JP6778565B2 - Organ substitute resin molded product - Google Patents

Description

The present invention relates to an organ substitute resin molded product. More specifically, the present invention relates to an organ substitute resin molded product used in a simulation of heating an organ using a medical device.

Conventionally, animal tissues such as pigs and cows have been used for simulations in medical practice of cauterizing organs using surgical instruments such as endoscopic surgical instruments, but in order to maintain animal tissues immediately after slaughter. It takes time and effort, and the use of animal tissue is not preferable in terms of hygiene and indoor environment.
Therefore, an organ model made of synthetic resin instead of animal tissue is disclosed (see, for example, Patent Document 1).
The organ model is a highly convenient simulated organ that does not need to maintain the tissue until use like animal tissue and does not care about hygiene and individual differences, but it is possible to clearly confirm the ablation site. It was difficult to do and could not be used for sufficient simulation (learning, training, training, proficiency, exercises, etc.).
Therefore, it is disclosed to confirm the temperature distribution by heating or the thermal action by irradiation with ultrasonic waves using a thermochromic material such as liquid crystal (see, for example, Patent Documents 2 to 4).

JP-A-2015-36809 JP-A-63-212356 Japanese Unexamined Patent Publication No. 2006-10320 Japanese Unexamined Patent Publication No. 2013-85898

The present invention is intended to provide this type of organ substitute resin composition.

In the present invention, as (a) electron-donating color-forming organic compounds, phenylindrylphthalides, indolylphthalides, diphenylmethaneazaphthalides, phenylindrillazaphthalides, fluorans, stylinoquinolines, Compounds selected from diazarodamine lactones, quinazolines, bisquinazolines, (b) electron-accepting compounds, (c) electron transfer reactions by the above-mentioned (a) and (b) components reversibly occur in a specific temperature range. A thermochromic color-memory microcapsule pigment containing a thermochromic color-memory composition comprising a reaction medium is contained in a molded product, and is added by a medical device that imitates the shape of an organ. An organ substitute resin compound for checking the temperature is a requirement.
Furthermore, the temperature-sensitive color-memory microcapsule pigment exhibits a large hysteresis characteristic with respect to the color density-temperature curve, exhibits mutual modification between the first hue and the second hue, and has a temperature in the first hue. the rising course and reaches the temperature t _3, the first color begins to discolor, become completely second color at higher temperatures t ₄ above temperature range than the temperature t _3, the temperature in the second color state descends In the process, when the temperature t ₂ is reached, the second hue begins to change color and becomes completely the first hue in the temperature range lower than the temperature t ₂ and below the temperature t ₁ , and is between the temperature t ₂ and the temperature t ₃ . It exhibits hysteresis characteristics in which the first hue or the second hue is maintained in the temperature range, the temperature t ₂ is a temperature below normal temperature, the temperature t ₄ is above normal temperature, and is a temperature below the heating temperature for the organ. It is a thermochromic color memory microcapsule pigment containing a thermochromic color memory composition, the temperature t ₄ is a temperature exceeding the body temperature, and the temperature t ₂ is a temperature of less than 5 ° C. There, the temperature _{t 4} is a temperature above 40 ° C., the temperature _{t 4} is a requirement such that it is a temperature of 50 to 100 ° C..

The present invention can provide a highly convenient organ substitute resin molded product capable of clearly and permanently confirming a heated part of an organ by a medical device and sufficiently performing a simulation in a medical practice. it can.

It is explanatory drawing which shows the discoloration behavior of the temperature-sensitive color-sensitive color memory composition used in this invention. It is explanatory drawing which shows the discoloration behavior of another temperature-sensitive discoloration color memory composition used in this invention. It is a vertical cross-sectional explanatory view of one Example of the organ substitute resin molded article of this invention. It is a vertical cross-sectional explanatory view which shows the state after heating of the organ substitute resin molded article of FIG.

The organ substitute resin molded product of the present invention contains a temperature-sensitive color-memory microcapsule pigment containing a temperature-sensitive color-memory composition in a resin molded product.

The temperature-sensitive color-memory composition is described in JP-A-4-17154, JP-A-7-179777, JP-A-7-33997, JP-A-8-39936, and the like. The discoloration temperature is opposite to the case where the shape of the curve showing the hysteresis characteristic (ΔH _B = 8 to 50 ° C.), that is, plotting the change in coloring density due to the temperature change, raises the temperature from the lower temperature side than the discoloration temperature range. The color changes by following a path that is significantly different from the case of lowering from the high temperature side of the range, and the color is developed in the low temperature range below the complete color development temperature (t ₁ ), or the high temperature range above the complete decolorization temperature (t ₄ ). decolored state in is decolorized by [temperature range (substantially two-phase retaining temperature region) between t ₂ ~t _3] in heat-decolorizable with color-memorizing (heating certain temperature range, by cooling It is a reversible thermochromic composition (which develops color) (see FIG. 1).
The hysteresis characteristics in the color density-temperature curve of the thermochromic color memory composition will be described.
In FIG. 1, the vertical axis represents the color density and the horizontal axis represents the temperature. The change in color density due to temperature change progresses along the arrow. Here, A is a point indicating the concentration at the temperature t ₄ (hereinafter referred to as the complete decolorization temperature) at which the complete decolorization state is reached, and B is the temperature t ₃ (hereinafter, the decolorization start temperature) at which the decolorization starts. The point indicates the density at (referred to as), C is the point indicating the density at the temperature t ₂ (hereinafter referred to as the color development start temperature) at which color development starts, and D is the temperature t ₁ (hereinafter referred to as complete) at which the color development state is reached. It is a point indicating the density at (called the color development temperature).
The discoloration temperature range is a temperature range between t ₁ and t ₄ , which can exhibit either a colored state or a decolored state, and is between t ₂ and t ₃ , which is a region having a large difference in color density. The temperature range of is the substantial discoloration temperature range.
Further, the length of the line segment EF is a measure indicating the contrast of discoloration, and the length of the line segment HG passing through the midpoint of the line segment EF is a temperature width indicating the degree of hysteresis (hereinafter referred to as hysteresis width ΔH). If this ΔH value is small, only one of the two states before and after discoloration can exist in the normal temperature range. Further, when the ΔH value is large, it becomes easy to maintain each state before and after discoloration.
The thermochromic color memory composition can selectively maintain either a color-developing state or a decoloring state over the entire color retention temperature range (t _3- t ₂ ), and color development starts. It has a normal temperature range between the temperature t ₂ and the decolorization start temperature t ₃ .
The normal temperature range is preferably in the range of 5 to 35 ° C. described in JIS Z 8703, and the color development state or the decolorization state can be selectively stored and retained at a general operating environment temperature. it can.
Further, when the temperature t ₂ is a temperature lower than the room temperature, the temperature t ₄ exceeds the room temperature, and the temperature is equal to or lower than the heating temperature for the organ, the temperature-sensitive discoloration color developed at the temperature t ₁ or lower. Since the memory composition is decolorized by heating with a medical device and its state is maintained in the normal temperature range, the heated part can be clearly confirmed, and sufficient simulation (learning, training, training, mastery, proficiency, etc.) It can be used for exercises, etc.).
Further, since the temperature t ₄ is a temperature exceeding the body temperature, a more realistic simulation can be performed.
The temperature t ₂ is a temperature of 5 ° C. or lower, which is lower than the room temperature range in which the thermochromic color memory composition does not develop color, and the temperature t ₄ is a temperature exceeding the room temperature and lower than the heating temperature for the organ. It is a temperature of 40 ° C. or higher.
Here, to explain why the temperature t ₄ exceeds the normal temperature and is equal to or lower than the heating temperature for the organ and the temperature t ₂ is lower than the normal temperature, the decoloring start temperature (decolorization start temperature) If the heating is stopped before the complete decolorization temperature (t ₄ ) is reached after t ₃ ), the phenomenon of returning to the first state occurs again, and the color development start temperature (t ₂ ) from the decolorization state. Even if the cooling is stopped before the complete color development temperature (t ₁ ) is reached, the color development state is maintained. Therefore, the complete decolorization temperature (t ₄ ) exceeds the normal temperature and is applied to the organs. If the temperature is below the temperature, the color development state will be maintained in the normal use state before heating, and if the color development start temperature (t ₂ ) is below the normal temperature range, the decolorization state will be warmed. It will be maintained in later normal use.
Therefore, the temperature setting is an important requirement for selectively visualizing the discolored state of the heated portion of the temperature-sensitive color-sensitive color memory composition, and can satisfy convenience and practicality. ..
In the temperature setting of the complete decolorization temperature (t ₄ ) described above, it is preferable that the temperature is higher in order for the color development state to be maintained in the normal use state.
Therefore, the complete decolorization temperature (t ₄ ) is preferably 50 to 100 ° C, more preferably 50 to 80 ° C.
A more suitable simulation can be performed by setting the complete decolorization temperature (t ₄ ) to a temperature suitable for practical use of the organ substitute resin molded product.
Further, in the temperature setting of the color development start temperature (t ₂ ) described above, in order to maintain the decolorized state in the normal use state, it is preferably a lower temperature, preferably 0 ° C. or lower, and −5. ℃ or less is more preferable.
In order to bring the temperature-sensitive color-memory composition into a color-developed state in advance, it is preferable to cool it in a general-purpose freezer as a cooling means, but considering the cooling capacity of the freezer, the limit is -50 ° C. Therefore, the complete color development temperature (t ₁ ) is preferably −50 ° C. to 0 ° C.

