JP2018049156A - Organ substitute resin molded material and evaluator for ablation catheter using thereof - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a highly convenient organ substitute resin molded material capable of clearly confirming ablated regions of the organ by an operating instrument and capable of sufficiently performing simulation in the medical activity.SOLUTION: An organ substitute resin molded material 1 exhibits interchangeability between a first color phase and a second color phase by showing large hysteresis characteristics with respect to color density-temperature curve and begins to turn in color when it reaches a temperature tin the first color phase in the course of the temperature rising. When the temperature becomes equal to or more than a temperature t, it becomes the second color phase. In the course of the temperature lowering, when the temperature reaches a temperature t, it begins to turn in color, and the temperature becomes the first color phase when it is below a temperature tand the first color phase or the second color phase is held in the temperature region between the temperature tand the temperature t. The temperature tis a temperature equal to or less than the normal temperature. The temperature texceeds the normal temperature, and includes a temperature sensitive microcapsule color-changeability storage microcapsule pigment in the molded material. An evaluator for ablation catheter using the organ substitute resin molded material is also provided.SELECTED DRAWING: Figure 3

Description

  The present invention relates to an organ substitute resin molding and an evaluation instrument for an ablation catheter using the same. More specifically, the present invention relates to an organ substitute resin molding used for simulation in a medical practice of cauterizing an organ using a surgical instrument and an evaluation instrument for an ablation catheter using the same.

Conventionally, animal tissues such as pigs and cattle have been used for simulations in medical practice of cauterizing organs using surgical instruments such as endoscopic surgical instruments. To maintain animal tissues immediately after slaughter It is time consuming and the use of animal tissue has not been preferred for hygiene and indoor environments.
Therefore, an organ model made of a synthetic resin instead of animal tissue has been disclosed (for example, see Patent Document 1).
The organ model is a highly convenient simulated organ that does not care about the maintenance of tissues until use like animal tissues, 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.).

Japanese Patent Laying-Open No. 2015-36809

  The present invention is intended to provide an organ substitute resin composition capable of clearly confirming the degree of cauterization of an organ model for procedure practice involving this type of cauterization, and an ablation catheter evaluation instrument using the same. is there.

In the present invention, (a) an electron-donating color-forming organic compound, (b) an electron-accepting compound, and (c) an electron transfer reaction by the components (a) and (b) is reversibly caused in a specific temperature range. A temperature-sensitive color-changing color memory composition comprising a reaction medium, exhibiting a large hysteresis characteristic with respect to a color density-temperature curve, exhibiting tautomerism between the first hue and the second hue, in the process the temperature rises 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, in the second color state temperature in the process but descending, reaches the temperature t _2, the second color begins to discolor, become completely the first color at a lower temperature t ₁ the following temperature range than the temperature t _2, the temperature t ₂ and the temperature t ₃ Hysteresis characteristics that keep the first hue or the second hue in the temperature range between The molded product contains a temperature-sensitive color-changing color memory microcapsule pigment having a temperature t ₂ of less than room temperature, a temperature t ₄ of more than room temperature, and a temperature below the cauterization temperature for the organ. Therefore, an organ substitute resin molded product for confirming cauterization by organ surgery equipment is required.
Furthermore, the temperature t ₄ is a temperature exceeding the body temperature, the temperature t ₂ is a temperature of 5 ° C. or less, the temperature t ₄ is a temperature of 40 ° C. or more, and the temperature t ₄ is 50 to 100 That the temperature t ₁ is a temperature of −50 to 0 ° C., a plurality of temperature-sensitive color-changing color memory compositions having different temperatures t ₄ are contained in the molded product, The requirement is to imitate the shape of an organ and to contain a conductive material.
Furthermore, it is an instrument for evaluating ablation using an ablation catheter, and contains a counter electrode and a liquid disposed on the counter electrode and used for evaluating the ablation, and is made of a conductive resin. An evaluation instrument for an ablation catheter provided with a configured container and the organ substitute resin molded article as a sample for evaluating the ablation disposed in the container is a requirement.

  The present invention can clearly confirm the ablation site of an organ by a surgical instrument, and can perform a simulation in medical practice with high convenience, and is used for evaluation of an ablation catheter using the same. An instrument can be provided.

It is explanatory drawing which shows the color-change behavior of the temperature-sensitive color-change color memory property composition used for this invention. It is explanatory drawing which shows the discoloration behavior of the other thermosensitive color-change color memory property composition used for this invention. It is a longitudinal cross-sectional explanatory drawing of one Example of the organ substitute resin molding of this invention. It is a longitudinal cross-sectional explanatory drawing which shows the state after cauterization of the organ substitute resin molding of FIG. It is a schematic diagram showing the example of schematic structure of the evaluation instrument for ablation catheters of this invention.

  The organ substitute resin molding of the present invention comprises a thermosensitive color-changing color memory microcapsule pigment encapsulating a temperature-sensitive color-changing color memory composition in a resin molding.

The temperature-sensitive color-changing color memory composition is a large one described in JP-B-4-17154, JP-A-7-179777, JP-A-7-33997, JP-A-8-39936, and the like. Hysteresis characteristics (ΔH _B = 8 to 50 ° C.), that is, the shape of the curve in which the change of the color density due to the temperature change is plotted is the color change temperature contrary to the case where the temperature is raised from the lower temperature side than the color change temperature range. The color changes following a path that differs greatly depending on whether it is lowered from the high temperature side, and the color development state in the low temperature range below the complete color development temperature (t ₁ ), or the high temperature range above the complete decoloration temperature (t ₄ ) The color erasing state is a heat decoloring type having color memory in a specific temperature range [temperature range between t _{2 and} t ₃ (substantially two-phase holding temperature range)]. It is a reversible thermochromic composition that develops color (Figure) 1).
The hysteresis characteristic in the color density-temperature curve of the temperature-sensitive color-changing color memory composition will be described.
In FIG. 1, the vertical axis represents color density and the horizontal axis represents temperature. The change in color density due to the temperature change proceeds along the arrow. Here, A is a point indicating a density at a temperature t ₄ (hereinafter referred to as a complete decoloring temperature) that reaches a completely decoloring state, and B is a temperature t ₃ (hereinafter referred to as a decoloring start temperature). C represents a density at a temperature t ₂ at which color development starts (hereinafter referred to as a color development start temperature), and D represents a temperature t ₁ at which a complete color development state is reached (hereinafter referred to as a complete color development state). This is a point indicating a density at a 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 color density difference. The temperature range is substantially the discoloration temperature range.
The length of the line segment EF is a scale indicating the discoloration contrast, 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 specific state can exist in the normal temperature range among both states before and after the color change. Further, when the ΔH value is large, it is easy to maintain each state before and after the color change.
The temperature-sensitive color-changing color memory composition can selectively hold either the colored state or the decolored state over the entire color holding temperature range (t ₃ -t ₂ ), and color development starts. There is 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 colored state or the decolored state can be alternatively stored and held at a general use environment temperature. it can.
Further, the temperature t ₂ is at a temperature below room temperature, the temperature t ₄ is greater than ambient temperature, and, by a temperature below the ablation temperature for organs, thermochromic coloring color-memory which was developed at a temperature t ₁ following The composition is discolored by cauterization with organ surgery equipment, and its state is maintained at room temperature, so the ablation site can be clearly confirmed, and sufficient simulation (learning, training, training, proficiency, exercises) Etc.).
Furthermore, 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 less below the normal temperature range where the temperature-sensitive color-changing color memory composition does not develop color, and the temperature t ₄ exceeds the normal temperature and is below the cauterization temperature for the organ. The temperature is 40 ° C. or higher.
Here, the reason why the temperature t ₄ is higher than the normal temperature and lower than the cauterization temperature for the organ and the temperature t ₂ is a temperature lower than the normal temperature will be described. ₃ ) If the heating is stopped without reaching the complete decoloring temperature (t ₄ ), the phenomenon of returning to the first state occurs again, and the color development start temperature (t ₂ ) is changed from the decolored state. After this, even if cooling is stopped in a state where the complete color development temperature (t ₁ ) has not been reached, the color developed state is maintained. Therefore, the complete color erasure temperature (t ₄ ) exceeds normal temperature, and the cauterization temperature for the organ If the temperature is below, the colored state is maintained in the normal use state before cauterization, and if the color development start temperature (t ₂ ) is lower than the normal temperature range, the decolored state is normal after cauterization. Maintained in use.
Therefore, the temperature setting is an important requirement for making the state where the ablation site of the temperature-sensitive color-changing color memory composition is discolored alternatively visible, and can satisfy convenience and practicality.
In the temperature setting of the complete decoloring temperature (t ₄ ), a higher temperature is preferable in order to maintain the color development state in a normal use state, and the temperature does not cause excessive cauterization of the organ. Is preferred.
Therefore, the complete decoloring temperature (t ₄ ) is preferably 50 to 100 ° C., more preferably 50 to 80 ° C.
Furthermore, in the temperature setting of the color development start temperature (t ₂ ) described above, a lower temperature is preferable for maintaining the decolored state in a normal use state, and 0 ° C. or less is preferable, and −5 C. or less is more preferable.
In order to bring the temperature-sensitive color-changing color memory composition into a colored 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 up to −50 ° C. Therefore, the complete color development temperature (t ₁ ) is preferably −50 ° C. to 0 ° C.

