JP784H - Printing ink - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention includes paper, synthetic paper, plastic, cloth, metal plate, and wood.
When a printed matter printed on a support such as a piece of paper is heated or cooled, it becomes warm.
Heat that gives printed matter that develops, erases or discolors in response to temperature
Discolorable printing ink. Conventionally, when printing ink is printed on a support such as paper,
The printed matter is durable and does not change due to external conditions.
The feature is to leave printed characters and images.
It was the main purpose. For example, resin and volatile organic solvent
Gravure mark with general pigment dispersed in a vehicle consisting of
Dispersion of general pigments in printing ink and oxidation polymerization type vehicle
The printed matter printed with the printed letterpress ink may change.
All that was left was to leave only static characters and images. Therefore, in conventional printed matter, the printed matter disappears in response to temperature.
Provide it for any application where you want to create, develop, or change color
I couldn't do it. Therefore, the present invention is based on a completely new principle.
New printing that incorporates dynamic elements not found in conventional printed materials
It provides ink. In other words, the color changes in response to temperature
It can be used for temperature detection. Also, various colors are available in response to temperature.
The features of fun, fun, and magic
To provide a variety of new and interesting and useful products
You can That is, the present invention relates to a colorless electron-donating color-forming organic compound and flux.
In compounds having enolic hydroxyl groups, phenol
Electron-donating color-forming organic compound in which the compound having a hydroxyl group is colorless
A reaction that acts on a compound and changes to a colored form
Higher aliphatic compounds without polar substituents in the child reaction
Monohydric alcohols and higher aliphatics without polar substituents
Monocarboxylic acid and chain-type aliphatic 1 having no polar substituent
Esters without polar substituents derived from polyhydric alcohols
Nonvolatile that desensitizes the color reaction of the two compounds selected from
Mix the three components of the volatile compound and dissolve it in the vehicle.
Dissolve or disperse into thermochromic printing ink, or
A three-component microcapsule encapsulated in a vehicle
Disperse into thermochromic printing ink. The present invention will be described below. It has an electron-donating color-forming organic compound and a phenolic hydroxyl group.
The coloration due to the reaction with the compound
And higher aliphatic monohydric alcohols that do not have a volatile substituent
Aliphatic monocarboxylic acids without polar substituents and polarities
Obtained from a chain aliphatic monohydric alcohol having no substituent
Said diamine selected from esters having no polar substituents
Compounds selected from non-volatile compounds that desensitize the color reaction of compounds
When a compound is added and reacted, the coloring phenomenon changes with temperature.
I got new knowledge that Printing ink with the above three components
Dissolve or disperse in vehicle for use or microcapsule of three components
Dispersed in a vehicle for printing ink and heat
No color-changing printing ink, using conventional printing techniques
It is possible to obtain thermochromic printed matter with excellent performance not found in
did it. The present invention will be described in more detail. (A) Electron-donating color developability
Organic compounds, compounds having (b) phenolic hydroxyl groups,
(C) Higher aliphatic monohydric alcohol having no polar substituent
And a higher aliphatic monocarboxylic acid having no polar substituent
And a chain aliphatic monohydric alcohol having no polar substituent
Before choosing from esters without polar substituents obtained from
Of non-volatile compounds that desensitize the color reaction of two compounds
The thermochromic colorant consisting of
Fully cover the daily living temperature range at -100 ° C to + 200 ° C.
- Also, below 0 ° C, especially at minus tens of degrees (° C)
The conventional thermochromic material enables discoloration in
A major feature that can not be seen at all is that the thermochromic material is at low temperature
The fact that we were able to expand to the industrial sector is related to industrial safety and convenience.
The contribution is extremely large. Further, the greatest feature of the thermochromic colorant according to the present invention is discoloration.
Freely select the combination of temperature and color type
Is possible. That is, a color is selected with an electron-donating color-developing organic compound, and
Color with a compound having a hydroxyl group to determine the concentration.
Higher aliphatic monohydric alcohol with no polar substituents
And a higher aliphatic monocarboxylic acid having no polar substituent
And a chain aliphatic monohydric alcohol having no polar substituent
Before choosing from esters without polar substituents obtained from
Nonvolatile compounds that desensitize the color reaction of the two compounds
Alternatively, the color change temperature can be determined by the blending amount. Paraphrase
At temperatures between approximately -100 ° C and 200 ° C.