The compounds for the components (a), (b), and (c) of the thermochromic color memory composition are illustrated below.
Examples of the electron-donating color-forming organic compound which is the component (a) of the present invention include phenylindrill phthalides, indolylphthalides, diphenylmethane azaphthalides, and phenylindrill azaphthalide having excellent light resistance. , Fluorones, styrylquinolins, diazarodamine lactones, quinazolines, bisquinazolines, preferably diphenylmethane azaphthalides, phenylindrill azaphthalides, fluorans, diazarodamine. It is a lactone, more preferably a fluorane.
By using the electron-donating color-developing organic compound, browning (color residue) in the decolorized state is unlikely to occur, and clear color change can be permanently exhibited.
Examples of these compounds are given below.
3- (4-Diethylaminophenyl) -3- (1-ethyl-2-methylindole-3-yl) phthalide,
3,3-Bis (1-n-butyl-2-methylindole-3-yl) phthalide,
3,3-Bis (2-ethoxy-4-diethylaminophenyl) -4-azaphthalide,
3- [2-ethoxy-4- (N-ethylanilino) phenyl] -3- (1-ethyl-2-methylindole-3-yl) -4-azaphthalide,
3,6-diphenylaminofluorane,
3,6-dimethoxyfluorane,
3,6-di-n-butoxyfluoran,
2-Methyl-6- (N-ethyl-N-p-trillamino) fluorane,
3-Chloro-6-cyclohexylaminofluorane,
2-Methyl-6-cyclohexylaminofluorane,
2- (2-Chloroamino) -6-dibutylaminofluorane,
2- (2-Chloroanilino) -6-di-n-butylaminofluorane,
2- (3-Trifluoromethylanilino) -6-diethylaminofluorane,
2- (N-Methylanilino) -6- (N-ethyl-N-p-trillamino) 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,
1,2-Benz-6-diethylaminofluorane,
1,2-Benz-6- (N-ethyl-N-isobutylamino) fluorane,
1,2-Benz-6- (N-ethyl-N-isoamylamino) fluorane,
2- (3-Methoxy-4-dodecoxystilyl) quinoline,
Spiro [5H- (1) benzopyrano (2,3-d) pyrimidine-5,1'(3'H) isobenzofuran] -3'-on,
2- (diethylamino) -8- (diethylamino) -4-methyl-spiro [5H- (1) benzopyrano (2,3-g) pyrimidine-5,1'(3'H) isobenzofuran] -3-one,
2- (Di-n-Butylamino) -8- (Di-n-Butylamino) -4-Methyl-Spiro [5H- (1) Benzopyrano (2,3-g) Pyrimidine-5,1'(3') H) Isobenzofuran] -3-one,
2- (Di-n-Butylamino) -8- (diethylamino) -4-methyl-spiro [5H- (1) benzopyrano (2,3-g) pyrimidine-5,1'(3'H) isobenzofuran] -3-on,
2- (Di-n-butylamino) -8- (N-ethyl-N-i-amylamino) -4-methyl-spiro [5H- (1) benzopyrano (2,3-g) pyrimidine-5,1'(3'H) Isobenzofuran] -3-one,
2- (Dibutylamino) -8- (dipentylamino) -4-methyl-spiro [5H- (1) benzopyrano (2,3-g) pyrimidine-5,1'(3'H) -isobenzofuran] -3 -On,
3- (2-Methoxy-4-dimethylaminophenyl) -3- (1-butyl-2-methylindole-3-yl) -4,5,6,7-tetrachlorophthalide,
3- (2-ethoxy-4-diethylaminophenyl) -3- (1-ethyl-2-methylindole-3-yl) -4,5,6,7-tetrachlorophthalide,
3- (2-ethoxy-4-diethylaminophenyl) -3- (1-pentyl-2-methylindole-3-yl) -4,5,6,7-tetrachlorophthalide,
4,5,6,7-Tetrachloro-3- [4- (diethylamino) -2-methylphenyl] -3- (1-ethyl-2-methyl-1H-indole-3-yl) -1 (3H) -Isobenzofuranone,
3', 6'-bis [phenyl (2-methylphenyl) amino] -spiro [isobenzofuran-1 (3H), 9'-[9H] xanthene] -3-one,
3', 6'-bis [phenyl (3-methylphenyl) amino] -spiro [isobenzofuran-1 (3H), 9'-[9H] xanthene] -3-one,
3', 6'-bis [phenyl (3-ethylphenyl) amino] -spiro [isobenzofuran-1 (3H), 9'-[9H] xanthene] -3-one,
2- (4'-dimethylaminophenyl) -4-methoxy-quinazoline,
4,4'-(ethylenedioxy) -bis [2- (4-diethylaminophenyl) quinazoline] and the like can be mentioned.
As fluorans, in addition to the above-mentioned compound having a substituent on the phenyl group forming the xanthene ring, a substituent (for example,) on the phenyl group having the substituent on the phenyl group forming the xanthene ring and forming the lactone ring. , An alkyl group such as a methyl group, or a halogen atom such as a chloro group) may be a compound exhibiting a blue color or black color.

