.)
Examples of the compounds include decyl 4-phenylbenzoate, lauryl 4-phenylbenzoate, myristyl 4-phenylbenzoate, cyclohexylethyl 4-phenylbenzoate, octyl 4-biphenylacetate, nonyl 4-biphenylacetate, and 4-biphenylacetic acid. Decyl, 4-biphenylacetate lauryl, 4-biphenylacetate myristyl, 4-biphenylacetate tridecyl, 4-biphenylacetate pentadecyl, 4-biphenylacetate cetyl, 4-biphenylacetate cyclopentyl, 4-biphenylacetate cyclohexylmethyl, 4-biphenylacetate hexyl , 4-biphenylacetate cyclohexylmethyl.

（式中、Ｒは炭素数３乃至１８のアルキル基、炭素数３乃至１８の脂肪族アシル基のいずれかを示し、Ｘは水素原子、炭素数１乃至３のアルキル基、炭素数１又は２のアルコキシ基、ハロゲン原子のいずれかを示し、Ｙは水素原子、メチル基のいずれかを示し、Ｚは水素原子、炭素数１乃至４のアルキル基、炭素数１又は２のアルコキシ基、ハロゲン原子のいずれかを示す。）
前記化合物としては、４－ブトキシ安息香酸フェノキシエチル、４－ペンチルオキシ安息香酸フェノキシエチル、４－テトラデシルオキシ安息香酸フェノキシエチル、４－ヒドロキシ安息香酸フェノキシエチルとドデカン酸とのエステル、バニリン酸フェノキシエチルのドデシルエーテルを例示できる。 Furthermore, a compound represented by the following general formula (8) can also be used as the component (c).

(Wherein, R represents either an alkyl group having 3 to 18 carbon atoms or an aliphatic acyl group having 3 to 18 carbon atoms, X is a hydrogen atom, an alkyl group having 1 to 3 carbon atoms, 1 or 2 carbon atoms is either an alkoxy group or a halogen atom, Y is a hydrogen atom or a methyl group, Z is a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 or 2 carbon atoms, a halogen atom indicates either.)
Examples of the compounds include phenoxyethyl 4-butoxybenzoate, phenoxyethyl 4-pentyloxybenzoate, phenoxyethyl 4-tetradecyloxybenzoate, esters of phenoxyethyl 4-hydroxybenzoate and dodecanoic acid, and phenoxyethyl vanillate. can be exemplified by the dodecyl ether of

（式中、Ｒは炭素数４乃至２２のアルキル基、炭素数４乃至２２のアルケニル基、シクロアルキルアルキル基、シクロアルキル基のいずれかを示し、Ｘは水素原子、アルキル基、アルコキシ基、ハロゲン原子のいずれかを示し、Ｙは水素原子、アルキル基、アルコキシ基、ハロゲン原子のいずれかを示し、ｎは０又は１を示す。）
前記化合物としては、ｐ－ヒドロキシ安息香酸オクチルの安息香酸エステル、ｐ－ヒドロキシ安息香酸デシルの安息香酸エステル、ｐ－ヒドロキシ安息香酸ヘプチルのｐ－メトキシ安息香酸エステル、ｐ－ヒドロキシ安息香酸ドデシルのo-メトキシ安息香酸エステル、ｐ－ヒドロキシ安息香酸シクロヘキシルメチルの安息香酸エステルを例示できる。 Furthermore, a compound represented by the following general formula (9) can also be used as the component (c).

(Wherein, R represents an alkyl group having 4 to 22 carbon atoms, an alkenyl group having 4 to 22 carbon atoms, a cycloalkylalkyl group, or a cycloalkyl group; X represents a hydrogen atom, an alkyl group, an alkoxy group, a halogen atom, Y is a hydrogen atom, an alkyl group, an alkoxy group, or a halogen atom, and n is 0 or 1.)
Examples of the above compounds include benzoic acid ester of octyl p-hydroxybenzoate, benzoic acid ester of decyl p-hydroxybenzoate, p-methoxybenzoic acid ester of heptyl p-hydroxybenzoate, and o- benzoic acid ester of dodecyl p-hydroxybenzoate. Examples include methoxybenzoic acid esters and benzoic acid esters of cyclohexylmethyl p-hydroxybenzoate.

（式中、Ｒは炭素数３乃至１８のアルキル基、炭素数６乃至１１のシクロアルキルアルキル基、炭素数５乃至７のシクロアルキル基、炭素数３乃至１８のアルケニル基のいずれかを示し、Ｘは水素原子、炭素数１乃至４のアルキル基、炭素数１乃至３のアルコキシ基、ハロゲン原子のいずれかを示し、Ｙは水素原子、炭素数１乃至４のアルキル基、メトキシ基、エトキシ基、ハロゲン原子のいずれかを示す。）
前記化合物としては、ｐ－ヒドロキシ安息香酸ノニルのフェノキシエチルエーテル、ｐ－ヒドロキシ安息香酸デシルのフェノキシエチルエーテル、ｐ－ヒドロキシ安息香酸ウンデシルのフェノキシエチルエーテル、バニリン酸ドデシルのフェノキシエチルエーテルを例示できる。 Furthermore, a compound represented by the following general formula (10) can also be used as the component (c).

