JP2009251440A - Reversible thermochromic display body - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a reversible thermochromic display body of high practicability capable of providing a plurality of content information by giving machine-decipherable codes on content information from each pattern changed according to a change of temperature. <P>SOLUTION: The reversible thermochromic display body is formed with the coexistence, on a support body, of a heat-colored thermochromic image containing a reversible thermochromic material colored by heating from a decolored state and decolored by a temperature drop from a colored state, and a heat-decolored thermochromic image containing a reversible thermochromic material decolored by heating from a colored state and colored by cooling from a decolored state. The heat-colored thermochromic image and the heat-decolored thermochromic image are given codes for different content information that can be deciphered by a machine having a reading function. <P>COPYRIGHT: (C)2010,JPO&INPIT

Description

  The present invention relates to a reversible thermochromic display. More specifically, the present invention relates to a reversible thermochromic display that coexists with a heat-colorable thermochromic image and a heat-erasable thermochromic image to which a code related to machine-readable content information is added.

Conventionally, a heat decoloring type thermochromic material, that is, a reversible thermochromic material that is decolored by heating from a colored state and a color is developed by cooling from the decolored state, and a heat decoloring type thermochromic material, that is, A display body is disclosed that combines a reversible thermochromic material that develops color by heating from a decolored state and decolorizes by lowering the temperature from the developed state.
However, although the display body has unexpectedness, a fascinating color change, a magic property, etc., it does not provide useful content information to the user.
JP 2000-194295 A

  The present invention can provide a plurality of types of content information by assigning a machine-readable code relating to content information to a design that has unexpectedness, a sensation of change, and a magic property, and that changes with temperature. The display body is to be provided.

The present invention relates to a heat-developable thermochromic image containing a reversible thermochromic material that develops color by heating from the decolored state and decolorizes by lowering the temperature from the developed state, and decolored by decoloring by heating from the developed state. A heat-decolorable thermochromic image containing a reversible thermochromic material that develops color by cooling from the state coexists on the support, and the heat-colorable thermochromic image and the heat-erasable thermochromic image include A reversible thermochromic display body provided with codes for different content information that can be read by a machine having a reading function is required.
Further, the heat-colorable thermochromic image and the heat-erasable thermochromic image are arranged in parallel or overprinted, and at 25 ° C., the heat-colorable thermochromic image is in a decolored state, The color-erasable thermochromic image is in a colored state, and at 25 ° C, the heat-colored thermochromic image and the heat-erasable thermochromic image are in a color-erased state. It is in a colored state, and the heat decoloring type thermochromic image is in a decoloring state, the content information includes URL information of the content providing server, identification information for identifying the content in the content providing server, and identification information for identifying the network It must be one of the attribute information.

  The reversible thermochromic display of the present invention has unexpectedness, the sensation of change, and magic, and gives a machine-readable code related to content information from each design that changes according to temperature change. Therefore, it is possible to provide a practical reversible thermochromic display that can provide a plurality of pieces of content information.

  Examples of the reversible thermochromic material that is decolored by heating from the colored state and develops color by cooling from the decolored state include (a) an electron-donating color-forming organic compound, (b) an electron-accepting compound, And (c) a material in which a reversible thermochromic composition containing three components of a reaction medium for determining the temperature at which the color reaction of both occurs is contained in a microcapsule is effective. Nos. 44706, 51-44708, 1-29398, 4-17154, etc. can be used.

  Examples of the (a) electron donating color-forming organic compound include known diphenylmethane phthalides, phenyl indolyl phthalides, indolyl phthalides, diphenyl methane azaphthalides, phenyl indolyl azaphthalides, fluorans , Stylinoquinolines, diazarhodamine lactones and the like can be applied.

The (b) electron-accepting compound includes a group of compounds having active protons, a group of pseudo-acidic compounds [a group of compounds that are not acids but act as acids in the composition to develop component (A)], electron vacancy There are compounds having pores and the like, and in particular, compounds having 2 or 3 aromatic rings are used.
As the compound, a compound having a phenolic hydroxyl group is preferable, and further a substituent having an alkyl group, an aryl group, an acyl group, an alkoxycarbonyl group, a carboxy group and its ester or amide group, a halogen group, and the like, and a bis type, A tris type phenol etc., phenol-aldehyde condensation resin, etc. are mentioned. Moreover, the metal salt of the compound which has the said phenolic hydroxyl group may be sufficient.

  (C) Examples of the reaction medium for determining the occurrence temperature of the color reaction of the two include alcohols, esters, ketones, ethers, and acid amides.

As the reversible thermochromic material that develops color by heating from the decolored state and decolorizes by lowering the temperature from the developed state, (i) an electron-donating color-forming organic compound, (b) a specific electron-accepting compound, And (c) a material in which a reversible thermochromic composition containing three components of a reaction medium that determines the temperature at which the color reaction of both occurs is contained in a microcapsule is effective. Specifically, an electron-accepting compound Specific alkoxyphenol compounds having a linear or side chain alkyl group having 3 to 18 carbon atoms (Japanese Patent Laid-Open No. 11-129623), hydroxybenzoic acid esters (Japanese Patent Laid-Open No. 2001-105732), gallic acid esters (special A heat-developable reversible thermochromic material using Japanese Unexamined Patent Publication No. 2003-253149 can be applied.
In the system using the hydroxybenzoic acid ester, a crystallization accelerator can be added as necessary, and the color can be quickly erased without applying a special cooling means after coloring by heating.

The microencapsulation of reversible thermochromic composition includes interfacial polymerization method, in situ polymerization method, liquid curing coating method, phase separation method from aqueous solution, phase separation method from organic solvent, melt dispersion cooling method, air suspension. A turbid coating method, a spray drying method, or the like is appropriately selected. Furthermore, a secondary resin film can be provided on the surface of the microcapsule according to the purpose to impart durability, or the surface characteristics can be modified for practical use.
The microencapsulation does not lower the function even when it comes into contact with a chemically active substance such as an acidic substance, a basic substance, or a peroxide or a solvent component. This is because the reversible thermochromic composition can be maintained in the same composition under the various use conditions and can exhibit the same effects.
A microcapsule having a particle size of 1 to 50 μm, preferably about 3 to 30 μm, is effective in terms of dispersibility, color development, endurance, and processability.