Red, blue, yellow, green, orange, purple and other color schemes to subtle colors
Before changing from colored to colorless and from colorless to colored
It is possible by combining the above substances appropriately.
And the required color and discoloration temperature like conventional thermochromic materials
When looking for a substance with a certain degree
Other than choosing more or waiting for a substance to be synthesized in the future
Compared to the lack of law, the present invention is a material that does not hitherto exist
It is a thermochromic material with a high degree of freedom in selection. In addition, the change in color changes from colored to colorless and from colorless to colored.
Unlike the conventional thermochromic material, it is always a remarkable change.
That is the point. However, general dyes, pigments, etc., for the above-mentioned colorants
Change from colored (I) to colored (II) by adding
It can also be done. On the other hand, it can transmit light
The main feature of the present invention is that, for example, a change in temperature.
It can be made transparent according to the requirements, and can be applied to display objects that represent the background.
It As described above, coloring agents with outstanding performance
By using printing ink, which will be described later, partially or entirely on the support
It can be printed and used for various purposes such as daily life materials and industrial materials.
You can. Here, if the printing ink of the present invention is specifically explained, for example,
For example, a as an electron-donating color-forming organic compound, 3. Diethyl
amino. 6-methyl. 50 g of 7-chlorfluorane
Bisphenol as a compound having an enolic hydroxyl group
As a compound of 200 g of (A)
Coal 1000g, as vehicle, microcrystalline
Add 2000 g of wax and homogenize by heating and melting at 100 ℃
Then, print by heating intaglio method under heating condition of 80 to 100 ℃
Then, it was cooled and set. The printed matter obtained is red at 20 ° C.
It exhibited a color and turned colorless when heated to 50 ° C. This
When it is returned to 20 ℃, it turns red again and has reversibility.
It was b As an electron-donating color-forming organic compound,
50 g of iolettolactone, having phenolic hydroxyl group
As a compound, 200 g of gallic acid lauryl ester,
As the compound of (C), myristyl alcohol 400
g, as a vehicle, microcrystalline wax 1
000g is heated and melted at 100 ℃ to homogenize, 80 ～ 1
Printing with the intaglio printing method under the heating condition of 00 ℃, and cooling
I set it. The printed matter obtained is colorless at 20 ° C, at 50 ° C
When heated, it turned blue. Return this to 20 ℃
Then, it became colorless again and had reversibility. On the other hand, printing using a special metal complex salt crystal than before
There is ink, and the printed material is used for temperature sensing.
It was However, this type of metal complex has a substantial discoloration temperature range.
Mostly discolored to 100 ° C or higher at about 50 ° C to 500 ° C
There is a temperature point, and no discoloring substance in the daily living temperature range is found.
Yes. The color and discoloration temperature can be freely selected.
Instead, it had to rely on the properties of the complex salt substance itself. Immediately
The types of substances that reversibly change color below 100 ° C are 2
Limited to 3 types and the discoloration is Ag ₂ HgI _Four At 50
Yellow to orange, Cu at ℃ ₂ HgI _Four Red at 70 ° C
Changes from brown to brown, and of course you can choose the color type
However, the discoloration is very similar. Furthermore
Most of these metal complex salts are compounds containing heavy metals, especially
Substances that change color below 100 ° C contain Hg as described above.
Therefore, when using it, it is necessary to pay attention to the danger.
At the same time, use of a large amount of this substance as it can be a source of pollution
Was extremely inconvenient. On the other hand, liquid crystals are also used in printing inks as thermochromic substances.
Started However, liquid crystals are extremely sensitive chemically.
However, there is a drawback that its action and effect deteriorates due to contact with other substances.
Therefore, when applied to printing inks, it is not
When it is not possible to handle it,
Can be used only. Moreover, the discoloration temperature range of the printed matter is roughly −
Those that change color at 20 ° C to 150 ° C, especially below 0 ° C are 1 to
There are two types, very few. Also, the same color and discoloration temperature as above
It is not possible to choose freely, depending on the nature of the liquid crystal substance itself.