(Wherein, R is an alkyl group having 3 to 18 carbon atoms, a cycloalkylalkyl group having 6 to 11 carbon atoms, a cycloalkyl group having 5 to 7 carbon atoms, or an alkenyl group having 3 to 18 carbon atoms, X is a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 3 carbon atoms, or a halogen atom; Y is a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, a methoxy group, or an ethoxy group; , indicates one of the halogen atoms.)
Examples of the compound include phenoxyethyl ether of nonyl p-hydroxybenzoate, phenoxyethyl ether of decyl p-hydroxybenzoate, phenoxyethyl ether of undecyl p-hydroxybenzoate, and phenoxyethyl ether of dodecyl vanillate.

（式中、Ｒは炭素数３乃至８のシクロアルキル基又は炭素数４乃至９のシクロアルキルアルキル基を示し、ｎは１乃至３の整数を示す。）
前記化合物としては、１，３－ビス（２－ヒドロキシエトキシ）ベンゼンとシクロヘキサンカルボン酸とのジエステル、１，４－ビス（２－ヒドロキシエトキシ）ベンゼンとシクロヘキサンプロピオン酸とのジエステル、１，３－ビス（２－ヒドロキシエトキシ）ベンゼンとシクロヘキサンプロピオン酸とのジエステルを例示できる。 Furthermore, a compound represented by the following general formula (11) can also be used as the component (c).

(In the formula, R represents a cycloalkyl group having 3 to 8 carbon atoms or a cycloalkylalkyl group having 4 to 9 carbon atoms, and n represents an integer of 1 to 3.)
Examples of the compounds include diesters of 1,3-bis(2-hydroxyethoxy)benzene and cyclohexanecarboxylic acid, diesters of 1,4-bis(2-hydroxyethoxy)benzene and cyclohexanepropionic acid, 1,3-bis A diester of (2-hydroxyethoxy)benzene and cyclohexanepropionic acid can be exemplified.

（式中、Ｒは炭素数３乃至１７のアルキル基、炭素数３乃至８のシクロアルキル基、炭素数５乃至８のシクロアルキルアルキル基を示し、Ｘは水素原子、炭素数１乃至５のアルキル基、メトキシ基、エトキシ基、ハロゲン原子を示し、ｎは１乃至３の整数を示す。）
前記化合物としては、４－フェニルフェノールエチレングリコールエーテルとシクロヘキサンカルボン酸とのジエステル、４－フェニルフェノールジエチレングリコールエーテルとラウリン酸とのジエステル、４－フェニルフェノールトリエチレングリコールエーテルとシクロヘキサンカルボン酸とのジエステル、４－フェニルフェノールエチレングリコールエーテルとオクタン酸とのジエステル、４－フェニルフェノールエチレングリコールエーテルとノナン酸とのジエステル、４－フェニルフェノールエチレングリコールエーテルとデカン酸とのジエステル、４－フェニルフェノールエチレングリコールエーテルとミリスチン酸とのジエステルを例示できる。 Furthermore, a compound represented by the following general formula (12) can also be used as the component (c).

(Wherein, R represents an alkyl group having 3 to 17 carbon atoms, a cycloalkyl group having 3 to 8 carbon atoms, a cycloalkylalkyl group having 5 to 8 carbon atoms, X is a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, group, methoxy group, ethoxy group, halogen atom, and n is an integer of 1 to 3.)
Examples of the compounds include a diester of 4-phenylphenol ethylene glycol ether and cyclohexanecarboxylic acid, a diester of 4-phenylphenoldiethylene glycol ether and lauric acid, a diester of 4-phenylphenoltriethylene glycol ether and cyclohexanecarboxylic acid, - diesters of phenylphenol ethylene glycol ethers with octanoic acid, diesters of 4-phenylphenol ethylene glycol ethers with nonanoic acid, diesters of 4-phenylphenol ethylene glycol ethers with decanoic acid, 4-phenylphenol ethylene glycol ethers with myristine A diester with an acid can be exemplified.

The ratio of each component in the reversible thermochromic composition depends on the concentration, color change temperature, color change form, and type of each component. For, (b) component 0.1 to 100, preferably 0.1 to 50, more preferably 0.5 to 20, (c) component 1 to 800, preferably 5 to 200, more preferably 10 to 100 range (all the above percentages are parts by weight).
Here, a colorant such as a non-thermochromic dye or pigment may be blended into the reversible thermochromic microcapsule pigment to exhibit a tautomatic color change from colored (1) to colored (2). can.