The heat-developable thermochromic image and the heat-decolorable thermochromic image in the present invention are a reversible thermochromic material that is decolored by heating from the above-described color-development state and develops color by cooling from the decolorization state, and a decolorization state Is a thermochromic image in which a reversible thermochromic material that develops color by heating from and then discolors by cooling from the colored state is fixed in a dispersed state in a binder resin, and is applied to a support by printing or spraying. It is formed by.
The thermochromic image is obtained by dispersing a reversible thermochromic material in a vehicle containing a binder resin, for example, various synthetic resin emulsions, water-soluble or oily synthetic resins, ultraviolet curable resins, and other adhesives. As a printing ink or paint, it is obtained by adhering and drying on a desired portion of the support by printing means such as screen printing, gravure printing, or spray coating.

The material of the support is not particularly limited as long as it has water resistance, and examples thereof include synthetic paper, fabric, film, plastic, rubber, synthetic leather, leather, glass, ceramics, wood, and stone.
The support is preferably in the form of a plane, but may be in the form of irregularities.

In the present invention, in a display system in which a heat-developable thermochromic image is in a decolored state at 25 ° C., the heat-decolorable thermochromic image is in a colored state. Is configured such that the color disappears and a heat-colored thermochromic image develops color.
In a system in which both the heat-colorable thermochromic image and the heat-erasable thermochromic image are decolored at 25 ° C., the heat-colorable thermochromic image is colored by heating, and the heat-erasable heat-dissipating heat is cooled. Examples include a configuration in which a discolored image is developed.
Further, in a display system in which a heat-erasable thermochromic image shows a decolored state at 45 ° C., the heat-colorable thermochromic image is in a colored state, and the heat-colorable thermochromic image is erased by cooling. And a configuration in which a heat-erasable thermochromic image develops color.

A printed matter such as a magazine or catalog contains a two-dimensional barcode (for example, a QR code) in which URL information of a Web site that presents detailed product information to the user is converted into encoded data. Reads a two-dimensional barcode with a machine equipped with a reading device such as a camera-equipped mobile phone, and sends it to a server by a communication function to obtain various contents information.
The content information includes characters, numbers, symbols, and the like, and includes URL information of the content providing server, identification information for specifying the content in the content providing server, identification information for specifying the network, attribute information, and the like.
The heating color-changing thermochromic image and the heating decoloring thermochromic image are images (designs) in which desired information is encoded, and it is possible to provide content information that can be read by a machine and guided to a content distribution site. And
The heating color-changing thermochromic image and the heating decoloring thermochromic image are each read by a machine equipped with a reading device, and can be read by the reading machine via a machine or a server connected via a network. A code is decoded and reproduced as content information from the decoding result.

Examples are shown below. In addition, the part in an Example shows a mass part.
Example 1
Preparation of heat-developable reversible thermochromic material 6 '-[Ethyl (4-methylphenyl) amino] -2'-(methylphenylamino) -spiro [isobenzofuran-1 (3H), 9 '-(9H) xanthene ] 3-one 4.5 parts, 8 parts dodecyl gallate, 12.5 parts cetyl caprate, 12.5 parts myristyl alcohol, 1 part behenyl behenate, 2- (3-t-butyl-5-methyl- Heat-colorable reversible thermochromic composition comprising 3 parts of 2-hydroxyphenyl) -5-chlorobenzotriazole encapsulates isocyanate resin as a wall film material to obtain a heat-colorable reversible thermochromic material in the form of a microcapsule It was.
The reversible thermochromic material exhibits a heat-developing color-changing behavior, is in a decolored state (colorless) at room temperature, begins to develop color at 34 ° C. (T ₃ ) when heated, and develops a green color at 43 ° C. Then (T ₄ ), when cooled, the color starts to be erased at 36 ° C. (T ₂ ), and is completely erased at 24 ° C. (T ₁ ).

Preparation of heat decolorable reversible thermochromic material 3- [2-Ethoxy-4- (N-ethylanilino) phenyl] -3- (1-ethyl-2-methylindol-3-yl) -4-azaphthalide 5 parts, 4,4 '-(2-methyl-propylidene) bisphenol 6 parts, 2- (3-tert-butyl-5-methyl-2-hydroxyphenyl) -5-chlorobenzotriazole 1 part, cetyl alcohol 25 parts Then, a heat decoloring type reversible thermochromic composition comprising 25 parts of stearyl caprate was encapsulated as a wall film material with an epoxy resin / amine curing agent to obtain a heat decoloring type reversible thermochromic material in the form of a microcapsule.
The reversible thermochromic material exhibits a decoloring behavior of a heat decoloring type, is in a colored state (blue) at room temperature, starts decoloring at 30 ° C. (t ₃ ) when heated, and completely disappears at 33 ° C. or higher. It becomes a colored (colorless) state (t ₄ ), and then starts to develop color at 30 ° C. (t ₂ ) upon cooling, and completely develops at 27 ° C. (t ₁ ).

Preparation of ink 15 parts of the heat-colorable reversible thermochromic material, 15 parts of vinyl chloride-vinyl acetate copolymer resin, 2 parts of UV absorber, 35 parts of cyclohexanone, 35 parts of high boiling aromatic solvent, 1 part of antifoaming agent Was dispersed in a vehicle containing a heat-colorable oily screen ink.
15 parts of the heat decoloring type reversible thermochromic material contains 15 parts of vinyl chloride-vinyl acetate copolymer resin, 2 parts of UV absorber, 35 parts of cyclohexanone, 35 parts of high boiling aromatic solvent, and 1 part of antifoaming agent. Dispersed in the vehicle to obtain a heat-erasable oil-based screen ink.