Examples of the compounds for the components (a), (b) and (c) of the thermosensitive color-change color memory composition are shown below.
Examples of the electron donating color-forming organic compound as component (a) of the present invention include diphenylmethane phthalides, phenyl indolyl phthalides, indolyl phthalides, diphenyl methane azaphthalides, and phenyl indolyl azaphthalides. Fluoranes, styrinoquinolines, diazarhodamine lactones, pyridines, quinazolines, bisquinazolines and the like.
Examples of these compounds are given below.
3,3-bis (p-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- (N-ethylanilino) phenyl] -3- (1-ethyl-2-methylindol-3-yl) -4-azaphthalide,
3,6-diphenylaminofluorane,
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- (2-chloroamino) -6-dibutylaminofluorane,
2- (2-chloroanilino) -6-di-n-butylaminofluorane,
2- (3-trifluoromethylanilino) -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,
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-dodecoxystyryl) quinoline,
Spiro [5H- (1) benzopyrano (2,3-d) pyrimidine-5,1 '(3'H) isobenzofuran] -3'-one,
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-one,
2- (Di-n-butylamino) -8- (N-ethyl-Ni-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-methylindol-3-yl) -4,5,6,7-tetrachlorophthalide,
3- (2-ethoxy-4-diethylaminophenyl) -3- (1-ethyl-2-methylindol-3-yl) -4,5,6,7-tetrachlorophthalide,
3- (2-ethoxy-4-diethylaminophenyl) -3- (1-pentyl-2-methylindol-3-yl) -4,5,6,7-tetrachlorophthalide,
4,5,6,7-tetrachloro-3- [4- (diethylamino) -2-methylphenyl] -3- (1-ethyl-2-methyl-1H-indol-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,
4- [2,6-bis (2-ethoxyphenyl) -4-pyridinyl] -N, N-dimethylbenzenamine,
2- (4'-dimethylaminophenyl) -4-methoxy-quinazoline,
4,4 '-(ethylenedioxy) -bis [2- (4-diethylaminophenyl) quinazoline] and the like.
In addition to the above compounds having a substituent on the phenyl group forming the xanthene ring, the fluoranes include a substituent on the phenyl group forming the lactone ring as well as the phenyl group forming the xanthene ring (for example, Or a blue or black compound having an alkyl group such as a methyl group or a halogen atom such as a chloro group.

As the electron-accepting compound of the component (b), a compound group having active protons, a pseudo-acidic compound group (a compound group that is not an acid but acts as an acid in the composition to cause the component (I) to develop color), There is a group of compounds having electron vacancies.
Examples of compounds having active protons include monophenols to polyphenols as compounds having phenolic hydroxyl groups, and alkyl groups, aryl groups, acyl groups, alkoxycarbonyl groups, carboxy groups and esters thereof as substituents. Alternatively, those having an amide group, a halogen group, etc., and bis-type and tris-type phenols, phenol-aldehyde condensation resins and the like can be mentioned. Moreover, the metal salt of the compound which has the said phenolic hydroxyl group may be sufficient.
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 N-octyl p-hydroxybenzoate, resorcin, 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- Droxyphenyl) 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, -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) Phenyl) -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 develop the most effective thermochromic property, but aromatic carboxylic acids and 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-triazole and derivatives thereof.