Each component may be a mixture of two or more compounds, and a light stabilizer may be added to the extent that the function is not hindered.
Examples of the light stabilizer include ultraviolet absorbers, visible light absorbers, infrared absorbers, antioxidants, carotenes, pigments, amines, Singlet oxygen quenchers such as phenols, nickel complexes, and sulfides, superoxide anion quenchers such as oxide dismutase and cobalt and nickel complexes, ozone quenchers, and compounds that suppress the oxidation reaction. , 0.3 to 24% by weight, preferably 0.8 to 16% by weight. Among them, a system in which the ultraviolet absorber is used in combination with an antioxidant and/or a singlet oxygen quencher is particularly effective in improving light resistance.
Furthermore, general dyes and pigments (non-thermochromic) can also be blended.
Examples of the general dyes and pigments include acid dyes, basic dyes, direct dyes, inorganic pigments, organic pigments, colored resin pigments, and titanium dioxide.

The reversible thermochromic composition can be used as a reversible thermochromic material by dispersing it in a thermoplastic resin or thermosetting resin, or encapsulating it in microcapsules.
In addition, microencapsulation is performed by known interfacial polymerization method, in situ polymerization method, in-liquid curing coating method, phase separation method from aqueous solution, phase separation method from organic solvent, melting dispersion cooling method, air suspension coating method. , spray-drying method, etc., which are appropriately selected according to the application.
Examples of materials for the capsule include epoxy resin, urea resin, urethane resin, isocyanate resin, and the like.
Furthermore, depending on the purpose, the surface of the microcapsules can be provided with a secondary resin film to impart durability, or the surface characteristics can be modified for practical use.
The microcapsule pigment preferably has a content/wall film ratio of 7/1 to 1/1 (mass ratio). Inclusions/wall film=6/1 to 1/1 (mass ratio) is more preferable because deterioration of clarity can be prevented.

The reversible thermochromic microcapsule pigment encapsulating the reversible thermochromic composition has a particle size of 0.1 to 30 μm, preferably 0.5 to 20 μm, more preferably 0.5 to 10 μm. .
In addition, the particle size and the average particle size are measured by determining the particle area using the image analysis type particle size distribution measurement software "MacView" manufactured by Mountec, and calculating the area of the particle area from the projected area circle equivalent diameter (Heywood diameter) is calculated, and the particle diameter and the average particle diameter of particles equivalent to a sphere of equal volume are measured based on the calculated value. In addition, when the particle diameter of all or most of the particles exceeds 0.2 μm, an isovolumetric sphere is measured by the Coulter method using a particle size distribution analyzer (manufactured by Beckman Coulter, Inc., product name: Multisizer 4e). It can also be measured as the particle size and mean particle size of the equivalent particles.
Furthermore, using a laser diffraction/scattering particle size distribution measuring device (device name: LA-960V2, manufactured by Horiba, Ltd.) calibrated based on the values measured using a measuring device according to the Coulter method, volume-based The particle size and average particle size (median size) may be measured.

The reversible thermochromic material is dispersed in an aqueous or oil-based vehicle containing a binder resin and applied as a coloring material such as ink or paint, and general-purpose printing or coating means such as screen printing, offset printing, process printing, Reversible thermochromic material (reversible thermochromic layer) can be formed.
The reversible thermochromic material is not limited to solid printing, and may be a reversible thermochromic image such as letters, numerals, symbols, and patterns.
The reversible thermochromic microcapsule pigment can be contained in the binder resin in an amount of 0.5 to 40% by weight, preferably 1 to 30% by weight. When the blending amount is less than 0.5% by weight, it is difficult to see a clear thermal discoloration effect, and when it exceeds 40% by weight, it is excessive, and the color is erased and residual color may be observed.
Also, the reversible thermochromic body can be adhered to the mask via an adhesive layer.

Furthermore, on the reversible thermochromic material, a bright layer or protective layer exhibiting optical properties such as transparent metallic luster, iris, and hologram is provided within a range that does not impair transparency, or a light stabilizer layer is provided. can also
The light stabilizer layer disperses a light stabilizer selected from ultraviolet absorbers, antioxidants, anti-aging agents, singlet oxygen quenchers, superoxide anion quenchers, ozone quenchers, visible light absorbers, and infrared absorbers. It is a state-fixed layer.
An antiaging agent, an antistatic agent, a polarizing agent, a thixotropic agent, an antifoaming agent, etc. may be added to each layer as necessary to improve the function.

The first reversible thermochromic body and the second reversible thermochromic body may be provided on one side of the mask. Preferably, the first reversible thermochromic body is provided and the second reversible thermochromic body is provided on the other surface. It is preferable that the user wears the mask with the side provided with the first reversible thermochromic material on the outside (the side in contact with the outside air) and the side provided with the second reversible thermochromic material on the inside (the side in contact with the face). This is because a third person can clearly see the color change of the first reversible thermochromic material, and the user can accurately see the color change of the second reversible thermochromic material.