Production of reversible thermochromic display body A heat-colored thermochromic image provided with a code for content information by screen printing is provided on white synthetic paper using the heat-colorable oil-based screen ink, and the heat decoloring is further performed. A reversible thermochromic display (reversible thermochromic display) is prepared by providing a heat-erasable thermochromic image with a code for another content information on the heat-colorable thermochromic image by screen printing using a mold oil-based screen ink. Printable material).

In the reversible thermochromic display, only a blue heat-erasable thermochromic image is visible at room temperature (25 ° C.).
The heat-erasable thermochromic image is imaged with a camera-equipped mobile phone as a machine having a reading function, code information is read, and the read code information is decoded. The mobile phone transmits the decode information to the server, uses the content information returned from the server, accesses the content server, and displays and browses a Web page that provides content data corresponding to the photographed code information.
Next, when the reversible thermochromic display is heated to 43 ° C. or higher, the heat-erasable thermochromic image is erased and a green heat-colorable thermochromic image appears.
The heat coloring color change image is picked up by a camera-equipped mobile phone to read the code information, and the read code information is decoded. The mobile phone transmits decode information to the server, uses the content information returned from the server, accesses the content server, and displays content data corresponding to the photographed code information. browse.
The state returned to its original state when left at room temperature, and could be reproduced repeatedly due to temperature changes.

Example 2
Preparation of heat-developing reversible thermochromic material 2- (dibutylamino) -8- (dipentylamino) -4-methyl-spiro [5H]-[1] benzopyrano [2,3-g] pyrimidine-5,1 ′ (3H) -isobenzofuran] -3-one 1 part, 8 parts dodecyl gallate, 12.5 parts stearyl laurate, 12.5 parts lauryl alcohol, 2- (3-tert-butyl-5-methyl-2- A heat-colorable reversible thermochromic composition comprising 3 parts of hydroxyphenyl) -5-chlorobenzotriazole was encapsulated with an isocyanate resin as a wall film material to obtain a heat-colorable reversible thermochromic material in the form of a microcapsule.
The reversible thermochromic material exhibits a heat-developing color change behavior, is in a decolored state (colorless) at room temperature, begins to develop color at 28 ° C. (T ₃ ), and develops a pink color at 43 ° C. When it is cooled (T ₄ ) and then cooled, it begins to lose its color at 32 ° C. (T ₂ ), and at 24 ° C. it becomes completely decolored (T ₁ ).

Preparation of heat decoloring type reversible thermochromic material 1,3-diethyl-6-diethylaminofluorane 1.5 parts, 4,4 '-(2-methyl-propylidene) bisphenol 6 parts, 2- (3-t- A heat decolorable reversible thermochromic composition comprising 1 part of butyl-5-methyl-2-hydroxyphenyl) -5-chlorobenzotriazole, 5 parts stearyl alcohol, 20 parts cetyl alcohol and 25 parts stearyl caprate A resin / amine curing agent was encapsulated as a wall film material to obtain a heat-decolorable reversible thermochromic material in the form of microcapsules.
The reversible thermochromic material exhibits a decoloring behavior of a heat decoloring type, and is in a colored state (orange) at room temperature, starts decoloring at 28 ° C. (t ₃ ) when heated, and completely disappears at 31 ° C. or higher. It becomes a colored (colorless) state (t ₄ ), and when it is cooled, it starts to develop color at 29 ° C. (t ₂ ) and completely develops a color at 25 ° C. (t ₁ ).

Preparation of ink 40 parts of the heat-colorable reversible thermochromic material is dispersed in a vehicle containing 50 parts of an ethylene vinyl acetate copolymer resin emulsion, 3 parts of an antifoaming agent, 1 part of a thickening agent, and 3 parts of a leveling agent. A heat-colorable screen ink was obtained.
40 parts of the heat erasable reversible thermochromic material is dispersed in a vehicle containing 50 parts of an ethylene vinyl acetate copolymer resin emulsion, 3 parts of an antifoaming agent, 1 part of a thickening agent, and 3 parts of a leveling agent, and heated. An erasable screen ink was obtained.

Production of reversible thermochromic display body On the white fine paper, a heating color developing type thermochromic image provided with a code for content information by screen printing is provided using the heating coloring type screen ink, and the heating decoloring type Using screen ink, a reversible thermochromic display (reversible thermochromic property) is provided by providing a heat decoloring thermochromic image with a code for another content information in the vicinity of the heat-coloring thermochromic image by screen printing. Printed matter).

In the reversible thermochromic display, only an orange heat-erasable thermochromic image is visible at room temperature (25 ° C.).
The heat-erasable thermochromic image is imaged with a camera-equipped mobile phone as a machine having a reading function, code information is read, and the read code information is decoded. The mobile phone transmits the decode information to the server, uses the content information returned from the server, accesses the content server, and displays and browses a Web page that provides content data corresponding to the photographed code information.
Next, when the reversible thermochromic display is heated to 43 ° C. or higher, the heat decoloring thermochromic image is erased and a pink heat coloring thermochromic image appears.
The heat coloring color change image is picked up by a camera-equipped mobile phone to read the code information, and the read code information is decoded. The mobile phone transmits decode information to the server, uses the content information returned from the server, accesses the content server, and displays content data corresponding to the photographed code information. browse.
The state returned to its original state when left at room temperature, and could be reproduced repeatedly due to temperature changes.

Example 3
Preparation of heat-developable reversible thermochromic material 3- [2-Ethoxy-4- (N-ethylanilino) phenyl] -3- (1-ethyl-2-methylindol-3-yl) -4-azaphthalide, 2 parts, 10 parts of stearyl gallate, 8.75 parts of stearyl caprate, 8.75 parts of n-docosane, 7.5 parts of lauryl alcohol, 1 part of octadecyl ether, 2- (5-t-butyl-2-hydroxyphenyl) benzotriazole A two-part heat-colorable reversible thermochromic composition was encapsulated with an isocyanate resin as a wall film material to obtain a heat-colorable reversible thermochromic material in the form of a microcapsule.
The reversible thermochromic material exhibits a heat-developing color change behavior, is in a decolored state (colorless) at room temperature, starts to develop color at 44 ° C. (T ₃ ), and is blue at 60 ° C. Then (T ₄ ), when cooled, the color starts to disappear at 34 ° C. (T ₂ ), and at 30 ° C. it becomes completely decolored (T ₁ ).