I have no choice. In other words, if you are looking for a substance with the required color and discoloration temperature
In the case of
There is no other way but to wait for a substance to be synthesized in the future. On the other hand, a cholesteric liquid crystal requires a black background.
That only extremely dark printed matter can be obtained, and discoloration
Is not clear, so expect a sufficient effect as a printed matter.
I can't come. Therefore, this kind of compound is very expensive.
Considering that there are various things, this can be used as printed matter.
There are many inconveniences when used for various purposes, and there are major restrictions.
It is said. Next, the electron-donating color-forming organic compound used in the present invention is prepared.
For diaryl phthalides, polyarylcarbino
Rules, leuco auramines, acyl auramines, ants
Auramines, rhodamine B lactams, indri
, Spiropyrans, fluoran, etc. These compounds are exemplified below. Crystal Violet Lactone, Malachite Green
Lactone, Michler hydrol, Crystal violet
Tocarbinol, malachite green. Carbinol,
N- (2.3-dichlorophenyl) leukoauramine,
N-benzoyl auramine, N-acetyl auramine,
N-phenyl auramine, rhodamine B lactam, 2-
(Phenyl imino ethanedilidene) 3.3-dimethyl
Ndrin, N.N. 3.3-Trimethylindolinobenzos
Pyropyran, 8'-methoxy-N. 3.3-Trimethyl
Indolinobenzospiropyran, 3-diethylamino-
6-methyl-7-chlorofluorane, 3-diethylami
No-7-methoxyfluorane, 3-diethylamino-6
-Benzyloxyfluorane, 1.2-benz-6-di
Examples include ethylaminofluorane. Compounds having sublimable or volatile phenolic hydroxyl groups
Examples are P-ethylphenol and O-ethylphenol.
Enol, P-cresol, O-cresol, m-cre
Sol, 2,4-xylenol, pyrocatechol, resor
Rucin, methylcatechol, ethylcatechol, propiyl
Lucatechol, tert-butyl catechol, α-na
Futor, thymol, eugenol, isoeugenol
Methyl P-oxybenzoate, P-oxybenzoic acid
Chill, propyl P-oxybenzoate, P-oxybenzoic acid
Butyl acid and the like. As a compound having a nonvolatile phenolic hydroxyl group,
For example, nonylphenol, dodecylphenol, styrene
Renated phenol, 2,2'-methylenebis (4
-Methyl-6-tert-butylphenol), 2,
4,6 Trichlorophenol, O-phenylphenol
L, P-phenylphenol, P- (P-chlorophenyl)
Le) phenol, O- (O-chlorophenyl) phenol
Octyl, P-oxybenzoic acid, P-oxybenzoic acid
Dodecyl, bisphenol A, 1,2-dioxynaphtha
Len, 2,3-dioxynaphthalene, phenolphthale
In, O-cresolphthalein, protocatechuic acid
Propyl, butyl protocatechuate, protocatechu
Octyl acid, dodecyl protocatechuate, 2, 3,
4-trioxyethylbenzene, methyl gallate, gallic acid
Ethyl acid, propyl gallate, butyl gallate, gallic
Hexyl acid salt, octyl gallate, dodecyl gallate, gallon
Cetyl gallate, stearyl gallate, 2,3,5 trio
Xinaphthalene, tannic acid, phenol resin initial condensation
There are things etc. Compounds having non-volatile and hydrophilic phenolic hydroxyl groups
Examples of the object include gallic acid, methyl gallate, and gallic acid.
Ethyl acid, ammonium gallate, tannic acid, proto
Catechuic acid, methyl protocatechuate, protocate
Ethyl citrate, ammonium protocatechuate, di
Examples include oxynaphthalene and sodium sulfonate. A higher aliphatic monohydric alcohol having no polar substituent,
Higher aliphatic monocarboxylic acids with no polar substituents and poles
From chain-type aliphatic monohydric alcohols that do not have a volatile substituent
The above-mentioned two selected from the obtained esters without polar substituents.