Furthermore, when the mask itself is the first reversible thermochromic body or the second reversible thermochromic body, the same effect can be obtained by providing the other reversible thermochromic body on the surface of the mask.
The configuration in which the mask itself is a reversible thermochromic body means that the mask is immersed in ink or paint containing a reversible thermochromic material, or that the mask fibers themselves are fibers formed using a reversible thermochromic material. is mentioned.

Furthermore, a first reversible thermochromic body is provided on one surface of the mask, and a second reversible thermochromic body is provided on the ear strap of the mask (a string immersed in ink or paint containing a reversible thermochromic material). ), the mask itself is the first reversible thermochromic body, and by providing the second reversible thermochromic body on the ear straps of the mask, the user can accurately visually recognize the discoloration of the ear straps. There may be.

Examples of the reversible thermochromic mask of the present invention are shown below, but the present invention is not limited thereto.
In addition, the part in an Example shows a mass part.
Example 1
Preparation of Reversible Thermochromic Microcapsule Pigment A (A) As a component, 2.5 parts of 1,3-dimethyl-6-diethylaminofluorane and (B) as a component, 2,2-bis(4-hydroxyphenyl) 5.0 parts of hexafluoropropane, 3.0 parts of 1,1-bis(4-hydroxyphenyl)n-decane, 40.0 parts of 3-methylbutyl behenate as the component (c), and behenic acid- A reversible thermochromic composition comprising 10.0 parts of 2-methylpentyl was encapsulated in microcapsules by an interfacial polymerization method to obtain a microcapsule suspension. The reversible thermochromic microcapsule pigment A was isolated by centrifuging the suspension.
The reversible thermochromic microcapsule pigment A has a complete color development temperature _t1 of 29°C, a color development start temperature _t2 of 39°C, a color disappearance start temperature _t3 of 37°C, a complete color change temperature _t4 of 40°C, and a hysteresis width of ΔH was 1° C., and the color changed from orange to colorless with temperature change.
Preparation of Reversible Thermochromic Microcapsule Pigment B (A) As a component, 1.0 parts of 3,3-bis(2-ethoxy-4-diethylaminophenyl)-4-azaphthalide and (B) as a component, 1,1 - A reversible thermochromic composition consisting of 8.0 parts of bis(4-hydroxyphenyl) n-decane and 50.0 parts of n-nonyl stearate as the component (C) is formed into microcapsules by an interfacial polymerization method. encapsulation to obtain a microcapsule suspension. The reversible thermochromic microcapsule pigment B with color memory was isolated by centrifuging the suspension.
The reversible thermochromic microcapsule pigment B has a complete color development temperature _t1 of 19°C, a color development start temperature _t2 of 26°C, a color disappearance start temperature _t3 of 31°C, a complete color change temperature _t4 of 38°C, and a hysteresis width of ΔH was 12° C., and the color changed from bluish green to colorless with temperature change.

Fabrication of reversible thermochromic mask (see Fig. 3)
30 parts of reversible thermochromic microcapsule pigment A, 62 parts of urethane emulsion, 2 parts of thickener, 0.5 parts of leveling agent, and antifoaming are added to the central portion of the outer surface (side in contact with the outside air) of mask body 2 made of non-woven fabric. A reversible thermochromic ink in which 0.5 parts of an agent and 5 parts of a cross-linking agent are uniformly dispersed is solidly printed using a 120-mesh screen, dried and cured to form a first reversible thermochromic body 3 (reversible thermochromic material 3). discoloration layer) was provided.
Next, 30 parts of reversible thermochromic microcapsule pigment B, 62 parts of urethane-based emulsion, 2 parts of thickener, 0.5 parts of leveling agent, and antifoaming agent were added to the central portion of the inner surface (the side in contact with the face) of mask body 2 . A reversible thermochromic ink in which 0.5 part and 5 parts of a cross-linking agent are uniformly dispersed is solidly printed using a 120-mesh screen plate, dried and cured to form a second reversible thermochromic body 4 (reversible thermochromic body 4). Layer) was provided to obtain a reversible thermochromic mask 1.
Elastic ear straps are provided on both sides of the mask (not shown).

When the reversible thermochromic mask is worn by a user whose body temperature is 38° C. due to heat generation, the first reversible thermochromic material changes color from orange to colorless due to exhaled breath of the mask user. When spitting is stopped, the reversible thermochromic material changes color from colorless to orange. was made.
In addition, the reversible thermochromic material of the second reversible thermochromic body changes color from bluish green to colorless when the mask user exhales, and this state is maintained, so the user can remove the mask and check for heat generation. It was possible to visually confirm, and the heat generation was able to be grasped.