Preparation of heat erasable reversible thermochromic material 3-dibutylamino-6-methyl-7-anilinofluorane 3 parts, 4,4 '-(2-methyl-propylidene) bisphenol 6 parts, 2- (3- t-butyl-5-methyl-2-hydroxyphenyl) -5-chlorobenzotriazole, 25 parts of stearyl alcohol, 25 parts of stearyl laurate, and a heat-erasable reversible thermochromic composition, epoxy resin / amine A curing agent was encapsulated as a wall film material to obtain a heat-decolorable reversible thermochromic material in the form of microcapsules.
The reversible thermochromic material exhibits a heat erasable color change behavior, is in a colored state (black) at room temperature, begins to lose color at 38 ° C. (t ₃ ) when heated, and completely disappears at 43 ° C. or higher. It becomes a colored (colorless) state (t ₄ ), and then starts to develop color at 38 ° C. (t ₂ ) upon cooling, and completely develops at 32 ° C. (t ₁ ).

Preparation of Ink 40 parts of the heat-colorable reversible thermochromic material was dispersed in a vehicle containing 60 parts of a hard epoxy resin, 1 part of an ultraviolet absorber, 2 parts of a thixotropic agent, and 8 parts of an additive, and then at room temperature. 28 parts of curable aliphatic polyamine was added to obtain a heat-colorable epoxy ink.
After 40 parts of the heat-erasable reversible thermochromic material is dispersed in a vehicle containing 60 parts of a hard epoxy resin, 1 part of an ultraviolet absorber, 2 parts of a thixotropic agent, and 8 parts of an additive, it is further cured at room temperature. 28 parts of aliphatic polyamine was added to obtain a heat-erasable epoxy ink.

Production of reversible thermochromic display body An image provided with a code for content information using the heat-colorable epoxy ink is provided on the side of a porcelain mug, and heat-cured color change by heating and curing at 70 ° C. for 1 hour. An image was formed. Furthermore, using the heat-erasable epoxy ink, an image with a code for another content information is provided on the heat-colorable thermochromic image, and heat-cured at 70 ° C. for 1 hour to heat-decolor heat A discolored image was formed to obtain a reversible thermochromic display (reversible thermochromic mug).
In the reversible thermochromic display, a heating color-changing thermochromic image is not visible in a room temperature environment, and only a black heating decoloring thermochromic image is visible.
The heat-erasable thermochromic image is imaged with a camera-equipped mobile phone as a machine having a reading function, code information is read, and the read code information is decoded. The mobile phone transmits the decode information to the server, uses the content information returned from the server, accesses the content server, and displays and browses a Web page that provides content data corresponding to the photographed code information.
When hot water at 70 ° C. is poured into the reversible thermochromic display, the heat decoloring thermochromic image is erased and a blue heat coloring thermochromic image appears.
The heat coloring color change image is picked up by a camera-equipped mobile phone to read the code information, and the read code information is decoded. The mobile phone transmits decode information to the server, uses the content information returned from the server, accesses the content server, and displays content data corresponding to the photographed code information. browse.
Next, when warm water was taken out and left at room temperature, it returned to its original state and could be reproduced repeatedly due to temperature changes.

Example 4
Preparation of heat-developable reversible thermochromic material 6 '-[Ethyl (4-methylphenyl) amino] -2'-(methylphenylamino) -spiro [isobenzofuran-1 (3H), 9 '-(9H) xanthene ] 3-one 4.5 parts, 8 parts dodecyl gallate, 12.5 parts cetyl caprate, 12.5 parts myristyl alcohol, 1 part behenyl behenate, 2- (3-t-butyl-5-methyl- Heat-colorable reversible thermochromic composition comprising 3 parts of 2-hydroxyphenyl) -5-chlorobenzotriazole encapsulates isocyanate resin as a wall film material to obtain a heat-colorable reversible thermochromic material in the form of a microcapsule It was.
The reversible thermochromic material exhibits a heat-developing color-changing behavior, is in a decolored state (colorless) at room temperature, begins to develop color at 34 ° C. (T ₃ ) when heated, and develops a green color at 43 ° C. Next (T
₄ ) Next, when cooled, the color starts to be erased at 36 ° C. (T ₂ ), and is completely erased at 24 ° C. (T ₁ ).

Preparation of heat decolorable reversible thermochromic material 3- [2-Ethoxy-4- (N-ethylanilino) phenyl] -3- (1-ethyl-2-methylindol-3-yl) -4-azaphthalide 5 parts, 4,4 '-(2-methyl-propylidene) bisphenol 6 parts, 2- (3-tert-butyl-5-methyl-2-hydroxyphenyl) -5-chlorobenzotriazole 1 part, myristyl alcohol 25 parts A heat-decolorable reversible thermochromic composition comprising 25 parts of decyl myristate encapsulated as an epoxy resin / amine curing agent as a wall film material, and a heat-decolorable reversible thermochromic material in the form of a microcapsule Obtained.
The reversible thermochromic material exhibits a decoloring behavior of a heat decoloring type, is in a decolored state (colorless) at room temperature, starts to color at 15 ° C. when cooled (t ₂ ), and is completely colored at 10 ° C. or lower ( The blue state is reached (t ₁ ), and when it is heated, the color starts to disappear at 16 ° C. (t ₃ ), and at 20 ° C. it is completely erased (t ₄ ).