The component (c) of the reaction medium that causes the electron transfer reaction by the components (a) and (b) to occur reversibly in a specific temperature range will be described.
Examples of the component (c) include alcohols, esters, ketones, and ethers.
As the component (c), the color density-temperature curve has a large hysteresis characteristic (a curve plotting a change in color density due to a temperature change changes the temperature from the low temperature side to the high temperature side, and the high temperature side to the low temperature side). A carboxylic acid ester compound exhibiting a ΔT value (melting point-cloud point) of 5 ° C. or more and less than 50 ° C., which can form a reversible thermochromic composition exhibiting color memory, which changes color when changing to , Stearyl 2-methylbenzoate, cetyl 4-tert-butylbenzoate, behenyl 4-cyclohexylbenzoate, myristyl 4-phenylbenzoate, lauryl 4-octylbenzoate, hexyl 3,5-dimethylbenzoate, 3-ethyl Stearyl benzoate, decyl 4-isopropylbenzoate, stearyl 4-benzoylbenzoate, phenyl 4-tert-butylbenzoate , 4-chlorobenzyl 2-methylbenzoate, stearyl 4-chlorobenzoate, myristyl 3-bromobenzoate, stearyl 2-chloro-4-bromobenzoate, decyl 3,4-dichlorobenzoate, 2,4- Octyl dibromobenzoate, cetyl 3-nitrobenzoate, cyclohexylmethyl 4-aminobenzoate, cetyl 4-diethylaminobenzoate, stearyl 4-anilinobenzoate, decyl 4-methoxybenzoate, cetyl 4-methoxybenzoate, 4- Octyl butoxybenzoate, cetyl 4-hydroxybenzoate, 4-methoxyphenylmethyl benzoate, stearyl p-chlorophenylacetate, cetyl p-chlorophenylacetate, benzyl salicylate, neopantil salicylate, 4-methoxymethylphenylmethyl salicylate, benzoic acid 4-chloroph Nylmethyl, 4-chlorophenylmethyl caprate, 4-methoxyphenylmethyl myristate, 4-methylphenylmethyl stearate, 4-nitrophenylmethyl stearate, 4-methylphenylmethyl caproate, 2-myristate 2- Carboxylic acid ester having a substituted aromatic ring in the molecule such as chlorophenylmethyl, 4-methoxyphenylmethyl caprate, 4-chlorophenyl 11-bromolaurate, 4-isopropylphenyl stearate, stearyl 1-naphthoate, Esters of carboxylic acids containing unsubstituted aromatic rings such as cetyl benzylate, stearyl benzylate, decyl 3-benzoylpropionate, stearyl benzoate, cetyl benzoate, myristyl benzoate and aliphatic alcohols having 10 or more carbon atoms, silica Cyclohexylmethyl cinnamate, Cyclohexyl in molecules such as cyclohexyl laurate, cyclohexyl myristate, cyclohexyl palmitate, cyclohexylmethyl stearate, cyclohexylethyl stearate, stearyl cyclohexylacetate, stearyl 2-cyclohexylpropionate, stearylcyclohexanecarboxylate, cyclohexyl 2-benzoylpropionate Carboxylic acid ester containing a group, benzyl caproate, benzyl palmitate, 4-methylbenzyl palmitate, 3-phenylpropyl stearate, phenyl 11-bromolaurate and the like and fatty alcohol and aromatic alcohol or phenol Esters of fatty acids having 8 or more carbon atoms such as neopentyl octylate and neopentyl laurate and branched aliphatic alcohols, Sebashi Dibenzylic acid, 4,4'-diphenyldicarboxylic acid dineopentyl, dicarboxylic acid such as dibenzyl azodicarboxylate and ester of aromatic alcohol or branched aliphatic alcohol, dibenzyl cinnamate, heptyl stearate, didecyl adipate, dilauryl adipate , Dimyristyl adipate, dicetyl adipate, distearyl adipate, trilaurin, trimyristin, tristearin, dimyristin, distearin and the like.

Also, fatty acid ester compounds obtained from an odd aliphatic monohydric alcohol having 9 or more carbon atoms and 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. A fatty acid ester compound having a total carbon number of 17 to 23 obtained from a group carboxylic acid is 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 ristinate, n-pentyl palmitate, n-heptyl palmitate, n-nonyl palmitate, n-undecyl palmitate, n-tridecyl palmitate, n-pentadecyl palmitate, n-nonyl stearate, stearic acid n-undecyl, n-tridecyl stearate, n-pentadecyl stearate, n-nonyl eicosanoate, n-undecyl eicosanoate, n-tridecyl eicosanoate, n-pentadecyl eicosanoate, n-nonyl behenate, n-behenate Examples include undecyl, n-tridecyl behenate, and n-pentadecyl behenate.

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. 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, laurone, stearone and the like.
Further, arylalkyl ketones having 12 to 24 carbon atoms in total, such as n-octadecanophenone, n-heptadecanophenone, n-hexadecanophenone, n-pentadecanophenone, n-tetradecano Phenone, 4-n-dodecanacetophenone, 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-pentylacetophene Emissions, cyclohexyl phenyl ketone, benzyl -n- butyl ketone, 4-n-butyl acetophenone, n- hexanophenone, 4-isobutyl acetophenone, 1-acetonaphthone, 2-acetonaphthone, may be mentioned cyclopentyl phenyl ketone.

  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. , Ditridecyl ether, ditetradecyl ether, dipentadecyl ether, dihexadecyl ether, dioctadecyl ether, decane diol dimethyl ether, undecane diol dimethyl ether, dodecane diol dimethyl ether, tridecane diol dimethyl ether, decane diol diethyl ether, undecane diol diethyl ether Etc.

〔式中、Ｒ₁は水素原子又はメチル基を示し、ｍは０〜２の整数を示し、Ｘ₁、Ｘ₂のいずれか一方は−（ＣＨ₂）_nＯＣＯＲ₂又は−（ＣＨ₂）_nＣＯＯＲ₂、他方は水素原子を示し、ｎは０〜２の整数を示し、Ｒ₂は炭素数４以上のアルキル基又はアルケニル基を示し、Ｙ₁及びＹ₂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、Ｒ₁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Ｒ₁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。 Moreover, the compound shown by following General formula (1) can also be used as said (c) component.

[Wherein, 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 represents — (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, 1 to 4 carbon atoms An alkyl group, a methoxy group, or halogen, and r and p each represent an integer of 1 to 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 is more preferably 0.
Of the compounds represented by the formula (1), a compound represented by the following general formula (2) is more preferably used.

R in the formula 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 compound include octanoic acid-4-benzyloxyphenylethyl, nonanoic acid-4-benzyloxyphenylethyl, decanoic acid-4-benzyloxyphenylethyl, undecanoic acid-4-benzyloxyphenylethyl, and dodecanoic acid. -4-benzyloxyphenylethyl, tridecanoic acid-4-benzyloxyphenylethyl, tetradecanoic acid-4-benzyloxyphenylethyl, pentadecanoic acid-4-benzyloxyphenylethyl, hexadecanoic acid-4-benzyloxyphenylethyl, heptadecanoic acid Examples thereof include -4-benzyloxyphenylethyl and octadecanoic acid-4-benzyloxyphenylethyl.

（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).

(In the formula, R represents an alkyl group or alkenyl group having 8 or more carbon atoms, m and n each represents an integer of 1 to 3, X and Y represent a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, carbon, respectively. (The alkoxy group of Formula 1-4 is shown, and a halogen.)
Specific examples of the compound include 1,1-diphenylmethyl octanoate, 1,1-diphenylmethyl nonanoate, 1,1-diphenylmethyl decanoate, 1,1-diphenylmethyl undecanoate, 1,1-dodecanoic acid 1,1- Diphenylmethyl, tridecanoic acid 1,1-diphenylmethyl, tetradecanoic acid 1,1-diphenylmethyl, pentadecanoic acid 1,1-diphenylmethyl, hexadecanoic acid 1,1-diphenylmethyl, heptadecanoic acid 1,1-diphenylmethyl, octadecanoic acid An example is 1,1-diphenylmethyl.

（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 compound include a diester of malonic acid and 2- [4- (4-chlorobenzyloxy) phenyl)] ethanol, a diester of succinic acid and 2- (4-benzyloxyphenyl) ethanol, succinic acid and 2- Diester with [4- (3-methylbenzyloxy) phenyl)] ethanol, diester with glutaric acid and 2- (4-benzyloxyphenyl) ethanol, glutaric acid and 2- [4- (4-chlorobenzyloxy) Phenyl)] ethanol diester, adipic acid and 2- (4-benzyloxyphenyl) ethanol diester, pimelic acid and 2- (4-benzyloxyphenyl) ethanol diester, suberic acid and 2- (4- Diester with benzyloxyphenyl) ethanol, suberic acid and 2- [4- (3-methyl Benzyloxy) phenyl)] ethanol diester, suberic acid and 2- [4- (4-chlorobenzyloxy) phenyl)] ethanol diester, suberic acid and 2- [4- (2,4-dichlorobenzyloxy) ) Phenyl)] ethanol diester, azelaic acid and 2- (4-benzyloxyphenyl) ethanol diester, 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-benzyloxyphenyl) ethanol diester, 1,18-octadecanedicarboxylic acid and 2- [4- (2-Methylbenzyloxy) phenyl)] die with ethanol It can be exemplified ether.