Examples of the electron-accepting compound of the component (b) include a group of compounds having an active proton, 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)). There are compounds having electron vacancies and the like.
Examples of compounds having an active proton include monophenols to polyphenols as compounds having a phenolic hydroxyl group, and alkyl groups, aryl groups, acyl groups, alkoxycarbonyl groups, carboxy groups and esters thereof as their substituents. Alternatively, those having an amide group, a halogen group and the like, bis-type and tris-type phenols and the like, phenol-aldehyde condensed resins and the like can be mentioned. Further, it may be a metal salt of the compound having a phenolic hydroxyl group.
Specific examples are given below.
Phenol, o-cresol, tertiary butylcatechol, nonylphenol, n-octylphenol, n-dodecylphenol, n-stearylphenol, p-chlorophenol, p-bromophenol, o-phenylphenol, n-butyl p-hydroxybenzoate , P-Hydroxybenzoate n-octyl, resorcin, dodecyl carbate, 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-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-peptane, 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) ethyl propionate, 2,2-bis (4-hydroxyphenyl) -4-methylpentane, 2,2-bis (4-hydroxyphenyl) Enyl) -4-methylhexane, 2,2-bis (4-hydroxyphenyl) hexafluoropropane, 2,2-bis (4-hydroxy-3-methylphenyl) propane and the like.
The compound having a phenolic hydroxyl group can exhibit the most effective thermal discoloration property, but is an aromatic carboxylic acid and an aliphatic carboxylic acid having 2 to 5 carbon atoms, a carboxylic acid metal salt, an acidic phosphoric acid ester and theirs. It may be a compound selected from a metal salt, 1,2,3-triazole and a derivative thereof.

The component (c) of the reaction medium that reversibly causes the electron transfer reaction by the components (a) and (b) in a specific temperature range will be described.
Examples of the component (c) include alcohols, esters, ketones, and ethers.
As the component (c), regarding the color density-temperature curve, a large hysteresis characteristic (a curve plotting a change in coloring density due to a temperature change changes the temperature from the low temperature side to the high temperature side, and a case where the temperature changes from the high temperature side to the low temperature side. A carboxylic acid ester compound having a ΔT value (melting point-cloud point) of 5 ° C. or higher and lower than 50 ° C., which can form a reversible thermochromic composition showing color memory, which changes color depending on the case of changing to , 2-Methylbenzoate stearyl, 4-tert-butylbenzoate cetyl, 4-cyclohexylbenzoate behenyl, 4-phenylbenzoate myristyl, 4-octylbenzoate lauryl, 3,5-dimethylbenzoate hexyl, 3-ethyl Stearyl benzoate, decyl 4-isopropylbenzoate, stearyl 4-benzoyl, phenyl 4-tert-butylbenzoate, 4-chlorobenzyl 2-methylbenzoate, stearyl 4-chlorobenzoate, myristyl 3-bromobenzoate , 2-Chloro-4-bromobenzoate stearyl, 3,4-dichlorobenzoate decyl, 2,4-dibromobenzoate octyl, 3-nitrobenzoate cetyl, 4-aminobenzoate cyclohexylmethyl, 4-diethylaminobenzoic acid Cetyl, stearyl 4-anilinobenzoate, decyl 4-methoxybenzoate, cetyl 4-methoxybenzoate, octyl 4-butoxybenzoate, cetyl 4-hydroxybenzoate, 4-methoxyphenylmethyl benzoate, p-chlorophenylacetic acid Stearyl, p-chlorophenylacetate, benzyl salicylate, neopancil salicylate, 4-methoxymethylphenylmethyl salicylate, 4-chlorophenylmethyl benzoate, 4-chlorophenylmethyl capricate, 4-methoxyphenylmethyl myristate, stearic acid 4-Methylphenylmethyl, 4-nitrophenylmethyl stearate, 4-methylphenylmethyl caproate, 2-chlorophenylmethyl myristate, 4-methoxyphenylmethyl capric acid, 4-chlorophenylmethyl 11-bromolaurate , 4-Isopropylphenyl stearate, carboxylic acid ester containing a substituted aromatic ring in the molecule, stearyl 1-naphthoate, cetyl benzylate, stearyl benzylate, decyl 3-benzoylpropionate, stearyl benzoate, benzoic acid Esters of carboxylic acids containing unsubstituted aromatic rings such as cetyl and myristyl benzoate and aliphatic alcohols having 10 or more carbon atoms, cyclohea silicate In molecules such as xylmethyl, cyclohexyl laurate, cyclohexyl myristate, cyclohexyl palmitate, cyclohexyl stearate, cyclohexyl stearate, stearyl cyclohexylacetate, stearyl 2-cyclohexylpropionate, stearyl cyclohexanecarboxylate, cyclohexyl 2-benzoylpropionate, etc. Fatty acids with 6 or more carbon atoms such as carboxylic acid esters containing cyclohexyl groups, benzyl caproate, benzyl palmitate, 4-methylbenzyl palmitate, 3-phenylpropyl stearate, phenyl 11-bromolaurate, and aromatic alcohols. Alternatively, an ester of a phenol, an ester of a fatty acid having 8 or more carbon atoms such as neopentyl octylate and neopentyl laurate and an ester of a branched aliphatic alcohol, a dicarboxylic acid such as dibenzyl sebacate, dineopentyl 4,4'-diphenyldicarboxylic acid, and dibenzyl azodicarboxylate. Esters of acids and aromatic alcohols or branched aliphatic alcohols, dibenzyl silicate, heptyl stearate, didecyl adipate, dilauryl adipate, dimyristyl adipate, disetyl adipate, distearyl adipate, trilaurin, trimyristin, tristearate , Dimyristin, distearate and the like are used.

Further, an odd aliphatic monohydric alcohol having 9 or more carbon atoms and a fatty acid ester compound obtained from an 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. Aliphatic ester compounds having a total carbon number of 17 to 23 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, laurate 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 eikosanate, n-undecyl eikosanate, n-tridecyl eikosanate, n-pentadecyl eikosanate, behenic acid Examples thereof include n-nonyl, n-undecyl behenate, n-tridecyl behenate, n-pentadecyl behenate and the like.