Preparation of ink 20 parts of the heat-colorable reversible thermochromic material, 45 parts of acrylic ester resin emulsion, 3 parts of antifoaming agent, 5 parts of alkali thickener, 0.5 part of preservative, ammonia water (25%) Dispersed in a vehicle containing 3 parts and 6 parts of an epoxy-based crosslinking agent to obtain a heat-colorable screen ink.
20 parts of the above heat decoloring type reversible thermochromic material, 45 parts of acrylic ester resin emulsion, 3 parts of defoaming agent, 5 parts of alkali thickener, 0.5 part of preservative, 3 parts of ammonia water (25%) And dispersed in a vehicle containing 6 parts of an epoxy crosslinking agent to obtain a heat-erasable screen ink.

Production of reversible thermochromic display body On the white 50-denier polyester tricot fabric, a heat-colored thermochromic image provided with a code for content information by screen printing is provided using the heat-colorable screen ink. A reversible thermochromic display using a heat decoloring type screen ink provided with a heat decoloring type thermochromic image provided with a code for another content information in the vicinity of the heat coloring type thermochromic image by screen printing. (Reversible thermochromic fabric) was obtained.

Nothing is visually recognized in the reversible thermochromic display body in a room temperature environment, and when it is cooled to 10 ° C. or lower, a blue heat-erasable thermochromic image appears.
The heating color-changing thermochromic image is captured by a camera-equipped mobile phone as a machine having a reading function to read code information, and the read code information is decoded. The mobile phone transmits the decode information to the server, uses the content information returned from the server, accesses the content server, and displays and browses a Web page that provides content data corresponding to the photographed code information.
Next, when the reversible thermochromic display is heated to 43 ° C. or higher, the heat-erasable thermochromic image is erased and a green heat-erasable thermochromic image appears.
The heat-erasable thermochromic image is captured by a camera-equipped mobile phone to read code information, and the read code information is decoded. The mobile phone transmits decode information to the server, uses the content information returned from the server, accesses the content server, and displays content data corresponding to the photographed code information. browse.
The state returned to its original state when left at room temperature, and could be reproduced repeatedly due to temperature changes.

Example 5
Preparation of heat-developable reversible thermochromic material 6 '-[Ethyl (4-methylphenyl) amino] -2'-(methylphenylamino) -spiro [isobenzofuran-1 (3H), 9 '-(9H) xanthene ] 3-one 4.5 parts, 8 parts dodecyl gallate, 12.5 parts cetyl caprate, 12.5 parts myristyl alcohol, 1 part behenyl behenate, 2- (3-t-butyl-5-methyl- Heat-colorable reversible thermochromic composition comprising 3 parts of 2-hydroxyphenyl) -5-chlorobenzotriazole encapsulates isocyanate resin as a wall film material to obtain a heat-colorable reversible thermochromic material in the form of a microcapsule It was.
The reversible thermochromic material exhibits a heat-developing color-changing behavior, is in a decolored state (colorless) at room temperature, begins to develop color at 34 ° C. (T ₃ ) when heated, and develops a green color at 43 ° C. Then (T ₄ ), when cooled, the color starts to be erased at 36 ° C. (T ₂ ), and is completely erased at 24 ° C. (T ₁ ).

Preparation of heat erasable reversible thermochromic material 6- (N-ethylisopentylamino) benzo [a] fluorane 3 parts, 4,4 '-(2-methyl-propylidene) bisphenol 6 parts, 2- (3- A heat-decolorable reversible thermochromic composition comprising 1 part of t-butyl-5-methyl-2-hydroxyphenyl) -5-chlorobenzotriazole, 5 parts stearyl alcohol, 20 parts cetyl alcohol and 25 parts stearyl caprate An epoxy resin / amine curing agent was encapsulated as a wall film material to obtain a heat-decolorable reversible thermochromic material in the form of microcapsules.
The reversible thermochromic material exhibits a decoloring behavior of a heat decoloring type, is in a colored state (pink color) in a normal temperature range, starts to decolor at 28 ° C. (t ₃ ) when heated, and is completely at 31 ° C. or higher. When it is cooled (colored) (t ₄ ) and then cooled, it starts to develop color at 29 ° C. (t ₂ ), and at 25 ° C. it becomes pink (t ₁ ).

Preparation of ink In a vehicle comprising 5 parts of the heat-colorable reversible thermochromic material, 45 parts of an acrylic resin xylene solution (solid content 50%), 15 parts of xylene, 25 parts of methyl isobutyl ketone, and 6 parts of a polyisocyanate curing agent. Dispersion was carried out to obtain a heating color developing type paint.
Stir and mix in a vehicle consisting of 5 parts of the heat decolorable reversible thermochromic material, 45 parts of an acrylic resin xylene solution (solid content 50%), 15 parts of xylene, 25 parts of methyl isobutyl ketone and 6 parts of a polyisocyanate curing agent. Thus, a heat-erasable paint was obtained.

Production of reversible thermochromic display body A heat-colorable thermochromic image provided with a code for content information by spray coating is provided on a miniature car made of ABS resin using the heat-colorable paint, and the heat erase A reversible thermochromic display was obtained by using a color-type paint to provide a heat-erasable thermochromic image provided with a code for another content information on the heat-colored thermochromic image by spray coating.

In the reversible thermochromic display, only a pink heat-erasable thermochromic image is visible at room temperature (25 ° C.).
The heat-erasable thermochromic image is imaged with a camera-equipped mobile phone as a machine having a reading function, code information is read, and the read code information is decoded. The mobile phone transmits the decode information to the server, uses the content information returned from the server, accesses the content server, and displays and browses a Web page that provides content data corresponding to the photographed code information.
When the reversible thermochromic display is heated to 43 ° C. or higher, the heat decoloring thermochromic image is erased and a green heating color developing thermochromic image appears.
The heat coloring color change image is picked up by a camera-equipped mobile phone to read the code information, and the read code information is decoded. The mobile phone transmits decode information to the server, uses the content information returned from the server, accesses the content server, and displays content data corresponding to the photographed code information. browse.
The state returned to its original state when left at room temperature, and could be reproduced repeatedly due to temperature changes.