（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).

(In the formula, R represents an alkyl group or 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 -Hydroxyethoxy) benzene and lauric acid diester, 1,3-bis (2-hydroxyethoxy) benzene and myristic acid diester, 1,4-bis (hydroxymethoxy) benzene and butyric acid diester, 1,4 Diesters of bis (hydroxymethoxy) benzene and isovaleric acid, diesters of 1,4-bis (2-hydroxyethoxy) benzene and acetic acid, and 1,4-bis (2-hydroxyethoxy) benzene and propionic acid Diester, diester of 1,4-bis (2-hydroxyethoxy) benzene and valeric acid Diester of 1,4-bis (2-hydroxyethoxy) benzene and caproic acid, diester of 1,4-bis (2-hydroxyethoxy) benzene and caprylic acid, 1,4-bis (2-hydroxyethoxy) benzene And diester of capric acid, 1,4-bis (2-hydroxyethoxy) benzene and lauric acid, and 1,4-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。 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.)
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, a diester of 1,10-decanedicarboxylic acid and 2-phenoxyethanol, An example is 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。 Furthermore, a compound represented by the following general formula (7) can also be used as the component (c).

(In the formula, R represents any of an alkyl group having 4 to 22 carbon atoms, a cycloalkylalkyl group, a cycloalkyl group, and an alkenyl group having 4 to 22 carbon atoms, and X represents a hydrogen atom and an alkyl having 1 to 4 carbon atoms. A group, an alkoxy group having 1 to 4 carbon atoms, or a halogen atom, and n represents 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, 4-biphenylacetic acid Decyl, 4-biphenyl lauryl acetate, 4-biphenyl acetate myristyl, 4-biphenyl acetate tridecyl, 4-biphenyl acetate pentadecyl, 4-biphenyl acetate cetyl, 4-biphenyl acetate cyclopentyl, 4-biphenyl acetate cyclohexyl methyl, 4-biphenyl acetate hexyl And cyclohexylmethyl 4-biphenylacetate.

（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).

(In the formula, R represents an alkyl group having 3 to 18 carbon atoms or an aliphatic acyl group having 3 to 18 carbon atoms, X represents a hydrogen atom, an alkyl group having 1 to 3 carbon atoms, or 1 or 2 carbon atoms. Y represents either a hydrogen atom or a methyl group, Z represents 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 one of these.)
Examples of the compound include phenoxyethyl 4-butoxybenzoate, phenoxyethyl 4-pentyloxybenzoate, phenoxyethyl 4-tetradecyloxybenzoate, esters of phenoxyethyl 4-hydroxybenzoate and dodecanoic acid, phenoxyethyl vanillate The dodecyl ether can be illustrated.

（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).

(In the formula, 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, and X represents a hydrogen atom, an alkyl group, an alkoxy group, a halogen atom, Any one of the atoms, Y represents any one of a hydrogen atom, an alkyl group, an alkoxy group, and a halogen atom, and n represents 0 or 1.)
Examples of the compound include benzoic acid ester of octyl p-hydroxybenzoate, benzoic acid ester of decyl p-hydroxybenzoic acid, p-methoxybenzoic acid ester of heptyl p-hydroxybenzoic acid, o-hydroxyl of dodecyl p-hydroxybenzoic acid. Examples thereof include methoxybenzoic acid ester and benzoic acid ester of cyclohexylmethyl p-hydroxybenzoate.

（式中、Ｒ₁及びＲ₂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、Ｒ₃及びＲ₄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。 Furthermore, a compound represented by the following general formula (10) can also be used as the component (c).

(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 represent a hydrogen atom, an alkyl group having 1 to 2 carbon atoms, or CF3 is shown.)
Examples of the compound include 4,4 ′-(hexafluoroisopropylidene) bisphenol dicaprate, 4,4 ′-(hexafluoroisopropylidene) bisphenol dilaurate, 4,4 ′-(hexafluoroisopropylidene) bisphenol dimyristate, 4,4 ′-(hexafluoroisopropylidene) bisphenol dipalmiate, 4,4 ′-(hexafluoroisopropylidene) bisphenol diundecanoate, 4,4 ′-(hexafluoroisopropylidene) bisphenol ditridecaate, 4 , 4 '-(isopropylidene) bisphenol dicaprate, 4,4'-(isopropylidene) bisphenol dilaurate, 4,4 '-(isopropylidene) bisphenol dimyristate, 4,4'-(isopropylidene) ) Bisphenol dipalmiate, 4,4 '-(isopropylidene) bisphenol diundecanoate, 4,4'-(isopropylidene) bisphenol ditridecanate, 4,4'-methylenebisphenol dicaplate, 4,4 ' -Methylene bisphenol dilaurate, 4,4'-methylene bisphenol dimyristate, 4,4'-methylene bisphenol dipalmitate, 4,4'-methylene bisphenol diundecanoate, 4,4'-methylene bisphenol ditridecanate 4 4,4'-ethylidenebisphenol dilaurate 4,4 '-(1-methylpropylidene) bisphenol dilaurate and 4,4'-(1-ethylpropylidene) bisphenol dilaurate.

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

  In addition, a specific alkoxyphenol compound having a linear or side chain alkyl group having 3 to 18 carbon atoms may be used as the electron-accepting compound (Japanese Patent Laid-Open Nos. 11-129623 and 11-5973). Hydroxybenzoic acid esters (Japanese Patent Laid-Open No. 2001-105732), gallic acid esters and the like (Japanese Patent Publication No. 51-44706, Japanese Patent Laid-Open No. 2003-253149) are used. Applying a thermochromic color-memory microcapsule pigment (reversible thermochromic microcapsule pigment) containing a thermochromic color-memory composition (reversible thermochromic composition) that is decolored by cooling) (See FIG. 2).

  The mixing ratio of the components (A), (B), and (C) depends on the concentration, the color change temperature, the color change form, and the type of each component. (B) Component 1 is in the range of (b) Component 0.1-50, preferably 0.5-20, (c) Component 1-800, preferably 5-200. Part by mass). Moreover, you may use each component in mixture of 2 or more types, respectively.

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 temperature-sensitive color-changing color memory composition can be maintained in the same composition under various usage conditions and can exhibit the same effects.
Methods for microencapsulating the thermochromic color memory composition include interfacial polymerization, interfacial polycondensation, in situ polymerization, in-liquid curing coating, phase separation from aqueous solution, and 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. Furthermore, a secondary resin film may be provided on the surface of the microcapsule according to the purpose to impart durability, or the surface characteristics may be modified for practical use.
Here, the mass ratio between the temperature-sensitive color-changing color memory composition and the microcapsule wall film satisfies the range of 7: 1 to 1: 1, preferably 6: 1 to 1: 1.
When the ratio of the temperature-sensitive color-changing color memory composition to the wall film is larger than the above range, the wall film becomes too thin, and the resistance to pressure and heat tends to decrease, and the temperature-sensitive color-changing color of the wall film. When the ratio with respect to the memory composition is larger than the above range, the color density and the sharpness during color development tend to be reduced.