As the ketones, aliphatic ketones having a total carbon number of 10 or more are effective, and 2-decanone, 3-decanone, 4-decanone, 2-undecanone, 3-undecanone, 4-undecanone, and 5-undecanone are effective. , 2-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, lauron, stearone and the like can be mentioned.
Also, arylalkyl ketones having a total carbon number of 12 to 24, for example, n-octadecanophenone, n-heptadecanophenone, n-hexadecanophenone, n-pentadecanophenone, n-tetradecano. Phenone, 4-n-dodecaacetophenone, n-tridecanophenone, 4-n-undecanoacetophenone, n-laurofenone, 4-n-decanoacetophenone, n-undecanophenone, 4-n-nonylacetophenone, n -Decanofenone, 4-n-octylacetophenone, n-nonanophenone, 4-n-heptylacetophenone, n-octanophenone, 4-n-hexylacetophenone, 4-n-cyclohexylacetophenone, 4-tert-butylpropiophenone, n-Heptaphenone, 4-n-pentylacetophenone, cyclohexylphenylketone, benzyl-n-butylketone, 4-n-butylacetophenone, n-hexanophenone, 4-isobutylacetophenone, 1-acetonaphthone, 2-acetonafton, cyclopentylphenylketone And so on.

As the 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, and didodecyl ether. , Ditridecyl 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.

〔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。 Further, as the component (c), a compound represented by the following general formula (1) can also be used.

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

R in the formula represents an alkyl group or an alkenyl group having 8 or more carbon atoms, preferably an alkyl group having 10 to 24 carbon atoms, and more preferably an alkyl group having 12 to 22 carbon atoms.
Specifically, 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 pentadecanoic acid, -4-benzyloxyphenylethyl hexadecanoic acid, heptadecanoic acid Examples thereof include -4-benzyloxyphenylethyl and -4-benzyloxyphenylethyl octadecanoic acid.

（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。 Further, as the component (c), a compound represented by the following general formula (3) can also be used.

(In the formula, R represents an alkyl group or an alkoxy group having 8 or more carbon atoms, m and n represent integers of 1 to 3 respectively, and X and Y represent a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, and carbon, respectively. Indicates the number 1 to 4 alkoxy groups and halogens.)
Specifically, the compounds include octanoic acid 1,1-diphenylmethyl, nonanoic acid 1,1-diphenylmethyl, decanoic acid 1,1-diphenylmethyl, undecanoic acid 1,1-diphenylmethyl, and dodecanoic acid 1,1-. Diphenylmethyl, tridecanoic acid 1,1-diphenylmethyl, tetradecanoic acid 1,1-diphenylmethyl, pentadecaneic acid 1,1-diphenylmethyl, hexadecanoic acid 1,1-diphenylmethyl, heptadecanoic acid 1,1-diphenylmethyl, 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。 Further, as the component (c), a compound represented by the following general formula (4) can also be used.

(In the formula, 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 compound include a diester of malonic acid and 2- [4- (4-chlorobenzyloxy) phenyl)] ethanol, a diester of oxalic acid and 2- (4-benzyloxyphenyl) ethanol, and a diester of oxalic acid and 2-. [4- (3-Methylbenzyloxy) phenyl)] Diester with ethanol, Diester with glutaric acid and 2- (4-benzyloxyphenyl) ethanol, Diester with glutaric acid and 2- [4- (4-chlorobenzyloxy) Phenyl)] Diester with ethanol, diester with adipic acid and 2- (4-benzyloxyphenyl) ethanol, diester with pimeric acid and 2- (4-benzyloxyphenyl) ethanol, suberic acid and 2- (4-benzyloxyphenyl) ethanol Diester with benzyloxyphenyl) ethanol, Sveric acid and 2- [4- (3-methylbenzyloxy) phenyl)] Diester with ethanol, Sveric acid and 2- [4- (4-chlorobenzyloxy) phenyl)] Diester with ethanol, diester with suberic acid and 2- [4- (2,4-dichlorobenzyloxy) phenyl)] ethanol, diester with azelaic acid and 2- (4-benzyloxyphenyl) ethanol, with sebacic acid Diester with 2- (4-benzyloxyphenyl) ethanol, diester with 1,10-decandicarboxylic acid and 2- (4-benzyloxyphenyl) ethanol, 1,18-octadecanedicarboxylic acid and 2- (4-benzyl) Examples thereof include a diester with oxyphenyl) ethanol, and a diester 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。 Further, as the component (c), a compound represented by the following general formula (5) can also be used.

(In the formula, R represents an alkyl group or an alkenyl group having 1 to 21 carbon atoms, and n represents an integer of 1 to 3).
Examples of the compound include a diester of 1,3-bis (2-hydroxyethoxy) benzene and capric acid, a diester of 1,3-bis (2-hydroxyethoxy) benzene and undecanoic acid, and 1,3-bis (2). Diester of -hydroxyethoxy) benzene and lauric acid, diester of 1,3-bis (2-hydroxyethoxy) benzene and myristic acid, diester of 1,4-bis (hydroxymethoxy) benzene and butyric acid, 1,4 -Diester of bis (hydroxymethoxy) benzene and isovaleric acid, diester of 1,4-bis (2-hydroxyethoxy) benzene and acetic acid, 1,4-bis (2-hydroxyethoxy) benzene and propionic acid Diester, diester of 1,4-bis (2-hydroxyethoxy) benzene and valerate, diester of 1,4-bis (2-hydroxyethoxy) benzene and caproic acid, 1,4-bis (2-hydroxyethoxy) ) Diester of benzene and capric acid, diester of 1,4-bis (2-hydroxyethoxy) benzene and capric acid, diester of 1,4-bis (2-hydroxyethoxy) benzene and lauric acid, 1,4 An example is an example of a diester of −bis (2-hydroxyethoxy) benzene and myristic acid.

（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。 Further, as the component (c), a compound represented by the following general formula (6) can also be used.

(In the formula, 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 compound include a diester of succinic acid and 2-phenoxyethanol, a diester of suberic acid and 2-phenoxyethanol, a diester of sebacic acid and 2-phenoxyethanol, and a diester of 1,10-decandycarboxylic acid and 2-phenoxyethanol. Examples thereof include a diester of 1,18-octadecanedicarboxylic acid and 2-phenoxyethanol.

（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。 Further, as the component (c), a compound represented by the following general formula (7) can also be used.

(In the formula, R represents any of an alkyl group having 4 to 22 carbon atoms, a cycloalkyl alkyl group, a cycloalkyl group, and an alkoxy group having 4 to 22 carbon atoms, and X is a hydrogen atom and an alkyl having 1 to 4 carbon atoms. Indicates a group, an alkoxy group having 1 to 4 carbon atoms, or a halogen atom, and n indicates 0 or 1).
Examples of the compound 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-Cyclohexylmethyl biphenylacetate can be exemplified.

（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。 Further, as the component (c), a compound represented by the following general formula (8) can also be used.

(In the formula, R represents any of an alkyl group having 3 to 18 carbon atoms and an aliphatic acyl group having 3 to 18 carbon atoms, and X is a hydrogen atom, an alkyl group having 1 to 3 carbon atoms, and 1 or 2 carbon atoms. Indicates either an alkoxy group or a halogen atom of, Y indicates either 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, or a halogen atom. Indicates one of.)
Examples of the compound include phenoxyethyl 4-butoxybenzoate, phenoxyethyl 4-pentyloxybenzoate, phenoxyethyl 4-tetradecyloxybenzoate, an ester of phenoxyethyl 4-hydroxybenzoate and dodecanoic acid, and phenoxyethyl vanirate. Dodecyl ether can be exemplified.