Example 2
Preparation of reversible thermochromic microcapsule pigment A (a) As a component, 3-dibutylamino-6-methyl-7-anilinofluorane 9-ethyl (3-methylbutyl) amino-spiro [12H-benzo (a) xanthene -12,1'(3'H)isobenzofuran]-3'-one 2.5 parts, (b) component 2,2-bis-(4-hydroxyphenyl)propane 8.0 parts, ( A reversible thermochromic composition comprising 50.0 parts of 3-methylbutyl behenate as component c) was encapsulated in microcapsules by an interfacial polymerization method to obtain a microcapsule suspension. The reversible thermochromic microcapsule pigment A was isolated by centrifuging the suspension.
The reversible thermochromic microcapsule pigment A has a complete color development temperature _t1 of 30°C, a color development start temperature _t2 of 40°C, a color disappearance start temperature _t3 of 38°C, a complete color change temperature _t4 of 41°C, and a hysteresis width. ΔH was 1° C., and the color changed from black to colorless with temperature change.
Preparation of Reversible Thermochromic Microcapsule Pigment B (A) As a component, 1.0 parts of 1,2-benz-6-(N-ethyl-N-isobutylamino)fluorane and (B) as a component, 2,2 -Bis-(4-hydroxyphenyl)propane 8.0 parts, and as the component (c), a reversible thermochromic composition consisting of 50.0 parts of p-tert-butyl stearyl benzoate was microfabricated by an interfacial polymerization method. It was encapsulated into a capsule to obtain a microcapsule suspension. The reversible thermochromic microcapsule pigment B with color memory was isolated by centrifuging the suspension.
The reversible thermochromic microcapsule pigment B has a complete color development temperature _t1 of 8°C, a color development start temperature _t2 of 15°C, a color disappearance start temperature _t3 of 32°C, a complete color change temperature _t4 of 39°C, and a hysteresis width of ΔH was 24° C., and the color changed from pink to colorless with temperature change.

Fabrication of reversible thermochromic mask (see Fig. 4)
30 parts of a reversible thermochromic microcapsule pigment A, 1 part of a red pigment, 61 parts of a urethane emulsion, 2 parts of a thickener, and 0.5 parts of a leveling agent were added to the central portion of the outer surface (the side in contact with the outside air) of the mask body 2 made of non-woven fabric. 5 parts of antifoaming agent, 0.5 part of antifoaming agent, and 5 parts of cross-linking agent are uniformly dispersed, and the reversible thermochromic ink is solidly printed using a 120-mesh screen, dried and cured to form the first reversible thermochromic ink. Body 3 (reversible thermochromic layer) was provided.
Next, 30 parts of reversible thermochromic microcapsule pigment B, 62 parts of urethane-based emulsion, 2 parts of thickener, 0.5 parts of leveling agent, and antifoaming agent were added to the inner surface (face-contacting side) of mask body 2. A reversible thermochromic ink in which 0.5 part and 5 parts of a cross-linking agent are uniformly dispersed is solidly printed using a 120-mesh screen plate, dried and cured to form a second reversible thermochromic body 4 (reversible thermochromic body 4). Layer) was provided to obtain a reversible thermochromic mask 1.
Elastic ear straps are provided on both sides of the mask (not shown).

When the reversible thermochromic mask is worn by a user whose body temperature is 39°C due to heat generation, the first reversible thermochromic material changes color from black to red due to exhaled breath of the mask user. When spitting is stopped, the reversible thermochromic material changes color from red to black, so a third party can visually confirm the repeated discoloration of the user's mask and grasp the heat generation. .
In addition, the second reversible thermochromic material changes color from pink to colorless due to the body temperature of the mask user's face, and the state is maintained, so the user can remove the mask and check for fever. was able to be confirmed by visual observation, and heat generation was able to be grasped.

Example 3
Preparation of Reversible Thermochromic Microcapsule Pigment A (a) As a component, 3-cyclohexylamino-7-methylfluorane 9-ethyl (3-methylbutyl) amino-spiro[12H-benzo(a)xanthene-12,1′ 2.5 parts of (3'H)isobenzofuran]-3'-one, 8.0 parts of 2,2-bis-(4-hydroxyphenyl)propane as component (B), and (C) as component A reversible thermochromic composition comprising 20.0 parts of n-butyl behenate and 30.0 parts of 3-methylbutyl behenate was encapsulated in microcapsules by an interfacial polymerization method to obtain a microcapsule suspension. rice field. The reversible thermochromic microcapsule pigment A was isolated by centrifuging the suspension.
The reversible thermochromic microcapsule pigment A has a complete color development temperature _t1 of 32°C, a color development start temperature _t2 of 42°C, a color disappearance start temperature _t3 of 40°C, a complete color change temperature _t4 of 43°C, and a hysteresis width of ΔH was 1° C., and the color changed from orange to colorless with temperature change.
Preparation of Reversible Thermochromic Microcapsule Pigment B (A) As a component, 9-ethyl(3-methylbutyl)amino-spiro[12H-benzo(a)xanthene-12,1′(3′H)isobenzofuran]-3 3.0 parts of ′-one, 6.0 parts of 2,2-bis-(4-hydroxyphenyl)propane as component (b), and 50.0 parts of neopentyl glycol dipalmitate as component (c) A reversible thermochromic composition consisting of was encapsulated in microcapsules by an interfacial polymerization method to obtain a microcapsule suspension. The reversible thermochromic microcapsule pigment B with color memory was isolated by centrifuging the suspension.
The reversible thermochromic microcapsule pigment B has a complete color development temperature _t1 of 11°C, a color development start temperature _t2 of 18°C, a color disappearance start temperature _t3 of 34°C, a complete color change temperature _t4 of 41°C, and a hysteresis width of ΔH was 23° C., and the color changed from red to colorless with temperature change.