Furthermore, by including a plurality of temperature-sensitive color-changing color memory compositions having different temperatures t ₄ in the organ substitute resin molding, the heat transfer condition of the ablation site is visually changed in stages. Therefore, a highly accurate simulation becomes possible.

The organ substitute resin molding can be obtained by blending a molding resin selected from thermoplastic resins and thermosetting resins with a thermochromic color-memory composition.
Examples of the molding resin include linear low density polyethylene, low density polyethylene, medium density polyethylene, ultra high density polyethylene, chlorinated polyethylene, polypropylene, chlorinated polypropylene, polyisobutylene, polybutadiene, polymethylpentene, polystyrene, polyethylene terephthalate. , Polybutylene terephthalate, polyvinyl acetate, vinyl chloride resin, chlorinated polyvinyl chloride, polyvinylidene chloride, acrylic ester resin, methacrylic ester resin, polyamide, copolymer polyamide, polyamide imide, polyacetal, polyvinyl alcohol, polyvinyl formal, Polyvinyl butyral, polyarylate, polyether imide, polyether ether ketone, polycarbonate, polyphenyl ether, polyphenyle 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 Composite resin, ethylene-vinyl acetate resin-vinyl chloride graft copolymer resin, methyl methacrylate-butadiene-styrene copolymer resin, styrene thermoplastic elastomer, olefin plastic elastomer, urethane plastic elastomer, polyester plastic elastomer, 1, 2-polybutadiene plastic elastomer, vinyl chloride plastic elastomer, petroleum hydrocarbon resin, cellulose acetate, cellulose acetate propionate, cellulose acetate butyrate, nitrocellulose, low molecular weight polyethylene, low molecular weight polypropylene, polybutene, coumarone-indene Polymer, thermoplastic resin such as phenoxy plastic, epoxy resin, xylene resin, toluene resin, guanamine resin, epoxy acrylate, phenol resin And thermosetting resins such as unsaturated polyester resin, furan resin, polyimide, poly (p-hydroxybenzoic acid), polyurethane, urea resin, melamine resin, and silicone resin.
Further, the organ substitute resin molding can be provided with conductivity by containing a conductive substance.

  The shape of the organ substitute resin molding is not particularly limited, and may be a square, a rectangle, a sphere, a cylinder, a cone, or the like, but a heart, a lung, a pancreas, a spleen, a gallbladder, a liver, It may be formed into a shape such as kidney, esophagus, stomach, duodenum, small intestine, large intestine, and bladder.

  As the surgical instrument, an endoscope that exfoliates and removes the submucosal layer while observing with an endoscope when the diseased tissue remains in the inner mucosa, such as early colorectal cancer, gastric cancer, and colorectal polyp In addition to high-frequency scalpels and high-frequency snares for endoscopic surgical instruments used for surgical mucosal resection, catheter ablation using a catheter (generally called “ablation catheter”) as a method for treating tachyarrhythmia Examples of the device used include a long and flexible catheter shaft that is inserted into a thick blood vessel (for example, a femoral artery or a femoral vein) at the base of the foot, and its tip reaches the heart. Next, an electrocardiogram is measured while the electrode at the tip of the catheter shaft is in contact with the inner wall of the heart to search for an abnormal site. When an abnormal site is found, a high-frequency (RF wave) current is generated from the electrode at the tip of the catheter shaft, the myocardium in the deep part is cauterized, and the cells at the site (lesion) causing the arrhythmia are necrotized.

An ablation catheter evaluation instrument used for evaluating ablation using an ablation catheter using the organ substitute resin molding will be described (see FIG. 5).
The ablation catheter evaluation instrument is an instrument for evaluating ablation using an ablation catheter, and contains a counter electrode and a liquid disposed on the counter electrode and used for evaluating the ablation, It consists of a container made of a conductive resin, and an organ substitute resin molding as a sample for evaluating cauterization is placed in the container. In this case, the organ substitute resin molding includes a conductive material.
The evaluation instrument for ablation catheter can grasp the temperature at the time of cauterization at a glance and can easily obtain a container. Therefore, it becomes possible to easily evaluate the ablation using the ablation catheter, and to easily manufacture the ablation catheter evaluation instrument.
In the ablation catheter evaluation instrument, since the organ substitute resin molding for evaluating ablation using an ablation catheter contains a thermosensitive color-changing color memory microcapsule pigment and a conductive material, the temperature during ablation (organ substitute) A dedicated element (such as a thermocouple temperature sensor) is not required to measure the temperature of the resin molding, and the temperature during cauterization can be grasped at a glance according to the discoloration of the organ substitute resin molding ( Can be visually recognized). In addition, since the container for storing the liquid used when evaluating shochu is composed of a conductive resin, the container can be simplified as compared with, for example, a container obtained using a special material or manufacturing method. Be able to get.
In the ablation catheter evaluation instrument, it is desirable that a recess for inserting and arranging the organ substitute resin molding is formed on the bottom surface of the container, and the recess is not penetrated to the counter electrode plate. In such a case, the organ substitute resin molded product is cauterized while being inserted and disposed in the recess, thereby preventing occurrence of a short circuit current during cauterization regardless of the concentration of the liquid contained in the container. As a result, the evaluation accuracy of shochu (measurement accuracy during evaluation) is improved. In addition, since this recess is not penetrating to the counter electrode plate, a container is interposed between the ablation object inserted and disposed in the recess and the counter electrode plate, so that the environment is closer to the actual treatment (more accurate). The impedance value in an environment simulating a human body can be obtained. As a result, for example, compared with the case where the dent penetrates to the counter electrode plate (when the through hole is formed instead of the dent), cauterization in an environment closer to the actual treatment is realized. The evaluation accuracy can be improved.
In this case, it is desirable for the recess to have a non-tapered sidewall. In this case, for example, when using an organ substitute resin molding having water absorption, the recess has a tapered side wall (a tapered side wall whose diameter gradually decreases toward the counter electrode). Unlike the case: That is, the possibility that the organ substitute resin molded product will jump out of the recess due to the liquid absorbing and swelling is reduced or avoided. As a result, convenience in evaluating shochu is improved.
In the ablation catheter evaluation instrument, it is desirable to further provide an inflow mechanism for allowing the liquid to flow into the container using a pump. In this case, the liquid will flow in the container, so cauterization can be achieved in an environment that is closer to the actual treatment (environment where the blood is flowing) (an environment that more accurately simulates the human body). As a result, the evaluation accuracy can be further improved.
In this case, it is desirable to further provide a discharge mechanism for discharging the liquid contained in the container to the outside. In this case, the risk of the liquid leaking out of the container due to the inflow of the liquid by the inflow mechanism is avoided, and the liquid flow in the container is more effective by discharging the liquid. Will be made. Therefore, convenience in evaluation is improved, and cauterization in an environment that simulates a human body is realized more accurately. As a result, evaluation accuracy is further improved.
In the ablation catheter evaluation instrument, it is desirable that the impedance of the container is substantially equal to the impedance of the organ substitute resin molding. In this case, cauterization in an environment closer to that during actual treatment can be realized, and the evaluation accuracy can be further improved.
Examples of the liquid include physiological saline, low-concentration saline, blood, and the like.
Further, the container of the ablation catheter evaluation instrument may have a through-hole penetrating to the counter electrode while inserting an organ substitute resin molded product for evaluating ablation, such as the concentration of liquid contained in the container. Regardless, the occurrence of short circuit current during cauterization is prevented. In the evaluation instrument for an ablation catheter, it is desirable that the through hole has a tapered side wall whose diameter gradually decreases toward the counter electrode. In this case, the liquid in the container may be more reliably prevented from leaking to the counter electrode side through the through-hole (gap between the organ substitute resin molding and the side wall) ( The water-stopping property against the liquid in the container is improved). Therefore, as a result of avoiding the occurrence of a short-circuit current due to such liquid leakage, the evaluation accuracy can be further improved.