Nonvolatile compounds that desensitize the color reaction of compounds are
It is a thing. Lauryl alcohol, myristyl alcohol
Ru, cetyl alcohol, stearyl alcohol, aiko
Syl alcohol, docosyl alcohol, myristate
Chill, butyl palmitate, methyl stearate, stearate
Ethyl arnate, propyl stearate, stearic acid
Butyl, octyl stearate, butyl oleate, etc.
There is. Electron-donating color organic compound, phenolic water
Compounds with acid groups, higher fats without polar substituents
Group monohydric alcohols and higher fats without polar substituents
Group Monocarboxylic Acids and Chain-Type Aliphatic Compounds with No Polar Substituents
S which does not have polar substituents obtained from monohydric alcohols
Volatile to desensitize the color reaction of the two compounds selected from
A colorant is formed by appropriately combining the three components of the effervescent compound.
It is okay to mix two or more of these ingredients.
Yes. As described above, the electron-donating color-forming organic compound and the pheno
Compounds with carboxylic acid hydroxyl groups and polar substituents
Has no higher aliphatic monohydric alcohols and polar substituents
No higher aliphatic monocarboxylic acids and no polar substituents
A polar substituent obtained from a chain-chain aliphatic monohydric alcohol
The color reaction of the two compounds selected from the ester which does not have
To properly select the three components of the desensitizing non-volatile compound
Changes according to external conditions such as changes with temperature.
Although it has the characteristic of a unique colorant that is not available in the past,
Some of the three-component compounds are liquid at room temperature or volatilize
Easy ones are also included. Also, it is safe to store when it is printed.
To increase the qualitativeness and make the color change more colorful, the above three
When using colorants that contain ingredients in microcapsules
There are combinations that can achieve superior effects. That is, in the color change type printed matter, the three-component colorant is usually used.
It is preferable to maintain the same system homogeneously in
Even one component may be separated from the system by volatilization or outflow.
Then, a significant change in the mixing ratio of the three components is due to thermal discoloration.
Not good for performance. Therefore, known microencapsulation
Applying technology to encapsulate the coloring agent in microcapsules
Solves the above disadvantages and improves the thermal discoloration performance.
It can be dramatically improved. This is a thermochromic colorant
Is protected by a capsule membrane, and each component is evaporated and separated.
Is prevented. Also, depending on the manufacturing conditions, particles
Microcapsules with diameters from a few microns to a few millimeters
You can also get Further, the thermochromic garment contained in the microcapsules according to the present invention
The greatest feature of colorants is heat that changes to various temperatures and colors.
Discoloring colorants are brought close to each other and the effect is maintained independently
There is a point that can be done. Specifically, for example, (1) a colorant that changes from yellow to colorless at 10 ° C (2) a colorant that changes from blue to colorless at 20 ° C (3) a color that changes from red to colorless at 30 ° C Uses three types of thermochromic colorants for printing inks
When (1) (2) (3) is simply mixed,
Change from black to colorless with no change in sharpness around ℃
The printed matter changes color. Because there is no isolation layer (1) (2) (3)
Colorants affect each other, and the color changes with only one mixed color
The result is a lack of sharpness. Here, the colorants (1), (2) and (3) are added to the fine particles of 20 to 30 μm
The colorant contained in the capsule is mixed and used in printing ink.
When printed, the thermochromic property of the printed matter is black at 10 ° C or less, 10
Purple at 20 ℃ to 20 ℃, Red at 20 ℃ to 30 ℃, Above 30 ℃
It changes to colorless and reversely cools from above 30 ℃
And changes from colorless-red-purple-black to the above principle.
However, more complex changes are possible. Also, the change
Be keen. This is due to inclusion in a microcapsule
Since each colorant operates independently,
This is one of the useful characteristics. Furthermore, it is protected by the capsule wall
Therefore, not only the colored materials but also highly reactive materials
Even if it comes into contact with the quality, it does not deteriorate the thermochromic performance,
Therefore, the range of application was extremely wide. For example, chemistry of acidic substances, alkaline substances, peroxides, etc.
Of thermochromic properties when mixed with thermally active substances
It was a long time ago. On the other hand, as a well-known microencapsulation technique used in the present invention,
Interfacial polymerization method, in situ polymerization method, in-liquid curing coating method,
Phase separation method from aqueous solution, Phase separation method from organic solution,
Melt dispersion cooling method, air suspension coating method, spray drying
There is a method, but next is a typical microencapsulation method for colorants.