Example 6
Preparation of heat-developing reversible thermochromic material 2- (dibutylamino) -8- (dipentylamino) -4-methyl-spiro [5H]-[1] benzopyrano [2,3-g] pyrimidine-5,1 ′ (3H) -isobenzofuran] -3-one 1 part, 8 parts dodecyl gallate, 12.5 parts stearyl laurate, 12.5 parts lauryl alcohol, 1 part octadecyl ether, 2- (3-t-butyl-5 -Methyl-2-hydroxyphenyl) -5-chlorobenzotriazole 3 parts heating coloring type reversible thermochromic composition encapsulating isocyanate resin as a wall film material, and heating coloring type reversible thermochromic form in the form of microcapsules Obtained material.
The reversible thermochromic material exhibits a heat-developing color change behavior, is in a decolored state (colorless) at room temperature, starts to develop color at 30 ° C. (T ₃ ), and develops a pink color at 40 ° C. When it is cooled (T ₄ ) and then cooled, it begins to lose color at 30 ° C. (T ₂ ), and at 22 ° C. it becomes completely erasable (T ₁ ).

Preparation of heat decolorable reversible thermochromic material 3- [2-Ethoxy-4- (N-ethylanilino) phenyl] -3- (1-ethyl-2-methylindol-3-yl) -4-azaphthalide 5 parts, 4,4 '-(2-methyl-propylidene) bisphenol 6 parts, 2- (3-tert-butyl-5-methyl-2-hydroxyphenyl) -5-chlorobenzotriazole 1 part, cetyl alcohol 5 parts In addition, a heat decolorable reversible thermochromic composition comprising 20 parts of myristyl alcohol and 25 parts of cetyl caprate encapsulates an epoxy resin / amine curing agent as a wall film material, and a heat decolorable reversible thermochromic form in the form of a microcapsule. Obtained material.
The reversible thermochromic material exhibits a heat decoloring behavior, and is in a decolored state (colorless) at room temperature, starts to develop color at 20 ° C. (t ₂ ) when cooled, and is completely colored at 17 ° C. or less. It becomes (blue) (t ₁ ), and when it is next heated, it starts decoloring at 20 ° C. (t ₃ ) and becomes completely decolored at 22 ° C. (t ₄ ).

Preparation of ink 100 parts of the heat-colorable reversible thermochromic material was dispersed in a vehicle containing 80 parts of an acrylic resin and 2 parts of an antifoaming agent to obtain a heat-colorable gravure ink.
100 parts of the heat erasable reversible thermochromic material was dispersed in a vehicle containing 80 parts of an acrylic resin and 2 parts of an antifoaming agent to obtain a heat erasable gravure ink.

Production of reversible thermochromic display body A heat-colorable thermochromic image provided with a code for content information using the heat-colorable gravure ink is provided on a transparent heat-shrinkable polyester resin film, and the heat decoloring is further performed. A heat-erasable thermochromic image provided with a code for another content information was provided in the vicinity of the heat-colorable thermochromic image using a mold gravure ink.
Next, after the end portions of the film are laminated in a cylindrical shape so that the printing surface is on the inside, the film is attached to a polyester resin beverage container and subjected to heat shrinkage processing, and a reversible thermochromic display (reversible thermochromic property). A beverage container) was obtained.
The reversible thermochromic display was filled with tea and stored in a heater set at 60 ° C.
In the reversible thermochromic display, when it is heated to 45 ° C. or higher, a heat-erasable thermochromic image is not visible, and only a pink heat-coloring thermochromic image is visible.
The heating color-changing thermochromic image is captured by a camera-equipped mobile phone as a machine having a reading function to read code information, and the read code information is decoded. The mobile phone transmits the decode information to the server, uses the content information returned from the server, accesses the content server, and displays and browses a Web page that provides content data corresponding to the photographed code information.
At this time, information on the raw material, the place of origin, etc. regarding “tea” in the reversible thermochromic display body could be browsed.
After drinking the contents (tea) of the reversible thermochromic display, in the winter environment of 15 ° C. or lower, the heat-colored thermochromic image disappears and a blue heat-erasable thermochromic image appears. .
The heat-erasable thermochromic image is captured by a camera-equipped mobile phone to read code information, and the read code information is decoded. The mobile phone transmits decode information to the server, uses the content information returned from the server, accesses the content server, and displays content data corresponding to the photographed code information. browse.
At this time, information on a questionnaire form, a present campaign, etc. regarding “tea” in the reversible thermochromic display body could be browsed.

Example 7
Preparation of heat-developable reversible thermochromic material 3- [2-Ethoxy-4- (N-ethylanilino) phenyl] -3- (1-ethyl-2-methylindol-3-yl) -4-azaphthalide, 2 parts, 10 parts of stearyl gallate, 8.75 parts of stearyl caprate, 8.75 parts of n-docosane, 7.5 parts of lauryl alcohol, 1 part of octadecyl ether, 2- (5-t-butyl-2-hydroxyphenyl) benzotriazole A two-part heat-colorable reversible thermochromic composition was encapsulated with an isocyanate resin as a wall film material to obtain a heat-colorable reversible thermochromic material in the form of a microcapsule.
The reversible thermochromic material exhibits a heat-developing color change behavior, is in a decolored state (colorless) at room temperature, starts to develop color at 44 ° C. (T ₃ ), and is blue at 60 ° C. Then (T ₄ ), when cooled, the color starts to disappear at 34 ° C. (T ₂ ), and at 30 ° C. it becomes completely decolored (T ₁ ).