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) 3 ', 6'-bis [phenyl (3-methylphenyl) amino] -spiro [isobenzofuran-1 (3H), 9'-[ 9H] xanthen] -3-one, 2.0 parts as component (b), 3.0 parts of 4,4 '-(2-ethylhexane-1,1-diyl) diphenol, 2,2-bis (4' -Hydroxyphenyl) -hexafluoropropane 5.0 parts, and (c) a temperature-sensitive color-changing color memory composition comprising 50.0 parts of 4-benzyloxyphenylethyl caprate as a component is dissolved by heating. A solution prepared by mixing 30.0 parts of an aromatic isocyanate prepolymer and 40.0 parts of a co-solvent was emulsified and dispersed in an aqueous 8% polyvinyl alcohol solution, and stirred while heating. 2.5 parts of min was added and 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 microcapsule pigment is 2.2 μm, and the hysteresis characteristics are t ₁ : −20 ° C., t ₂ : −10 ° C., t ₃ : 46 ° C., t ₄ : 56 ° C., ΔH: 66 ° C. The color changed reversibly from blue to colorless and from colorless to blue.

Preparation of organ substitute resin molding (see Figs. 3 and 4)
30 parts of the temperature-sensitive color-changing color memory microcapsule pigment A previously cooled to −20 ° C. or less to blue, 100 parts of polyvinyl alcohol (polymerization degree 1800, saponification degree 87.0-89.0), cetylpyridinium chloride 0.5 part and 400 parts of water were mixed and stirred while heating to obtain a mixed solution.
The mixed solution was put in a container, irradiated with an electron beam using an electron beam irradiation apparatus, and polyvinyl alcohol was crosslinked to obtain a cylindrical organ substitute resin molded product.
In the organ substitute resin molded product, a blue color due to the thermochromic color-memory microcapsule pigment is visually recognized at room temperature (25 ° C.), and the state is maintained in the room temperature range (FIG. 3).
Next, when catheter ablation is applied to the organ substitute resin molded product and heated to 60 ° C., the thermosensitive color-changing color memory microcapsule pigment is decolored and the ablation site becomes translucent. Since it was maintained and the ablation site was clearly visible, it could be used for a simulation in a medical practice of cauterizing an organ (FIG. 4).
When the organ substitute resin molded product having a translucent ablation site was cooled to −20 ° C. or lower, the temperature-sensitive color-changing color memory microcapsule pigment developed a blue color again and could be used repeatedly.

Example 2
Preparation of thermosensitive color-changing color memory microcapsule pigment B (I) 2- (dibutylamino) -8- (dipentylamino) -4-methyl-spiro [5H- [1] benzopyrano [2,3-g as component (a) ] Pyrimidine-5,1 '(3'H) -isobenzofuran] -3-one 1.0 part, (4) 4'-(2-ethylhexane-1,1-diyl) diphenol 3 as component (b) 0.02 parts, 2,2-bis (4'-hydroxyphenyl) -hexafluoropropane 5.0 parts, and (c) thermosensitive color-changing color comprising 50.0 parts of 4-benzyloxyphenylethyl caprate as component (c) A memory composition is heated and dissolved, and a solution prepared by mixing 30.0 parts of an aromatic isocyanate prepolymer and 40.0 parts of a cosolvent as a wall film material is emulsified and dispersed in an aqueous 8% polyvinyl alcohol solution, and heated. Na After continuing the stirring, 2.5 parts of a water-soluble aliphatic modified amine was added, and stirring was further continued to obtain a microcapsule suspension. The suspension was centrifuged to isolate a thermochromic color memory microcapsule pigment.
The average particle diameter of the microcapsule pigment is 2.3 μm, and hysteresis characteristics of 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 organ substitute resin molding 30 parts of the temperature-sensitive color-changing color-memory microcapsule pigment previously cooled to -20 ° C. or less, and polyvinyl alcohol (polymerization degree 1800, saponification degree 87.0-89. 0) 100 parts, cetylpyridinium chloride 0.5 part and 400 parts of water were mixed and stirred while heating to obtain a mixed solution.
The mixed solution was put in a container, irradiated with an electron beam using an electron beam irradiation apparatus, and polyvinyl alcohol was cross-linked to obtain an organ substitute resin molded product having a heart shape.
In the organ substitute resin molded product, a pink color due to the temperature-sensitive color-changing color-memory microcapsule pigment is visually recognized at room temperature (25 ° C.), and the state is maintained in the room temperature range.
Next, when catheter ablation is applied to the organ substitute resin molded product and heated to 60 ° C., the thermosensitive color-changing color memory microcapsule pigment is decolored and the ablation site becomes translucent. Since it was maintained and the ablation site was clearly visible, it could be used for simulation in medical practice of cauterizing the organ.
When the organ substitute resin molded article having a translucent ablation site was cooled to −20 ° C. or lower, the temperature-sensitive color-changing color memory microcapsule pigment was colored again to become pink and could be used repeatedly.

Example 3
Preparation of thermosensitive color-change color memory microcapsule pigment C (a) 9-ethyl (3-methylbutyl) amino-spiro [12H-benzo (a) xanthene-12,1 '(3'H) isobenzofuran] as component -3'-one 2.0 parts, (b) Component 1,5-bis (4-hydroxyphenyl) n-decane 5.0 parts, 2,2-bis (4'-hydroxyphenyl) -hexafluoro A temperature-sensitive color-changing color memory composition composed of 5.0 parts of propane and 50.0 parts of 4-methylbenzyl palmitate as the component (c) is dissolved by heating, and an aromatic isocyanate prepolymer 35.0 is used as a wall film material. Part of the solution and 40.0 parts of the co-solvent were emulsified and dispersed in an 8% aqueous polyvinyl alcohol solution, and the mixture was stirred while warming. Then, 2.5 parts of a water-soluble aliphatic modified amine was added and further stirred. Stirring was continued to obtain a microcapsule suspension. The suspension was centrifuged to isolate a thermochromic color memory microcapsule pigment.
The microcapsule pigment has an average particle size of 2.4 μm, and has hysteresis characteristics of t ₁ : −3 ° C., t ₂ : 5 ° C., t ₃ : 37 ° C., t ₄ : 43 ° C., ΔH: 39 ° C. The color changed reversibly from pink to colorless and from colorless to pink.