The manufacturing method will be specifically described below. The three components used to explain the microcapsule manufacturing method
An example of a colorant formulation (hereinafter referred to as colorant A) is described below.
The color materials are not limited to this, and can be any combination as described above.
Applicable to microencapsulation. (A), (B), and (C) are dissolved by heating at 80 ° C. to obtain colorant A. Production Example 1 0.5 g of hexamethylene bischloroformate as a colorant
Dissolve in 30 g of A by heating at 80 ℃, and add this to 5% gelatin water.
Add dropwise to 200 g of solution and stir to form fine droplets. Continued
Dissolve 3g of hexamethylenediamine in 50g of water
Then, add this gradually to the solution that is being stirred first.
Then, if you keep stirring at about 50 ℃ for 4 hours,
Lenbischloroformate is a boundary between the microdroplets of colorant A and water.
Reacts with hexamethylenediamine on the surface, water and colorant A
It produces a solid polyurethane insoluble in water, which is a colorant.
By coating A, a capsule containing colorant A is obtained. The capsules manufactured as above are filtered and filtered.
It may or may not be subjected to post-treatment such as heart concentration and drying.
Use as it is. The same applies to the following manufacturing examples.
Mr. Production Example 2 5 g of Epicoat 834 (epoxy resin manufactured by Ciel Oil Co., Ltd.
(Fat) is dissolved in 30 g of colorant A by heating at 80 ° C.
% Drops in 150% gelatin aqueous solution so that it becomes a minute drop
Stir. To this, 3 g of curing agent U (Epo
The amine adduct of xy resin) was dissolved in 20 g of water.
Is gradually added to the solution which is continuously stirred, and the liquid temperature is adjusted.
If you keep stirring at 80 ℃ for about 4 hours, Epicoat 83
4 reacts with the curing agent U at the interface between the microdroplets of colorant A and water
To produce a solid polymer insoluble in water and colorant A,
This coats the colorant A to obtain a colorant A-containing capsule.
Be done. Production Example 3 1.0 g of Desmodule N-75 (manufactured by Bayer GmbH, Germany,
Polyvalent isocyanate) dissolved in 30 g of colorant A with heating
3% Gohsenol GM-14 (Nippon Gosei Kagaku)
Dropping into 150g of polyvinyl alcohol) solution
And stir to form fine droplets. 2g of hardener T
(Made by Ciel Oil Co., Ltd., amine adduct of epoxy resin) 2
Dissolve it in 0 g of water and add it to the solution that is being stirred first.
To the solution, keep the liquid temperature at 50 ° C and stir for about 5 hours.
If you continue, Desmodule N-75
It reacts with the curing agent T at the interface with water and does not react with water and colorant A.
It produces a soluble solid polyurea which covers the colorant A.
A colorant A-containing capsule is obtained by covering. Production Example 4 4 g of bisphenol A was added to 200 g of 0.8% sodium hydroxide.
Dissolved in an aqueous solution of um and terephthalic acid dichloride
Add 30 g of colorant A, which is a solution of 3 g heated and dissolved,
Stir until dry. Next, keep the solution temperature at 50 ° C.
After stirring for about 1 hour, terephthalic acid dichloride
At the interface between the microdroplets of colorant A and water, the reaction with bisphenol A
However, solid saturated polyester insoluble in water and colorant A
Of the colorant A, which is coated with the colorant A and is contained in the colorant A.
You get a psel. Production Example 5 6 g of styrene monomer and 0.6 g in 30 g of colorant A
Dissolve 10mg of divinylbenzene benzoyl peroxide by heating
Understand. This solution was added to 150 g of 2% aqueous gum arabic solution.