Preparation of heat decolorable reversible thermochromic material 3- [2-Ethoxy-4- (N-ethylanilino) phenyl] -3- (1-ethyl-2-methylindol-3-yl) -4-azaphthalide 5 parts, 4,4 '-(2-methyl-propylidene) bisphenol 6 parts, 2- (3-tert-butyl-5-methyl-2-hydroxyphenyl) -5-chlorobenzotriazole 1 part, myristyl alcohol 25 parts A heat-decolorable reversible thermochromic composition comprising 25 parts of decyl myristate encapsulated as an epoxy resin / amine curing agent as a wall film material, and a heat-decolorable reversible thermochromic material in the form of a microcapsule Obtained.
The reversible thermochromic material exhibits a decoloring behavior of a heat decoloring type, is in a decolored state (colorless) at room temperature, starts to color at 15 ° C. when cooled (t ₂ ), and is completely colored at 10 ° C. or lower ( The blue state is reached (t ₁ ), and when it is heated, the color starts to disappear at 16 ° C. (t ₃ ), and at 20 ° C. it is completely erased (t ₄ ).

Preparation of ink 40 parts of the heat-colorable reversible thermochromic material is dispersed in a vehicle containing 50 parts of a urethane resin dispersion, 2 parts of an antifoaming agent, 1 part of a thickening agent, and 1 part of a leveling agent. A mold screen ink was obtained.
40 parts of the heat decoloring type reversible thermochromic material is dispersed in a vehicle containing 50 parts of urethane resin dispersion, 2 parts of defoaming agent, 1 part of thickening agent, and 1 part of leveling agent, and the heat decoloring type A screen ink was obtained.

Production of reversible thermochromic display body A heat-colored thermochromic image in which a code for content information is given by screen printing on the white polyester base material provided with an adhesive layer on the back surface is provided. In addition, a heat-erasable thermochromic image in which a code for another content information was given in the vicinity of the heat-colorable thermochromic image by screen printing was provided using the heat-erasable screen ink.
Next, a protective layer made of a transparent polyester resin is laminated on the heat-colorable thermochromic image and the heat-erasable thermochromic image, and the adhesive layer side is attached to a heat / cool heat storage body so as to be reversibly thermochromic. A characteristic display (reversible thermochromic heat storage) was obtained.

The reversible thermochromic display is not visually recognized at room temperature (25 ° C.), and a blue heat-erasable thermochromic image appears when cooled to 10 ° C. or lower for use in cold storage. The heat-erasable thermochromic image is imaged with a camera-equipped mobile phone as a machine having a reading function, code information is read, and the read code information is decoded. The mobile phone transmits the decode information to the server, uses the content information returned from the server, accesses the content server, and displays and browses a Web page that provides content data corresponding to the photographed code information.
At this time, it was possible to browse information such as precautions when using the reversible thermochromic display for cold storage and effective usage.
Next, when the reversible thermochromic display is heated to 43 ° C. or more in order to use it for heat storage, a heat decoloring thermochromic image is erased and a blue heating color developing thermochromic image appears.
The heat coloring color change image is picked up by a camera-equipped mobile phone to read the code information, and the read code information is decoded. The mobile phone transmits decode information to the server, uses the content information returned from the server, accesses the content server, and displays content data corresponding to the photographed code information. browse.
At this time, information such as precautions when using the reversible thermochromic display for heat storage and effective usage could be browsed.
The state returned to its original state when left at room temperature, and could be reproduced repeatedly due to temperature changes.

Example 8
Preparation of heat-developable reversible thermochromic material 3- [2-Ethoxy-4- (N-ethylanilino) phenyl] -3- (1-ethyl-2-methylindol-3-yl) -4-azaphthalide, 2 parts, 10 parts of stearyl gallate, 8.75 parts of stearyl caprate, 8.75 parts of n-docosane, 7.5 parts of lauryl alcohol, 1 part of octadecyl ether, 2- (5-t-butyl-2-hydroxyphenyl) benzotriazole The two-part heat-colorable reversible thermochromic composition was encapsulated with an isocyanate resin as a wall film material to obtain a heat-colorable reversible thermochromic material A in the form of a microcapsule.
Next, the electron-donating color-forming organic compound in the heat-colorable reversible thermochromic material A is converted to 1 part of 3-cyclohexylamino-7-methylfluorane, 6- (N-ethylisopentylamino) benzo [a A heat-developing reversible thermochromic material B was obtained in the same manner except that 1 part of fluorane was used.
In the same manner, a heat-colorable reversible thermochromic material C in which the electron-donating color-forming organic compound is 3-part 2- (2-chloroanilino) -6-dibutylaminofluorane, the electron-donating color-forming organic compound 6 '-[ethyl (4-methylphenyl) amino] -2'-(methylphenylamino) -spiro [isobenzofuran-1 (3H), 9 '-(9H) xanthen] -3-one 4.5 parts Heat-developable reversible thermochromic material D was obtained.
The reversible thermochromic materials A to D exhibit a heat-developing color change behavior, are in a decolored state (colorless) at room temperature, start to develop color at 44 ° C. (T ₃ ), and develop color at 60 ° C. When it is cooled (T ₄ ) and then cooled, it begins to lose color at 34 ° C. (T ₂ ), and at 30 ° C. it becomes completely erasable (T ₁ ).
The color tones of the reversible thermochromic materials A to D were A for blue, B for red, C for black, and D for green.