Preparation of organ-replacement resin molded product The temperature-sensitive color-changing color-memory microcapsule pigment C 20 parts previously cooled to −3 ° C. or lower to be pink, polyvinyl alcohol (polymerization degree 1800, saponification degree 87.0-89. 0) 100 parts, cetylpyridinium chloride 0.5 part and 400 parts of water were mixed and stirred while heating to obtain a mixed solution.
The mixed solution was put into a container, irradiated with an electron beam using an electron beam irradiation device, and polyvinyl alcohol was crosslinked to obtain a square organ substitute resin molded product.
In the organ substitute resin molded product, a pink color due to the temperature-sensitive color-changing color-memory microcapsule pigment is visually recognized at room temperature (25 ° C.), and the state is maintained in the room temperature range.
Next, when catheter ablation is applied to the organ substitute resin molded product and heated to 60 ° C., the thermosensitive color-changing color memory microcapsule pigment is decolored and the ablation site becomes translucent. Since it was maintained and the ablation site was clearly visible, it could be used for simulation in medical practice of cauterizing the organ.
When the organ substitute resin molded article having a translucent ablation site was cooled to −3 ° C. or lower, the temperature-sensitive color-changing color-memory microcapsule pigment was colored again to become pink and could be used repeatedly.

Example 4
Preparation of organ-replacement resin molded article Temperature-sensitive color-changing color-memory microcapsule pigment A 20 parts previously cooled to -20 ° C. or lower, blue, temperature-sensitive color change previously cooled to −3 ° C. or lower to pink While mixing color warming microcapsule pigment C20 parts, polyvinyl alcohol (polymerization degree 1800, saponification degree 87.0-89.0) 100 parts, cetylpyridinium chloride 0.5 parts, water 400 parts while heating The mixture was obtained by stirring.
The mixed solution was put in a container, irradiated with an electron beam using an electron beam irradiation apparatus, and polyvinyl alcohol was crosslinked to obtain a cylindrical organ substitute resin molded product.
In the organ substitute resin molded product, a purple color in which blue and pink colors are mixed by the temperature-sensitive color-changing color memory microcapsule pigment is visually recognized at normal temperature (25 ° C.), and the state is maintained in the normal temperature range.
Next, when catheter ablation is applied to the organ substitute resin molding and heated to 50 ° C., the thermosensitive color-changing color memory microcapsule pigment C is discolored and the ablation site becomes blue, and further, the organ substitute resin When catheter ablation is applied to the molded article and heated to 60 ° C., the temperature-sensitive color-changing color memory microcapsule pigment A is decolored and the ablation site becomes translucent, and the state is maintained in the normal temperature range and Since the heat transfer condition of the ablation site changes color stepwise and is clearly visible, it can be used for highly accurate simulation in the medical practice of cauterizing the organ.
When the organ substitute resin molded product having a translucent ablation site was cooled to −20 ° C. or lower, the temperature-sensitive color-changing color memory microcapsule pigment was colored again to become purple and could be 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- Yl) furo [3,4-b] pyridin-5 (7H) -one 1 part, (ro) component 2,2-bis (4'-hydroxyphenyl) hexafluoropropane 5.0 part, (c) component As a wall film material, 35.0 parts of an aromatic isocyanate prepolymer was prepared by heating and dissolving a temperature-sensitive color-changing color memory composition comprising 50 parts of a diester of pimelic acid and 2- (4-benzyloxyphenyl) ethanol as The solution in which 40.0 parts of the co-solvent was mixed was emulsified and dispersed in an 8% aqueous polyvinyl alcohol solution. After stirring while heating, 2.5 parts of a water-soluble aliphatic modified amine was added and further stirred. To obtain a microcapsule suspension. The suspension was centrifuged to isolate a thermochromic color memory microcapsule pigment.
The average particle diameter of the microcapsule pigment is 2.5 μm, and has hysteresis characteristics of t ₁ : −10 ° C., t ₂ : 1 ° C., t ₃ : 70 ° C., t ₄ : 79 ° C., ΔH: 79 ° C. The color changed reversibly from blue to colorless and from colorless to blue.

Preparation of resin substitute for organ substitute Mixing 30 parts of the above thermosensitive color-changing color memory microcapsule pigment D, 100 parts of polysiloxane, and 1 part of cross-linking agent, which were cooled to -10 ° C. or less in advance and heated with a press. A plate-shaped organ substitute resin molding was obtained by pressing.
In the organ substitute resin molded product, a blue color due to the temperature-sensitive color-changing color memory microcapsule pigment is visually recognized 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 molding and heated to 100 ° C., the thermosensitive color-changing color memory microcapsule pigment is decolored and the ablation site becomes translucent, and its state is in the normal temperature range. Since it was maintained and the ablation site was clearly visible, it could be used for simulation in medical practice of cauterizing the organ.
When the organ substitute resin molded product having a translucent ablation site was cooled to −10 ° C. or lower, the temperature-sensitive color-changing color-memory microcapsule pigment developed a blue color again and could be used repeatedly.

Example 6
Preparation of thermochromic color memory microcapsule pigment E (a) As component 7,7-bis [4- (diethylamino) -2-ethoxyphenyl] furo [3,4-b] pyridine-5 (7H)- 2.0 parts of on, 3.0 parts of 4,4 ′-(2-ethylhexane-1,1-diyl) diphenol as component (b), 2,2-bis (4′-hydroxyphenyl) -hexafluoro Propane 5.0 parts, (c) as a component, heat-dissolving a temperature-sensitive color-change color memory composition comprising 50.0 parts of a diester of 1,3-bis (2-hydroxyethoxy) benzene and caprylic acid, A solution prepared by mixing 30.0 parts of an aromatic isocyanate prepolymer and 40.0 parts of a co-solvent as a wall film material is emulsified and dispersed in an 8% aqueous polyvinyl alcohol solution. Degeneration 2.5 parts of amine was added and 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 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 organ substitute resin molded product The temperature-sensitive color-changing color memory microcapsule pigment A 30 parts previously cooled to -16 ° C. or less to blue-green, polyvinyl alcohol (polymerization degree 1800, saponification degree 87.0-89. 0) 100 parts, cetylpyridinium chloride 0.5 part and 400 parts of water were mixed and stirred while heating to obtain a mixed solution.
The mixed solution was put in a container, irradiated with an electron beam using an electron beam irradiation apparatus, and polyvinyl alcohol was crosslinked to obtain a cylindrical organ substitute resin molded product.
In the organ substitute resin molded product, blue-green color due to the thermochromic color-memory microcapsule pigment is visually recognized at room temperature (25 ° C.), and the state is maintained in the room temperature range.
Next, when catheter ablation is applied to the organ substitute resin molded product and heated to 55 ° C., the thermosensitive color-changing color memory microcapsule pigment is discolored and the ablation site becomes translucent. Since it was maintained and the ablation site was clearly visible, it could be used for simulation in medical practice of cauterizing the organ.
When the organ substitute resin molded product having a translucent translucent part was cooled to -16 ° C. or lower, the temperature-sensitive color-changing color memory microcapsule pigment developed a blue-green color again and could be used repeatedly.