Add dropwise and stir to form fine droplets. Keep at about 60 ℃ 5
When the stirring is continued for a while, the polymerized polymer is
It becomes insoluble in water, which covers the colorant A
A capsule is obtained. Production Example 6 15 g of chloramine P-1500 (manufactured by Mitsui Toatsu Chemicals,
Urea formalin initial condensate) was dissolved in 135 g of water
30 g of coloring agent A heated to 80 ° C was dropped into the solution, and
Stir to form small droplets. Add citric acid to lower the pH to 4
And coloring at 45 to 50 ° C while stirring for 5 hours
A polymer insoluble in colorant A and water is produced, which
After coating, a colorant A-containing capsule is obtained. Production Example 7 Colorant heated to 80 ° C. in 80 g of 5% gelatin aqueous solution
Add 30 g of A and stir to form fine droplets. 5 more
Add 80 g of gum arabic and add acetic acid under constant stirring.
To lower the pH to 5 and add 200 g of water to the core cell
Raise the bass and lower the PH to 4.4, then
Add 37g formalin 1g for dura,
Keep the temperature at 50 ° C during the operation, and then gel the thick liquid film.
Cooling to 10 ℃ to raise the pH to 9
After leaving for several hours, colorant A-containing capsules are obtained. Next, the colorant described above and a dressing containing it in microcapsules
A method of converting a color material into a printing ink will be described. Printing ink type
In the formula, cooling and solidification type, evaporation drying type, permeation drying type, precipitation drying
Type, gelation dry type, oxidation polymerization type, thermosetting type, etc.
Natural resin, natural processed resin, synthetic resin, wax,
Although it is composed of a vehicle such as a solvent, it is a typical colorant.
The method of forming a printing ink will be illustrated. In addition, the compounding example of the coloring agent used for the explanation
(A or C), but the colorant is not limited to this
If it is a combination as described above, it is suitable for printing ink.
Wear. Dissolve (a), (b) and (c) with heating at 80 ℃ to homogenize and
And Colorant C Colorant A was encapsulated in microcapsules by the method of Production Example 2.
Isolated colorants. Dissolve by heating at 100 ° C. This ink is not suitable as a cold set ink.
I am. Dissolve by heating at 100 ° C. This ink is not suitable as a cold set ink.
I am. Stir well to dissolve colorant and resin. This ink is suitable as a gravure ink
It Stir well to make uniform. This ink is suitable as an aqueous gravure ink
ing. Stir well to dissolve the colorant. This ink is used as gravure ink and flexo ink.
It has aptitude. Stir well to make uniform. This ink is not suitable as a water-based screen ink.
I am. Stir well to dissolve colorant and resin. This ink is suitable for oil-based screen inks.
It This ink is suitable for letterpress ink. An example of a vehicle for printing ink used in the present invention is shown here.
Then, it is cooled and solidified (wax type) Karunaba wax, paraf
Inwax, microcrystalline wax, etc. Evaporative dry type (resin / solvent type) rosin, maleic acid logic
, Sierra, casein, alkyd resin, cellulos
Derivative, petroleum resin, low molecular weight polyethylene, police
Tylene, polyvinyl chloride, polyvinyl acetate, polyvinyl
Alcohol, petroleum solvent, aromatic solvent, alcohol
Kinds, ketones, esters, water, etc. Permeation dry type (resin / petroleum solvent type) rosin, rosin derivative, machine oil, spindle oil, kerosene
etc. Gelled dry type (emulsion type) vinyl copolymer latte
Tux, synthetic rubber lattex, etc. (Resin / solvent type) Alkyd resin, modified
Rubber, petroleum solvent, etc. Oxidation polymerization type (dry oil type) Polymerized linseed oil, tung oil, dehydrated oil
Mashi oil, Oiteshka oil, etc. (Oil-modified Alkyd type) Soybean oil-modified Alky
Tudd resin, coconut oil modified alkyd resin, linseed oil modified a
Lucky resin, etc. Thermosetting type (thermosetting resin type) Epoxy resin, amino resin
Fat, heat-reactive unsaturated hydrocarbon resin, etc. Also, depending on the type of material to be printed, if resin is not required
There is also. As described above, depending on the type of colorant, its use, etc., the vehicle
Select printing ink appropriately, printing ink, intaglio, letterpress, planographic,
A desired printed matter can be obtained by using a stencil or the like. Examples will be specifically shown below, but the present invention is not limited thereto.