Fabrication of reversible thermochromic mask (see Fig. 5)
Reversible heat obtained by uniformly dispersing 30 parts of reversible thermochromic microcapsule pigment A, 62 parts of urethane emulsion, 2 parts of thickener, 0.5 parts of leveling agent, 0.5 parts of antifoaming agent, and 5 parts of cross-linking agent The mask body 2 made of non-woven fabric was immersed in the discoloring ink and then dried.
Next, 30 parts of a reversible thermochromic microcapsule pigment B, 0.5 parts of a blue pigment, 61.5 parts of a urethane emulsion, 2 parts of a thickener, and leveling are added to the peripheral portion of the inner surface (the side that contacts the face) of the mask body 2. 0.5 parts of an antifoaming agent, 0.5 parts of an antifoaming agent, and 5 parts of a cross-linking agent are uniformly dispersed in a reversible thermochromic ink. 4 (reversible thermochromic layer) was provided to obtain a reversible thermochromic mask 1 .
Elastic ear straps are provided on both sides of the mask (not shown).

When the reversible thermochromic mask is worn by a user whose body temperature is 41 ° C. due to heat generation, the mask body containing the reversible thermochromic microcapsule pigment A is exhaled by the mask user, and the reversible thermochromic material changes from orange to orange. It turns colorless, and when you stop breathing, the reversible thermochromic material changes color from colorless to orange. , was able to grasp the fever.
In addition, the reversible thermochromic material of the second reversible thermochromic material changes color from purple to blue due to the body temperature of the mask user's face, and this state is maintained, so the user can remove the mask and check for fever. It was possible to visually confirm, and the heat generation was able to be grasped.

Example 4
Preparation of Reversible Thermochromic Microcapsule Pigment A (A) As a component, 2.5 parts of 1,3-dimethyl-6-diethylaminofluorane and (B) as a component, 2,2-bis(4-hydroxyphenyl) 5.0 parts of hexafluoropropane, 3.0 parts of 1,1-bis(4-hydroxyphenyl) n-decane, and 20.0 parts of n-butyl behenate as the component (c), and behenic acid- A reversible thermochromic composition comprising 30.0 parts of 3-methylbutyl was encapsulated in microcapsules by an interfacial polymerization method to obtain a microcapsule suspension. The reversible thermochromic microcapsule pigment A was isolated by centrifuging the suspension.
The reversible thermochromic microcapsule pigment A has a complete color development temperature _t1 of 32°C, a color development start temperature _t2 of 42°C, a color disappearance start temperature _t3 of 40°C, a complete color change temperature _t4 of 43°C, and a hysteresis width of ΔH was 1° C., and the color changed from orange to colorless with temperature change.
Preparation of Reversible Thermochromic Microcapsule Pigment B (A) As a component, 1.0 parts of 3,3-bis(2-ethoxy-4-diethylaminophenyl)-4-azaphthalide and (B) as a component, 1,1 - A reversible thermochromic composition comprising 8.0 parts of bis(4-hydroxyphenyl) n-decane and 50.0 parts of 2-acetonaphthone as component (C) is encapsulated in microcapsules by an interfacial polymerization method. , to obtain a microcapsule suspension. The reversible thermochromic microcapsule pigment B with color memory was isolated by centrifuging the suspension.
The reversible thermochromic microcapsule pigment B has a complete color development temperature _t1 of -15°C, a color development start temperature _t2 of -8°C, a color disappearance start temperature _t3 of -2°C, and a complete color change temperature _t4 of 40°C. , the hysteresis width ΔH was 22° C., and the color changed from bluish green to colorless with temperature change.