（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。 Further, as the component (c), a compound represented by the following general formula (9) can also be used.

(In the formula, R represents any of an alkyl group having 4 to 22 carbon atoms, an alkenyl group having 4 to 22 carbon atoms, a cycloalkylalkyl group, and a cycloalkyl group, and X is a hydrogen atom, an alkyl group, an alkoxy group, and a halogen. Indicates any of the atoms, Y indicates any of a hydrogen atom, an alkyl group, an alkoxy group, and a halogen atom, and n indicates 0 or 1).
Examples of the compound 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-decyl of dodecyl p-hydroxybenzoate. Examples thereof include methoxybenzoic acid ester and benzoic acid ester of cyclomethylmethyl p-hydroxybenzoate.

（式中、Ｒ_１及びＲ_２は、炭素数７〜２１の直鎖又は分岐のアルキル基又はアルケニル基を示し、Ｒ_３及びＲ_４は、水素原子、炭素数１〜２のアルキル基、又はＣＦ３を示す。）
前記化合物としては、４，４′−（ヘキサフルオロイソプロピリデン）ビスフェノールジカプレート、４，４′−（ヘキサフルオロイソプロピリデン）ビスフェノールジラウレート、４，４′−（ヘキサフルオロイソプロピリデン）ビスフェノールジミリステート、４，４′−（ヘキサフルオロイソプロピリデン）ビスフェノールジパルミエート、４，４′−（ヘキサフルオロイソプロピリデン）ビスフェノールジウンデカノエート、４，４′−（ヘキサフルオロイソプロピリデン）ビスフェノールジトリデカエート、４，４′−（イソプロピリデン）ビスフェノールジカプレート、４，４′−（イソプロピリデン）ビスフェノールジラウレート、４，４′−（イソプロピリデン）ビスフェノールジミリステート、４，４′−（イソプロピリデン）ビスフェノールジパルミエート、４，４′−（イソプロピリデン）ビスフェノールジウンデカノエート、４，４′−（イソプロピリデン）ビスフェノールジトリデカエート、４，４′−メチレンビスフェノールジカプレート、４，４′−メチレンビスフェノールジラウレート、４，４′−メチレンビスフェノールジミリステート、４，４′−メチレンビスフェノールジパルミエート、４，４′−メチレンビスフェノールジウンデカノエート、４，４′−メチレンビスフェノールジトリデカエート４，４′−エチリデンビスフェノールジラウレート４，４′−（１−メチルプロピリデン）ビスフェノールジラウレート、４，４′−（１−エチルプロピリデン）ビスフェノールジラウレートを例示できる。 Further, as the component (c), a compound represented by the following general formula (10) can also be used.

(In the formula, R ₁ and R ₂ represent a linear or branched alkyl group or alkenyl group having 7 to 21 carbon atoms, and R ₃ and R ₄ are hydrogen atoms, alkyl groups having 1 to 2 carbon atoms, or CF3 is shown.)
Examples of the compound include 4,4'-(hexafluoroisopropylidene) bisphenol dicaplate, 4,4'-(hexafluoroisopropylidene) bisphenol dilaurate, 4,4'-(hexafluoroisopropyridene) bisphenol dimyristate, and the like. 4,4'-(hexafluoroisopropylidene) bisphenol dipalmiate, 4,4'-(hexafluoroisopropylidene) bisphenol diundecanoate, 4,4'-(hexafluoroisopropyridene) bisphenol ditridecaate, 4 , 4'-(isopropylidene) bisphenol dicaplate, 4,4'-(isopropylidene) bisphenol dilaurate, 4,4'-(isopropyridene) bisphenol dimyristate, 4,4'-(isopropyridene) bisphenol dipalmi Ate, 4,4'-(isopropylidene) bisphenol diundecanoate, 4,4'-(isopropyridene) bisphenol ditridecaate, 4,4'-methylene bisphenol dicaplate, 4,4'-methylenebisphenol dilaurate, 4,4'-Methylenebisphenol dimylistate, 4,4'-Methylenebisphenol dipalmiate, 4,4'-Methylenebisphenol diundecanoate, 4,4'-Methylenebisphenol ditridecaate 4,4'-Echiliden Bisphenol dilaurate 4,4'-(1-methylpropylidene) bisphenol dilaurate, 4,4'-(1-ethylpropylidene) bisphenol dilaurate can be exemplified.

Further, as the component (c), 4-hydroxymethylbiphenyldecanoic acid ester, phenyl-n-decylether benzoate, 4-hydroxybenzophenone lauryl ether, 4-chloro-4'-hydroxybenzophenone lauric acid ester, 4-hydroxymethyl Biphenyl decyl ether can also be used.

Further, as the electron-accepting compound, a specific alkoxyphenol compound having a linear or side-chain alkyl group having 3 to 18 carbon atoms may be used (Japanese Patent Laid-Open No. 11-129623, JP-A-11-5973), or a specific one. A hydroxybenzoic acid ester (Japanese Patent Laid-Open No. 2001-105732) or a gallic acid ester (Japanese Patent Laid-Open No. 51-44706, Japanese Patent Application Laid-Open No. 2003-253149) is used for heating and coloring (coloring by heating, Applying a thermochromic color-memory microcapsule pigment (reversible thermochromic microcapsule pigment) containing a thermochromic color-memory composition (reversible thermochromic composition) (which is decolorized by cooling). Can also be done (see Figure 2).

The blending ratios of the components (a), (b), and (c) depend on the concentration, discoloration temperature, discoloration form, and type of each component, but in general, the component ratio at which the desired discoloration characteristics can be obtained is determined. The range of (b) component 0.1 to 50, preferably 0.5 to 20, and (c) component 1 to 800, preferably 5 to 200 with respect to (a) component 1 (all of the above ratios). It is a mass part). Further, each component may be used as a mixture of two or more kinds.

The thermochromic color memory composition is encapsulated in a microcapsule wall film and used as a thermochromic color memory microcapsule pigment (reversible thermochromic microcapsule pigment). This is because the thermochromic color memory composition can be kept in the same composition under various usage conditions and can exert the same action and effect.
Examples of the method for microencapsulating the thermochromic color memory composition include an interfacial polymerization method, an interfacial polycondensation method, an in-Situ polymerization method, an in-liquid curing coating method, a phase separation method from an aqueous solution, and an organic solvent. There are a phase separation method, a melt dispersion cooling method, an air suspension coating method, a spray drying method, and the like, which are appropriately selected according to the application. Further, a secondary resin film may be provided on the surface of the microcapsules according to the purpose to impart durability, or the surface characteristics may be modified for practical use.
Here, the mass ratio of the thermochromic color memory composition to the microcapsule wall film satisfies the range of 7: 1 to 1: 1, preferably 6: 1 to 1: 1.
When the ratio of the thermochromic color memory composition to the wall film is larger than the above range, the thickness of the wall film becomes too thin, and the resistance to pressure and heat tends to decrease, and the thermochromic color of the wall film tends to decrease. When the ratio to the memory composition is larger than the above range, the color density and sharpness at the time of color development are likely to decrease.