Example 7
Preparation of thermosensitive color-changing color memory microcapsule pigment F (a) 3 ', 6'-bis [phenyl (3-methylphenyl) amino] -spiro [isobenzofuran-1 (3H), 9'-[ 9H] Xanthen] -3-one 2.0 parts, (ro) 8.0 parts of myristyl hydroxybenzoate as component, and (c) 20.0 parts of hexadecane as component (c) Thermochromic color change color memory property The composition was dissolved by heating, and a solution prepared by mixing 30.0 parts of an aromatic isocyanate prepolymer and 40.0 parts of a co-solvent as a wall film material was emulsified and dispersed in an 8% aqueous polyvinyl alcohol solution and stirred while heating. Then, 2.5 parts of a water-soluble aliphatic modified amine was added, and stirring was continued to obtain a microcapsule suspension. The suspension was centrifuged to isolate a thermochromic color memory microcapsule pigment.
The microcapsule pigment has an average particle size of 2.2 μm, starts to develop color at 28 ° C. or higher (t ′ ₃ ), completely develops blue color at 45 ° C. or higher (t ′ ₄ ), and below 0 ° C. A behavior of starting to disappear (t ′ ₂ ) was exhibited, and the color changed reversibly from blue to colorless and from colorless to blue.

Preparation of organ substitute resin molding 30 parts of temperature-sensitive color-changing color memory microcapsule pigment A previously made colorless, 100 parts of polyvinyl alcohol (polymerization degree 1800, saponification degree 87.0-89.0), cetylpyridinium chloride 0 .5 parts and 400 parts of water were mixed and stirred while heating to obtain a mixed solution.
The mixed solution was put in a container, irradiated with an electron beam using an electron beam irradiation apparatus, and polyvinyl alcohol was crosslinked to obtain a cylindrical organ substitute resin molded product.
The organ-replacement resin molded product is visually recognized as being translucent at normal temperature (25 ° C.), and this state is maintained in the normal temperature range.
Next, when catheter ablation is applied to the organ substitute resin molding and heated to 50 ° C., the thermosensitive color-changing color memory microcapsule pigment develops a color and the ablation site becomes blue, and the state is maintained in the normal temperature range. In addition, since the ablation site can be clearly seen, it can be used for a simulation in a medical practice of cauterizing an organ.
When the organ substitute resin molded product having a blue ablation site was cooled to 0 ° C. or lower, it began to decolor, and kept translucent at room temperature and could be used repeatedly.

DESCRIPTION OF SYMBOLS 1 Organ substitute resin molding 1B Evaluation instrument 11 Container 110 Indentation 12 Counter electrode 13 Ablation object 14 Inflow path 15 Pump 16 Discharge path (discharge mechanism)
2 Liquid 3 Ablation catheter 30 Catheter tube 31 Ring electrode 32 Tip electrode I1, I2 ... Current Is Short-circuit current S1 Bottom S2 Side (side wall)
Lin, Lout liquid t ₁ Full color development temperature of microcapsule pigment encapsulating thermochromic color memory composition of heat decoloring type t ₂ Micro encapsulating thermochromic color memory composition of heat decoloring type the color development initiation temperature t ₃ heating decolorizable the thermochromic coloring color-memory composition decolorization initiation temperature of a microcapsule pigment enclosing t ₄ heating decolorizable the thermochromic coloring color-memory composition of the capsule pigment Complete discoloration temperature of the encapsulated microcapsule pigment t ′ ₁ Heat-development type thermosensitive color-changing color memory composition Completely decoloration temperature of the microcapsule pigment encapsulating the heat-development type t ′ ₂ Heat-development type thermosensitive color-change color memory Decoloration Start Temperature of Microcapsule Pigment Encapsulating Coloring Composition t ′ ₃ Heating Color Change Type Temperature Sensitive Color Change Start Temperature of Microcapsule Pigment Encapsulating Color Memory Composition t ′ ₄ Temperature Color Change of Heating Color Type Contains sexual color memory composition Development temperature of the microcapsule pigments

Claims (16)

(B) an electron-donating color-forming organic compound, (b) an electron-accepting compound, and (c) a reaction medium that reversibly causes an electron-donating reaction by the components (a) and (b) above in a specific temperature range. The temperature-sensitive color-change color memory composition is contained, exhibits a large hysteresis characteristic with respect to the color density-temperature curve, exhibits tautomerism between the first hue and the second hue, and rises in temperature in the first hue. In the process, when the temperature reaches t ₃ , the first hue starts to change color, completely becomes the second hue in the temperature range higher than the temperature t _{3 and} is equal to or higher than the temperature t ₄ , and the temperature drops in the second hue state. in reaches the temperature t _2, the second color begins to discolor, become completely the first color at a lower temperature t ₁ the following temperature range than the temperature t _2, the temperature range between the temperature t ₂ and the temperature t ₃ Shows the hysteresis characteristics that hold the first hue or the second hue, and the temperature The molded product contains a temperature-sensitive color-changing color memory microcapsule pigment in which t ₂ is a temperature lower than normal temperature, temperature t ₄ is higher than normal temperature, and lower than the cauterization temperature for the organ. Organ substitute resin molding for confirming cauterization with surgical instruments. The temperature t ₄ organ substitutes resin molded article according to claim 1, wherein a temperature above body temperature. The temperature t ₂ is at a temperature below 5 ° C., according to claim 1 or 2 organ substitutes resin molded product at the temperature t ₄ is a temperature above 40 ° C.. The temperature t ₄ organ substitutes resin molded product according to any one of claims 1 to 3 at a temperature of 50 to 100 ° C.. It said temperature t ₁ is the organ substitute resin molded product according to any one of claims 1 to 4 at a temperature of -50 to 0 ° C.. Organ substitute resin molded product according to any one of claims 1 to 5 temperature t ₄ is comprising a plurality of different thermochromic coloring color-memory composition during molding.   The organ-replacement resin molded product according to any one of claims 1 to 6, simulating the shape of an organ.   The organ substitute resin molded product according to any one of claims 1 to 7, comprising a conductive material.   An instrument for evaluating ablation using an ablation catheter, comprising a counter electrode plate and a liquid disposed on the counter electrode plate and used for evaluating the ablation and made of a conductive resin An ablation catheter evaluation instrument comprising: a container; and the organ substitute resin molded product according to claim 8 as a sample for evaluating the ablation disposed in the container.   The ablation catheter evaluation instrument according to claim 9, wherein a depression for inserting and arranging the organ substitute resin molding is formed on a bottom surface of the container, and the depression is not penetrated to the counter electrode plate. .   The ablation catheter evaluation instrument according to claim 10, wherein the recess has a non-tapered side wall.   The ablation catheter evaluation instrument according to claim 9, wherein the container has a through-hole penetrating to the counter electrode plate while inserting an organ substitute resin molding for evaluating the ablation.   The ablation catheter evaluation instrument according to claim 13, wherein the through hole has a tapered side wall whose diameter gradually decreases toward the counter electrode.   The ablation catheter evaluation instrument according to any one of claims 9 to 13, further comprising an inflow mechanism for allowing the liquid to flow into the container using a pump.   The ablation catheter evaluation instrument according to claim 14, further comprising a discharge mechanism for discharging the liquid contained in the container to the outside.   The ablation catheter evaluation instrument according to any one of claims 9 to 15, wherein an impedance of the container is substantially equal to an impedance of the organ substitute resin molding.

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