Fabrication of reversible thermochromic mask (see Fig. 3)
30 parts of reversible thermochromic microcapsule pigment A, 62 parts of urethane emulsion, 2 parts of thickener, 0.5 parts of leveling agent, and antifoaming are added to the central portion of the outer surface (side in contact with the outside air) of mask body 2 made of non-woven fabric. A reversible thermochromic ink in which 0.5 parts of an agent and 5 parts of a cross-linking agent are uniformly dispersed is solidly printed using a 120-mesh screen, dried and cured to form a first reversible thermochromic body 3 (reversible thermochromic material 3). discoloration layer) was provided.
Next, 30 parts of reversible thermochromic microcapsule pigment B, 62 parts of urethane-based emulsion, 2 parts of thickener, 0.5 parts of leveling agent, and antifoaming agent were added to the central portion of the inner surface (the side in contact with the face) of mask body 2 . A reversible thermochromic ink in which 0.5 part and 5 parts of a cross-linking agent are uniformly dispersed is solidly printed using a 120-mesh screen plate, dried and cured to form a second reversible thermochromic body 4 (reversible thermochromic body 4). Layer) was provided to obtain a reversible thermochromic mask 1.
Elastic ear straps are provided on both sides of the mask (not shown).

When the reversible thermochromic mask is worn by a user whose body temperature is 41° C. due to heat generation, the first reversible thermochromic material changes color from orange to colorless due to exhaled breath of the mask user. When spitting is stopped, the reversible thermochromic material changes color from colorless to orange. was made.
In addition, the reversible thermochromic material of the second reversible thermochromic body changes color from bluish green to colorless when the mask user exhales, and this state is maintained, so the user can remove the mask and check for heat generation. It was possible to visually confirm, and the heat generation was able to be grasped.

Example 5
Preparation of reversible thermochromic microcapsule pigment A (a) As a component, 3-dibutylamino-6-methyl-7-anilinofluorane 9-ethyl (3-methylbutyl) amino-spiro [12H-benzo (a) xanthene -12,1'(3'H)isobenzofuran]-3'-one 2.5 parts, (b) component 2,2-bis-(4-hydroxyphenyl)propane 8.0 parts, ( A reversible thermochromic composition comprising 50.0 parts of 3-methylbutyl behenate as component c) was encapsulated in microcapsules by an interfacial polymerization method to obtain a microcapsule suspension. The reversible thermochromic microcapsule pigment A was isolated by centrifuging the suspension.
The reversible thermochromic microcapsule pigment A has a complete color development temperature _t1 of 30°C, a color development start temperature _t2 of 40°C, a color disappearance start temperature _t3 of 38°C, a complete color change temperature _t4 of 41°C, and a hysteresis width. ΔH was 1° C., and the color changed from black to colorless with temperature change.
Preparation of Reversible Thermochromic Microcapsule Pigment B (A) As a component, 1.0 parts of 1,2-benz-6-(N-ethyl-N-isobutylamino)fluorane and (B) as a component, 2,2 - A reversible thermochromic composition comprising 8.0 parts of bis-(4-hydroxyphenyl)propane and 50.0 parts of hexyl 4-biphenylacetate as component (C) is encapsulated in microcapsules by an interfacial polymerization method. to obtain a microcapsule suspension. The reversible thermochromic microcapsule pigment B with color memory was isolated by centrifuging the suspension.
The reversible thermochromic microcapsule pigment B has a complete color development temperature _t1 of −30° C., a color development start temperature _t2 of −22° C., a color disappearance start temperature _t3 of 29° C., and a complete color change temperature _t4 of 39° C. The hysteresis width ΔH was 60° C., and the color changed from pink to colorless with temperature change.

Fabrication of reversible thermochromic mask (see Fig. 4)
30 parts of a reversible thermochromic microcapsule pigment A, 1 part of a red pigment, 61 parts of a urethane emulsion, 2 parts of a thickener, and 0.5 parts of a leveling agent were added to the central portion of the outer surface (the side in contact with the outside air) of the mask body 2 made of non-woven fabric. 5 parts of antifoaming agent, 0.5 part of antifoaming agent, and 5 parts of cross-linking agent are uniformly dispersed, and the reversible thermochromic ink is solidly printed using a 120-mesh screen, dried and cured to form the first reversible thermochromic ink. Body 3 (reversible thermochromic layer) was provided.
Next, 30 parts of reversible thermochromic microcapsule pigment B, 62 parts of urethane-based emulsion, 2 parts of thickener, 0.5 parts of leveling agent, and antifoaming agent were added to the inner surface (face-contacting side) of mask body 2. A reversible thermochromic ink in which 0.5 part and 5 parts of a cross-linking agent are uniformly dispersed is solidly printed using a 120-mesh screen plate, dried and cured to form a second reversible thermochromic body 4 (reversible thermochromic body 4). Layer) was provided to obtain a reversible thermochromic mask 1.
Elastic ear straps are provided on both sides of the mask (not shown).

When the reversible thermochromic mask is worn by a user whose body temperature is 39°C due to heat generation, the first reversible thermochromic material changes color from black to red due to exhaled breath of the mask user. When spitting is stopped, the reversible thermochromic material changes color from red to black, so a third party can visually confirm the repeated discoloration of the user's mask and grasp the heat generation. .
In addition, the second reversible thermochromic material changes color from pink to colorless due to the body temperature of the mask user's face, and the state is maintained, so the user can remove the mask and check for fever. was able to be confirmed by visual observation, and heat generation was able to be grasped.