Not something. The meanings of the abbreviations used in the examples are as follows. Component (a); electron-donating color-developing organic compound component (b); compound component (ha) having phenolic hydroxyl group; compound (c) CVL; crystal violet lactone PSD-G; manufactured by Nisso Kako Co., Ltd. Fluoran-based compound PSD-R; Fluoran-based compound PSD-V manufactured by Nisso Kako Co., Ltd .; Fluoran-based compound PSD-O manufactured by Nisso Kako Co., Ltd. Fluoran-based compound Orient B manufactured by Nisso Kako Co .; Orient Chem. Leuco made by Kogyo Co., Ltd.
-Lamine compound Y-1; Leuco compound ZU-P manufactured by Yamamoto Chemical Synthesis Co .; Spiropyran compound phenol resin PP810 manufactured by Yamamoto Chemical Synthesis Co .; phenol tree manufactured by Gunei Chemical Co., Ltd.
Fat tinuvin 327; benzotriazole manufactured by Ciba Geigy
UV absorber TBS; tertiary. Bityl phenyl salicylate Seesorb 103; Shiroishi Calcium Co., Ltd. 2-hydroxy
Ci-4-dodecyloxybenzophenone rasmit; dilauryl thiodip manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd.
Ropionate Marotherm S; diallyl dime manufactured by Hüls Chemical, West Germany
Tan isomer mixture VFY3107; Orient Chemical Co., Ltd. Vali Fas
t Yellow # 3107 Spirit dye BOS; Orient Chemical Industry Co., Ltd. Oil Blue BOS
Spirit dye ASY-GRH; Hodogaya Chemical Co., Ltd., Aizen Spilon Yell
ow GRH The number in the spirit dye (); the compounding amount g is shown. Next, the test results of the printed materials obtained in the examples will be described. The description of the test results is as follows. Indicates a colored area, and the unmarked area indicates a non-colored area. For example, in the above example, it is colored blue below 42 ℃, and colorless above 42 ℃.
Means that. Indicates a colored area, and a portion without description indicates a non-colored area. Also, after the test results, the printed matter according to the present invention and the conventional printed matter
The performance comparison with Next, the relationship between the present invention and conventional products (only those existing in the market)
Compare Noh. (A) Thermochromic type A printed matter using the printing ink according to the present invention as described above
Is a peculiarity that is decolorized, colored and discolored in response to temperature.
It has properties and the types of colors that can be used are red,
Subtle color variations such as blue, yellow, green, orange, purple, and black.
It is also possible to select materials such as temperature points and changing temperature points.
It has a feature that is not available in conventional printing inks.
As a result, various new applications have been opened. Thermochromic printing inks are used, for example, for colors in various industries.
Temperature detection, especially in low temperature industry, chemical reaction
Monitoring due to color change of temperature rise and fall, etc.
Preventing disasters by instructing color change temperature of containers or storage, chemical
For measuring temperature distribution in machinery, overloading electric circuits and equipment
Temperature indicator for early detection of fever due to fever, refrigeration at home
Temperature of storage, frozen foods, coolers, various heaters, baths, etc.
Signs and other things that change in a variety of ways: fun, fun, serious
Taking advantage of the characteristics of luck, display, advertising paper, teaching materials,
There are uses such as toys.

Claims (1)

[Correction] [Claims] [Claim 1] (a) an electron-donating color-forming organic compound, (b) a compound having a phenolic hydroxyl group, and (c) a higher-grade compound having no polar substituent Ester having no polar substituent obtained from an aliphatic monohydric alcohol, a higher aliphatic monocarboxylic acid having no polar substituent, and a chain aliphatic monohydric alcohol having no polar substituent A thermochromic printing ink obtained by dissolving or dispersing three components of a non-volatile compound which desensitizes the color reaction of the above-mentioned two compounds selected as essential components in a vehicle. 2. An (a) electron-donating color developing organic compound, (b) a compound having a phenolic hydroxyl group, (c) a higher aliphatic monohydric alcohol having no polar substituent, and a polar substituent. A color reaction of the above two compounds selected from a polar substituent-free ester obtained from a higher aliphatic monocarboxylic acid having no substituent and a chain aliphatic monohydric alcohol having no polar substituent. A thermochromic printing ink in which three components of a desensitizing non-volatile compound are essential components, and a mixture of these is encapsulated in microcapsules and dispersed in a vehicle.