The organ substitute resin molded product can be obtained by blending a temperature-sensitive discoloration color memory composition with a molding resin selected from a thermoplastic resin and a thermosetting resin, and molding the product.
Examples of the molding resin include linear low-density polyethylene, low-density polyethylene, medium-high-density polyethylene, ultra-high-density polyethylene, chlorinated polyethylene, polypropylene, chlorinated polypropylene, poloisobutylene, polybutadiene, polymethylpentene, polystyrene, and polyethylene terephthalate. , Polybutylene terephthalate, polyvinyl acetate, vinyl chloride resin, chlorinated polyvinyl chloride, polyvinylidene chloride, acrylic acid ester resin, methacrylate ester resin, polyamide, copolymerized polyamide, polyamideimide, polyacetal, polyvinyl alcohol, polyvinylformal, Polyvinyl butyral, polyarylate, polyetherimide, polyether ether ketone, polycarbonate, polyphenyl ether, polyphenylene sulfide, polysulfone, fluororesin, ionomer resin, ethylene-propylene copolymer resin, ethylene-vinyl acetate copolymer resin, ethylene-vinyl Alcohol copolymer resin, ethylene-acrylic acid ester copolymer resin, ethylene-methacrylic acid ester copolymer resin, ethylene-vinyl chloride copolymer resin, vinyl chloride-propylene copolymer resin, vinyl chloride-vinylidene chloride copolymer resin, styrene- Butadiene copolymer resin, acrylonitrile-vinylidene chloride copolymer resin, acrylonitrile-styrene copolymer resin, acrylonitrile-ethylene-styrene copolymer resin, acrylonitrile-butadiene-styrene copolymer resin, acrylonitrile-chlorinated polyethylene-styrene copolymer resin, acrylonitrile -Acrylic acid ester-styrene copolymer resin, ethylene-vinyl acetate resin-vinyl chloride graft copolymer resin, methyl methacrylate-butadiene-styrene copolymer resin, styrene-based thermoplastic elastomer, olefin-based plastic elastomer, urethane-based plastic elastomer, Polystel-based plastic elastomer, 1,2-polybutadiene-based plastic elastomer, vinyl chloride-based plastic elastomer, petroleum hydrocarbon resin, cellulose acetate, cellulose acetate propionate, cellulose acetate butyrate, nitrocellulose, low-molecular-weight polyethylene, low-molecular-weight polypropylene , Polybutene, Kumaron-Inden copolymer, thermoplastic resins such as phenoxyplastics, epoxy resins, xylene resins, toluene resins, guanamine resins, epoxy acrylates, phenol resins , Unsaturated polyester resin, furan resin, polyimide, poly (p-hydroxybenzoic acid), polyurethane, urea resin, melamine resin, silicone resin and other thermosetting resins.
Further, it is also possible to impart conductivity by containing a conductive substance in the organ substitute resin molded product.

The shape of the organ substitute resin molded product is not particularly limited.

The surgical device is an endoscope that removes and excises the submucosa while observing with an endoscope when the diseased tissue remains in the inner mucosa such as early colorectal cancer, gastric cancer, and colorectal polyps. Examples include high-frequency scalpels and high-frequency snares of endoscopic surgical instruments used for surgical mucosal resection.

Examples are shown below, but the present invention is not limited to the examples. In addition, the part in an Example shows a mass part.
Example 1
Preparation of thermochromic color memory microcapsule pigment A (a) As a component, 3', 6'-bis [phenyl (3-methylphenyl) amino] -spiro [isocyanbenzofuran-1 (3H), 9'-[ 9H] xanthene] -3-one 2.0 parts, (b) component 4,4'-(2-ethylhexane-1,1-diyl) diphenol 3.0 parts, 2,2-bis (4') A thermochromic color memory composition consisting of 5.0 parts of -hydroxyphenyl) -hexafluoropropane and 50.0 parts of 4-benzyloxyphenylethyl capricate as a component (c) was heated and dissolved to prepare a wall film material. A solution obtained by mixing 30.0 parts of an aromatic isocyanate prepolymer and 40.0 parts of an auxiliary solvent was emulsified and dispersed in an 8% polyvinyl alcohol aqueous solution, and after continuing stirring while heating, a water-soluble aliphatic modified amine was added. 2.5 parts were added and further stirring was continued to obtain a microcapsule suspension. The suspension was centrifuged to isolate a thermochromic color-memory microcapsule pigment.
The average particle size of the microcapsule pigment is 2.2 μm, and the behavior has hysteresis characteristics of t1: -20 ° C, t2: -10 ° C, t3: 46 ° C, t4: 56 ° C, and ΔH: 66 ° C. It was shown that the color changed reversibly from blue to colorless and from colorless to blue.

Preparation of resin molded article for organ substitute (see FIGS. 3 and 4)
30 parts of the temperature-sensitive color-memory microcapsule pigment A, 100 parts of polysiloxane, and 1 part of a cross-linking agent, which have been cooled to -20 ° C or lower in advance to make them blue, are mixed and heat-pressed with a press to make a plate-shaped organ. A substitute resin molded product was obtained.
At room temperature (25 ° C.), the organ substitute resin molded product is visually recognizable in blue due to the temperature-sensitive color-memory microcapsule pigment, and the state is maintained in the room temperature range (FIG. 3).
Next, when a high-frequency scalpel is applied to the organ substitute resin molded product and heated to 100 ° C., the thermochromic color-memory microcapsule pigment is decolorized and the heated portion becomes translucent, and the state is in the normal temperature range. Since the heating site can be clearly seen while being maintained at, it could be used for simulation in medical practice of heating an organ (Fig. 4).
When the organ substitute resin molded product having a translucent heating site is cooled to -20 ° C or lower, the temperature-sensitive color-memory microcapsule pigment develops color again and turns blue, and a clear color change is permanently exhibited. It was possible to use it repeatedly.

Example 2
Preparation of thermochromic color-memory microcapsule pigment B (a) 2- (dibutylamino) -8- (dipentylamino) -4-methyl-spiro [5H- [1] benzopyrano [2,3-g) as a component ] Pyrimidine-5,1'(3'H) -isocyanbenzofuran] -3-one 1.0 part, 4,4'-(2-ethylhexane-1,1-diyl) diphenol 3 as (b) component A thermochromic color consisting of 0.0 part, 5.0 parts of 2,2-bis (4'-hydroxyphenyl) -hexafluoropropane, and 50.0 parts of 4-benzyloxyphenylethyl capricate as a component (c). The memory composition was heated and dissolved, and a solution obtained by mixing 30.0 parts of an aromatic isocyanate prepolymer and 40.0 parts of an auxiliary solvent as a wall film material was emulsified and dispersed in an 8% polyvinyl alcohol aqueous solution and heated. After continuing stirring, 2.5 parts of water-soluble aliphatic modified amine was added, and further stirring was continued to obtain a microcapsule suspension. The suspension was centrifuged to isolate a thermochromic color-memory microcapsule pigment.
The average particle size of the microcapsule pigment is 2.3 μm, and the hysteresis characteristics are t ₁ : -20 ° C, t ₂ : -10 ° C, t ₃ : 48 ° C, t ₄ : 58 ° C, ΔH: 68 ° C. The color changed reversibly from pink to colorless and from colorless to pink.