Comparative example 1
Preparation of reversible thermochromic microcapsule pigment (A) As a component, 2.5 parts of 1,3-dimethyl-6-diethylaminofluorane and (B) as a component, 2,2-bis(4-hydroxyphenyl)hexa 5.0 parts of fluoropropane, 3.0 parts of 1,1-bis(4-hydroxyphenyl)n-decane, 40.0 parts of 3-methylbutyl behenate as component (c), and 2 behenate A reversible thermochromic composition comprising 10.0 parts of -methylpentyl was encapsulated in microcapsules by an interfacial polymerization method to obtain a microcapsule suspension. The suspension was centrifuged to isolate the reversible thermochromic microcapsule pigment.
The reversible thermochromic microcapsule pigment has a complete color development temperature _t1 of 29°C, a color development start temperature _t2 of 39°C, a color disappearance start temperature _t3 of 37°C, a complete color change temperature _t4 of 40°C, and a hysteresis width ΔH. was 1° C., and the color changed from orange to colorless as the temperature changed.

Preparation of reversible thermochromic mask 30 parts of reversible thermochromic microcapsule pigment, 62 parts of urethane emulsion, 2 parts of thickener, and 0 parts of leveling agent are added to the center of the outer surface (side in contact with the outside air) of the mask body made of non-woven fabric. .5 parts, 0.5 parts of antifoaming agent, and 5 parts of cross-linking agent are uniformly dispersed in the reversible thermochromic ink. (reversible thermochromic layer) was provided.
In addition, elastic ear straps are provided on both sides of the mask.

When the reversible thermochromic mask is worn by a user whose body temperature is 38° C. due to heat generation, the first reversible thermochromic material changes color from orange to colorless due to exhaled breath of the mask user. When spitting is stopped, the reversible thermochromic material changes color from colorless to orange. However, since the user himself/herself cannot confirm the state of discoloration, he/she could not grasp the heat generation.

t ₁ Complete color development temperature of the heat color erasable reversible thermochromic microcapsule pigment t ₂ Color development start temperature of the heat color erasable reversible thermochromic microcapsule pigment t ₃ Heat color erasable reversible thermochromic microcapsule pigment Discoloration start temperature t ₄ Complete discoloration temperature of heat-discolorable reversible thermochromic microcapsule pigment ΔH Hysteresis width 1 Reversible thermochromic mask 2 Mask main body 3 First reversible thermochromic body 4 Second reversible thermochromic body

Claims (5)

A mask comprising a reversible thermochromic body containing a first reversible thermochromic material and a reversible thermochromic body containing a second reversible thermochromic material, wherein the reversible thermochromic material is (a) an electron donor; (b) an electron-accepting compound; and (c) a reaction medium for controlling the color reaction of (a) and (b) above. A reversible thermochromic microcapsule pigment, or a reversible thermochromic resin particle obtained by dispersing the reversible thermochromic composition in a thermoplastic or thermosetting resin, and exhibits a hysteresis characteristic with respect to a color density-temperature curve to develop color. In the process of increasing the temperature from the colored state, the color begins to fade when it reaches the color-discoloring start temperature _t3 , and the temperature range of the complete color-discoloring temperature _t4 or higher, which is higher than the temperature _t3 . In the process of decreasing the temperature from the colorless state, coloration begins when the coloration start temperature _t2 is reached, and coloration is completed in the temperature range of the complete coloration temperature _t1 or lower, which is lower than the temperature _t2 . The first reversible thermochromic material has a discoloration start temperature _t3 of 37 to 42° C. and a hysteresis width (ΔH) of 3° C. or less with respect to the color density-temperature curve. , The second reversible thermochromic mask is a reversible thermochromic mask which has a complete decoloring temperature t ₄ of 37 to 42° C. and a hysteresis width (ΔH) of 10° C. or more with respect to the color density-temperature curve. 2. The reversible according to claim 1, wherein one surface of the mask is provided with a reversible thermochromic body containing the first reversible color-changing material, and the other surface is provided with a reversible thermochromic body containing the second reversible thermochromic material. Thermochromic mask. The mask itself is either a reversible thermochromic body containing a first reversible thermochromic material or a reversible thermochromic body containing a second reversible thermochromic material, and the other reversible thermochromic body is applied to the surface of the mask. The reversible thermochromic mask according to claim 1, comprising: The first reversible thermochromic material has a discoloration start temperature t ₃ of 37.5 to 40°C, and the second reversible thermochromic material has a complete discoloration temperature t ₄ of 37.5 to 40°C. The reversible thermochromic mask according to any one of claims 1 to 3. The reversible thermochromic mask according to any one of claims 1 to 4, wherein the second reversible thermochromic material is a material exhibiting a hysteresis width (ΔH) of 20°C or more with respect to a color density-temperature curve.

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