Preparation of heat-decolorable reversible thermochromic material 3- [2-Ethoxy-4- (N-ethylanilino) phenyl] -3- (1-ethyl-2-methylindole-3) as an electron-donating color-forming organic compound -Yl) -4-azaphthalide 1.5 parts, 4,4 '-(2-methyl-propylidene) bisphenol 6 parts, 2- (3-tert-butyl-5-methyl-2-hydroxyphenyl) -5-chloro A heat decolorable reversible thermochromic composition comprising 1 part of benzotriazole, 25 parts of myristyl alcohol, and 25 parts of decyl myristate encapsulates an epoxy resin / amine curing agent as a wall film material, and heat decolors in the form of a microcapsule. A type reversible thermochromic material a was obtained.
Next, 1.5 parts of 3-cyclohexylamino-7-methylfluorane and 6- (N-ethylisopentylamino) are used as the electron-donating color-forming organic compound in the heat-decolorable reversible thermochromic material a. A heat-erasable reversible thermochromic material b was obtained in the same manner except that the amount of benzo [a] fluorane was 1.5 parts.
In the same manner, the heat-decolorable reversible thermochromic material c, 2-dibenzylamino-, having 3 parts of 3-dibutylamino-6-methyl-7-anilinofluorane as the electron-donating color-forming organic compound. Heat decoloring type reversible thermochromic material d having 2 parts of 6-diethylaminofluorane was obtained.
The reversible thermochromic materials a to d show a color erasing behavior of a heat decoloring type, are in a decolored state (colorless) in a normal temperature range, and start to develop color at 15 ° C. when cooled (t ₂ ) at 10 ° C. or less. The color is completely developed (t ₁ ), and when heated, the color starts to be erased at 16 ° C. (t ₃ ), and the color is completely erased at 20 ° C. (t ₄ ).
The color tone of the reversible thermochromic materials a to d was a for blue, b for red, c for black, and d for green.

Preparation of ink 40 parts of the heat-developing reversible thermochromic material is dispersed in a vehicle containing 60 parts of a hard epoxy resin, 1 part of an ultraviolet absorber, 2 parts of a thixotropic agent, and 8 parts of an additive, and further cured at room temperature. Heat-colorable epoxy inks A to D were obtained by adding 28 parts of aliphatic aliphatic polyamine.
After 40 parts of the heat-erasable reversible thermochromic material is dispersed in a vehicle containing 60 parts of a hard epoxy resin, 1 part of an ultraviolet absorber, 2 parts of a thixotropic agent, and 8 parts of an additive, it is further cured at room temperature. Heat-erasable epoxy inks a to d were obtained by adding 28 parts of an aliphatic polyamine.

Production of reversible thermochromic display body On the side surface of the heat-resistant glass cup, the color code 1 (4 colors are arranged in a 5 × 5 square) for content information registered in advance using the heat-colorable epoxy inks A to D. ) Was formed, and heat-cured at 70 ° C. for 1 hour to provide a heat-colored thermochromic image. Further, color codes 2 (4 colors are arranged in a 5 × 5 square) for another previously registered content information in the vicinity of the heat-colored thermochromic image using the heat-erasable epoxy inks a to d. ) Was formed, and heat-cured at 70 ° C. for 1 hour to provide a heat-decolorable thermochromic image to obtain a reversible thermochromic display (reversible thermochromic cup).
The reversible thermochromic display is not visually recognized at room temperature (25 ° C.), and when it is cooled to 10 ° C. or less by pouring a chilled beverage, a blue, red, black, green heat-erasable thermochromic image ( Color code 2) appears.
Code information obtained by photographing the heat-erasable thermochromic image with a camera-equipped mobile phone as a machine having a reading function, transmitting the image to the server, accessing the content server using the content information returned from the server, and photographing the code information A web page that provides content data according to the content is displayed and browsed.
At this time, we were able to browse advertisements related to beverages and various information on beverages according to the four seasons.
Next, when the heated beverage is poured onto the reversible thermochromic display body and the temperature reaches 60 ° C. or higher, the heat-erasable thermochromic image is erased and the blue, red, black, and green heat-colored thermochromic image. (Color code 1) appears.
The heating color-changing thermochromic image is captured by a camera-equipped mobile phone as a machine having a reading function, transmitted to the server, the content information returned from the server is used to access the content server, and the captured code information Display and browse web pages that provide the corresponding content data.
At this time, advertisements relating to beverages different from the information obtained from the heat-erasable thermochromic image and various information on beverages adapted to the four seasons could be viewed.
The state returned to its original state when left at room temperature, and could be reproduced repeatedly due to temperature changes.

It is explanatory drawing which shows the discoloration behavior of a heat decoloring type reversible thermochromic composition. It is explanatory drawing which shows the discoloration behavior of a heat coloring type reversible thermochromic composition.

Explanation of symbols

t ₁ Complete color development temperature of reversible thermochromic material of heating decoloring type t ₂ Color development start temperature of reversible thermochromic material of heat decoloring type t ₃ Decolorization start temperature of reversible thermochromic material of heat decoloring type t ₄ Complete decolorization temperature of reversible thermochromic material of heat decoloring type T ₁ Complete decoloration temperature of reversible thermochromic material of reversible thermochromic material of heating type T ₂ Decolorization start temperature of reversible thermochromic material of reversible thermochromic material of ₂ heating color development T ₃ Color development start temperature of reversible thermochromic material of heat coloring type T ₄ Full color temperature of reversible thermochromic material of heat coloring type T ₄

Claims (6)

  Heat-colored thermochromic image containing a reversible thermochromic material that develops color by heating from the decolored state and decolorizes by dropping the temperature from the colored state, and decolorizes by heating from the colored state and cools from the decolored state A heat-decolorable thermochromic image containing a reversible thermochromic material that develops color by the coexistence on the support, and the heat-colorable thermochromic image and the heat-erasable thermochromic image have a reading function. A reversible thermochromic display that is provided with codes for different content information that can be read by a machine.   The reversible thermochromic display body according to claim 1, wherein the heat-colorable thermochromic image and the heat-erasable thermochromic image are juxtaposed or overprinted.   The reversible thermochromic display according to claim 1 or 2, wherein the heat-decolorable thermochromic image is in a decolored state and the heat-decolorable thermochromic image is in a decolored state at 25 ° C.   The reversible thermochromic display according to claim 1 or 2, wherein the heat-developing thermochromic image and the heat-erasable thermochromic image are in a decolored state at 25 ° C.   The reversible thermochromic display according to claim 1 or 2, wherein the heat-developable thermochromic image is in a colored state and the heat-decolorable thermochromic image is in a decolored state at 45 ° C.   6. The content information is any one of URL information of a content providing server, identification information for specifying content in the content providing server, identification information for specifying a network, and attribute information. Reversible thermochromic display.

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