Preparation of resin molded article for organ substitute 30 parts of the temperature-sensitive color-remembering color-memory microcapsule pigment B, 100 parts of polysiloxane, and 1 part of a cross-linking agent, which had been cooled to -20 ° C or lower in advance to make them pink, were mixed and pressed with a press machine. Heat pressing was performed to obtain a plate-shaped resin molded product for organ substitution.
At room temperature (25 ° C.), the pink color of the organ substitute resin molded product due to the temperature-sensitive color-memory microcapsule pigment is visually recognized, and the state is maintained in the room temperature range.
Next, when a high-frequency scalpel is applied to the organ substitute resin molded product and heated to 100 ° C., the thermochromic color-memory microcapsule pigment is decolorized and the heated portion becomes translucent, and the state is in the normal temperature range. Since the heating site can be clearly seen while being maintained at, it could be used for simulation in medical practice of heating an organ.
When the resin molded article for organ substitute whose ablation site is translucent is cooled to -20 ° C or lower, the temperature-sensitive color-memory microcapsule pigment develops color again and turns pink, and a clear color change is permanently exhibited. It was possible to use it repeatedly.

Example 3
Preparation of thermochromic color-memory microcapsule pigment C (a) 9-ethyl (3-methylbutyl) amino-spiro [12H-benzo (a) xanthene-12,1'(3'H) isocyanatefuran] as a component -3'-On 2.0 parts, as (b) component, 1,1-bis (4-hydroxyphenyl) n-decane 5.0 parts, 2,2-bis (4'-hydroxyphenyl) -hexafluoro A thermochromic color memory composition consisting of 5.0 parts of propane and 50.0 parts of 4-methylbenzyl palmitate as a component (c) was heated and dissolved, and an aromatic isocyanate prepolymer 35.0 was used as a wall film material. A solution obtained by mixing 40.0 parts of a part and an auxiliary solvent was emulsified and dispersed in an 8% aqueous solution of polyvinyl alcohol, and stirring was continued while heating, then 2.5 parts of water-soluble aliphatic modified amine was added, and further stirring was performed. Continued to obtain a microcapsule suspension. The suspension was centrifuged to isolate a thermochromic color-memory microcapsule pigment.
The average particle size of the microcapsule pigment is 2.4 μm, and the hysteresis characteristics are t ₁ : -3 ° C, t ₂ : 5 ° C, t ₃ : 37 ° C, t ₄ : 43 ° C, ΔH: 39 ° C. It showed the behavior of having, and the color changed reversibly from pink to colorless and from colorless to pink.

Preparation of resin molded article for organ substitute 30 parts of the temperature-sensitive color-memory microcapsule pigment B, 100 parts of polysiloxane, and 1 part of a cross-linking agent, which had been cooled to -3 ° C or lower to make them pink in advance, were mixed and pressed with a press machine. Heat pressing was performed to obtain a plate-shaped resin molded product for organ substitution.
At room temperature (25 ° C.), the pink color of the organ substitute resin molded product due to the temperature-sensitive color-memory microcapsule pigment is visually recognized, and the state is maintained in the room temperature range.
Next, when ultrasonic waves are applied to the organ substitute resin molded product and heated to 45 ° C., the temperature-sensitive color-memory microcapsule pigment is decolorized and the heated portion becomes translucent, and the state is in the normal temperature range. Since the heating site can be clearly seen while being maintained at, it could be used for simulation in medical practice of heating an organ.
When the resin molded article for organ substitute whose heating part is translucent is cooled to -3 ° C or lower, the temperature-sensitive color-memory microcapsule pigment develops a color again and turns pink, and a clear color change is permanently maintained. It was able to be expressed and used repeatedly.

Example 5
Preparation of thermochromic color memory microcapsule pigment D (a) 7- [4- (diethylamino) -2-ethoxyphenyl] -7- (1-ethyl-2-methyl-1H-indole-3-) as a component Il) Flo [3,4-b] pyridine-5 (7H) -one part, (b) component 2,2-bis (4'-hydroxyphenyl) hexafluoropropane 5.0 part, (c) component As a wall film material, an aromatic isocyanate prepolymer (35.0 parts) was prepared by heating and dissolving a thermochromic color memory composition consisting of 50 parts of a diester of pimelli acid and 2- (4-benzyloxyphenyl) ethanol. A solution mixed with 40.0 parts of an auxiliary solvent was emulsified and dispersed in an 8% aqueous solution of polyvinyl alcohol, and stirring was continued while heating, then 2.5 parts of water-soluble aliphatic modified amine was added, and further stirring was continued. Obtained a microcapsule suspension. The suspension was centrifuged to isolate a thermochromic color-memory microcapsule pigment.
The average particle size of the microcapsule pigment is 2.5 μm, and the microcapsule pigment exhibits behavior having hysteresis characteristics of t1: -10 ° C, t2: 1 ° C, t3: 70 ° C, t4: 79 ° C, and ΔH: 79 ° C. The color changed reversibly from blue to colorless and from colorless to blue.

Preparation of resin molded article for organ substitute 30 parts of the temperature-sensitive color-memory microcapsule pigment D, 100 parts of polysiloxane, and 1 part of a cross-linking agent, which were previously cooled to -10 ° C or lower to make them blue, were mixed and heated with a press. Pressing was performed to obtain a plate-shaped resin molded product for organ substitution.
At room temperature (25 ° C.), the organ substitute resin molded product has a blue color due to the temperature-sensitive color-memory microcapsule pigment, and the state is maintained in the room temperature range.
Next, when a high-frequency scalpel is applied to the organ substitute resin molded product and heated to 100 ° C., the thermochromic color-memory microcapsule pigment is decolorized and the ablated site becomes translucent, and the state is at room temperature. Since the ablation site can be clearly seen while being maintained, it can be used for simulation in medical practice of ablation of an organ.
When the organ substitute resin molded product having a translucent ablation site is cooled to -10 ° C or lower, the temperature-sensitive color-memory microcapsule pigment develops color again and turns blue, and a clear color change is permanently exhibited. It was possible to use it repeatedly.

Example 6
Preparation of thermochromic color memory microcapsule pigment E (a) As a component, 7,7-bis [4- (diethylamino) -2-ethoxyphenyl] flo [3,4-b] pyridine-5 (7H)- 2.0 parts on, 3.0 parts of 4,4'-(2-ethylhexane-1,1-diyl) diphenol as component (b), 2,2-bis (4'-hydroxyphenyl) -hexafluoro A thermochromic color memory composition consisting of 5.0 parts of propane and 50.0 parts of a diester of 1,3-bis (2-hydroxyethoxy) benzene and capric acid as a component (c) was heated and dissolved. A solution obtained by mixing 30.0 parts of aromatic isocyanate prepolymer and 40.0 parts of an auxiliary solvent as a wall film material was emulsified and dispersed in an 8% polyvinyl alcohol aqueous solution, and after continuing stirring while heating, a water-soluble fat. 2.5 parts of group-modified amine was added, and further stirring was continued to obtain a microcapsule suspension. The suspension was centrifuged to isolate a thermochromic color-memory microcapsule pigment.
The average particle size of the microcapsule pigment is 2.2 μm, and the hysteresis characteristics are t ₁ : -16 ° C, t ₂ : -8 ° C, t ₃ : 38 ° C, t ₄ : 52 ° C, ΔH: 57 ° C. The color changed reversibly from blue-green to colorless and from colorless to blue-green.

Preparation of resin molded article for organ substitute 30 parts of the temperature-sensitive color-memory microcapsule pigment E, 100 parts of polysiloxane, and 1 part of cross-linking agent, which had been cooled to -16 ° C or lower to make it blue-green, were mixed and pressed with a press machine. Heat pressing was performed to obtain a plate-shaped resin molded product for organ substitution.
At room temperature (25 ° C.), the organ substitute resin molded product has a blue-green color due to a temperature-sensitive color-memory microcapsule pigment, and the state is maintained in the room temperature range.
Next, when a high-frequency scalpel is applied to the organ substitute resin molded product and heated to 100 ° C., the thermochromic color-memory microcapsule pigment is decolorized and the heated portion becomes translucent, and the state is in the normal temperature range. Since the heating site can be clearly seen while being maintained at, it could be used for simulation in medical practice of heating an organ.
When the resin molded article for organ substitute whose heating part is translucent is cooled to -16 ° C or lower, the temperature-sensitive color-memory microcapsule pigment develops color again and turns blue-green, and a clear color change is permanently maintained. It was able to be expressed and used repeatedly.

Example 7
Preparation of thermochromic color-memory microcapsule pigment F (a) As a component, 3', 6'-bis [phenyl (3-methylphenyl) amino] -spiro [isocyanbenzofuran-1 (3H), 9'-[ 9H] xanthene] -3-one 2.0 parts, (b) component myristyl hydroxybenzoate 8.0 parts, (c) component hexadecane 20.0 parts, heat-coloring type thermochromic color memory The composition was heated and dissolved, and a solution obtained by mixing 30.0 parts of aromatic isocyanate prepolymer and 40.0 parts of an auxiliary solvent as a wall film material was emulsified and dispersed in an 8% aqueous solution of polyvinyl alcohol, and stirred while heating. After that, 2.5 parts of water-soluble aliphatic modified amine was added, and further stirring was continued to obtain a microcapsule suspension. The suspension was centrifuged to isolate a thermochromic color-memory microcapsule pigment.
The average particle diameter of the above microcapsule pigment was 2.2 .mu.m, it began to color at 28 ℃ above (t _'3), completely blue color at 45 ° C. or higher (t' _4), at 0 ℃ below It indicates start decolorized (t _'2) behavior and reversibly color change colorless blue, from colorless to blue.

Preparation of resin molded article for organ substitutes 30 parts of thermochromic color-memory microcapsule pigment F, 100 parts of polysiloxane, and 1 part of cross-linking agent, which have been made colorless in advance, are mixed and heat-pressed with a press machine to form a plate-shaped organ substitute resin. A molded product was obtained.
The organ substitute resin molded product is visually recognized as being translucent at room temperature (25 ° C.), and the state is maintained in the room temperature range.
Next, when a high-frequency scalpel is applied to the organ substitute resin molded product and heated to 100 ° C., the thermochromic color-memory microcapsule pigment develops color and the heated portion turns blue, and the state is maintained in the normal temperature range. At the same time, the ablated site can be clearly seen, so that it can be used for simulation in medical practice of warming organs.
When the organ substitute resin molded product having a blue heating part is cooled to 0 ° C. or lower, the color begins to fade, and the translucent state is maintained at room temperature, and a clear color change can be permanently exhibited. It was possible and could be used repeatedly.

t ₁ Complete color development temperature of the microcapsule pigment containing the heat-decoloring type thermochromic color memory composition t ₂ Color development of the microcapsule pigment containing the heat-decoloring type thermochromic color memory composition Start temperature t ₃ Microcapsules containing a heat-decoloring type thermochromic color memory composition Decolorization start temperature of pigment t ₄ Microcapsules containing a heat-decoloring type thermochromic color memory composition the complete decoloring temperature t _'1 heating color development type thermochromic coloring color-memory composition of the microcapsule pigment enclosing a complete decoloring temperature t' ₂ heating color development type thermochromic coloring color-memory composition of the pigment contained the decoloring starting temperature t ₄ heating-coloring type of thermochromic coloring color-memory _'3 heating color development initiation temperature t of the color microcapsules pigment containing a thermochromic coloring color-memory composition of' the microcapsule pigment Complete color development temperature of microcapsule pigment containing composition ΔH Hysteresis width 1 Organ substitute resin molded product

Claims (6)

(B) As electron-donating color-forming organic compounds, phenylindrylphthalides, indolylphthalides, diphenylmethaneazaphthalides, phenylindrillazaphthalides, fluorans, styrylquinolines, diazarodamine. A reaction medium that reversibly causes an electron transfer reaction by a compound selected from lactones, quinazolines and bisquinazolines, (b) an electron-accepting compound, and (c) the above-mentioned (a) and (b) components in a specific temperature range. Confirmed heating by a medical device that imitates the shape of an organ by containing a thermochromic color-memory microcapsule pigment containing a thermochromic color-memory composition. Organ substitute resin molded product. The temperature-sensitive color-memory microcapsule pigment exhibits a large hysteresis characteristic with respect to the color density-temperature curve, exhibits mutual modification between the first hue and the second hue, and is a process in which the temperature rises in the first hue. Then, when the temperature reaches t ₃ , the first hue begins to change color, becomes completely the second hue in the temperature range above the temperature t ₄ higher than the temperature t ₃ , and in the process of lowering the temperature in the second hue state. When the temperature t ₂ is reached, the second hue begins to change color and becomes completely the first hue in the temperature range lower than the temperature t ₂ and below the temperature t ₁ , and in the temperature range between the temperature t ₂ and the temperature t _3. Shows hysteresis characteristics in which the first hue or the second hue is retained, temperature t ₂ is a temperature below room temperature, temperature t ₄ is above room temperature, and is a temperature below the cauterization temperature for organs. The organ substitute resin molded product according to claim 1, which is a temperature-sensitive color-memory microcapsule pigment containing a color-memory composition. The organ substitute resin molded product according to claim 2, wherein the temperature t ₄ exceeds the body temperature. The organ substitute resin molded product according to claim 2 or 3, wherein the temperature t ₂ is a temperature of less than 5 ° C. and the temperature t ₄ is a temperature of 40 ° C. or higher. The organ substitute resin molded product according to any one of claims 2 to 4, wherein the temperature t ₄ is a temperature of 50 to 100 ° C. The organ substitute resin molded product according to any one of claims 2 to 5, wherein the temperature t ₁ is a temperature of −50 to 0 ° C.

Images