JPS64427B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to an ink composition that easily discolors with heat, and more specifically, an extremely stable ink composition that exhibits reversible thermal discoloration upon appropriate external temperature changes on paper, fabric, synthetic resin moldings, ceramics, etc. It is an object of the present invention to provide a thermoreversibly color-changing ink composition capable of forming designs with excellent properties. As is known in the art, certain substances are colorless at a certain temperature, but when an appropriate temperature is applied, they develop color and become recognizable, or they are colored at room temperature but fade or change color when exposed to high temperatures. Printing inks, paints, etc. were prepared using specific substances that exhibit a phenomenon known as thermochromism, and were used in various applications requiring temperature-sensitive markings. Examples of such specific substances or analogs exhibiting the above effects include mercury iodide, solid solutions of mercury iodide and silver iodide or copper iodide, ammonium vanadate, ammonium diuranate, dipyridyl copper thiocyanate, and cobalt phosphate. There are many transition metal compounds such as cobalt blue, cobalt rhodan, nickel chloride-urotropin double salt, etc. However, the above-mentioned compounds have any of the following drawbacks, and their applicability is extremely narrow. (1) Significant toxicity. (2) Discoloration occurs only when paper, fabric, etc. are exposed to unbearably high temperatures. (3) Effective only in the presence of moisture. (4) Color recovery is slow or irreversible discoloration. (5) There is no optional selection of color change temperature and color. Next, among the azo dyes, especially disperse dyes used for synthetic fibers such as acetate and polyester, there are many that exhibit considerable thermal discoloration. However, the discoloration mode of these pigments generally involves many indistinct changes to similar hues, and none of them lead to decolorization, and the speed of color restoration is generally poor.
It is hardly practical. Next, we will use cholesterin esters, which belong to the cold-temperature type, or mixtures of cholesteric and nematic liquid crystals, among the various substances called liquid crystals that have been making remarkable progress in recent years, and use them to investigate the extremely subtle characteristics of these substances. There is a method that takes advantage of changes in temperature and color. However, although these liquid crystals are generally quite unstable substances, difficult to handle, and extremely expensive, their color density is incomparably poorer than that of ordinary pigments, and they are simply It is difficult to notice any color change when directly printing or painting. Therefore, it has the disadvantage that it requires complicated ingenuity and its uses are greatly restricted. Furthermore, the recent expansion of pressure-sensitive copying methods has been remarkable, and it is possible to apply the combined coloring action of electron-donating coloring dyes and organic acids, especially phenols, which is the coloring mechanism of this method. , said 2
There is a method in which, in addition to the components, various organic solvents such as alcohols, esters, ketones, or amides are allowed to coexist, thereby making it possible to adjust the coloring as desired. The principle of this method is to take advantage of the relatively slow nature of the color-forming bonding state between the dyes and acids, especially phenols, and when the organic solvent reaches an appropriate temperature, the bonding state is established by its dissolving action. This is based on the fact that one of the phenols is taken away to inhibit the coloration, and that the temperature difference in the action causes reversible dissociation. By the way, the advantages of the above method are as follows. (1) The color-forming dye can be synthesized in a wide variety of hues and can be selected arbitrarily. (2) The color is deep and economical as only a relatively small amount of pigment is needed. (3) Compounded ink etc. can be applied directly without being affected by the type of adherend. (4) Depending on the type of solvent, the discoloration temperature can be set over a wide range of low and high temperatures. (5) Compared to liquid crystal, it is slightly inferior in chromaticity and sharpness of color change, but the ability to change color, fade, and restore color by mixing various pigments is sufficient for practical use. This method is considered the best method today due to the above advantages. However, there is one significant drawback to this method. In other words, the phenols, which are essential components, have extremely poor resistance to oxidation in the atmosphere and exposure to sunlight, and the phenols themselves gradually turn brown or lose their phenolic properties, resulting in printing etc. according to this method. There is a risk that it will deteriorate over time and become difficult to change color. The present inventor has investigated various substances that have excellent stability and exhibit a dissociation function equivalent to that of the phenols, and has developed a 1, 2, 3 triazole ring compound that can be substituted for such unstable phenols. The present invention was completed based on the new discovery that the compound completely satisfies these conditions and is extremely stable and effective. Next, the configuration of the present invention will be explained in detail. The present invention provides electron-donating coloring pigments and 1.
2.3 triazole compound and boiling point of 150℃ at room temperature
This is a thermoreversible color-changing ink composition which contains three components selected from the above alcohols and amides in coexistence. The electron-donating coloring dyes used in the present invention include 4,4,6'tris(dimethylamino)triphenylmethane/2'lactone, 4,4bis(dimethylamino)6'chlortriphenylmethane/2' Lactone, 4,4,6'tris(dimethylamino)triphenylmethane/2'phthalide, 2,7bis(dimethylamino)10benzoylphenothiazine,
Examples include 4,4bis(dimethylamino)triphenylmethane/2'lactone, 3diethylamino/7chlorofluoran, 3diethylamino/7,8benzfluorane, dibenzofluorane, etc. Many types of basic dyes and cationic dyes, which have been widely used in the dyeing industry, and some acidic dyes, are synthesized in large numbers and are easily available for pressure copying. It will be done. The electron-donating color pigments alone have yellow,
Each one is selected according to the color development of all hues ranging from red, blue, green, and even black, or multiple ones are mixed,
For example, 3,6 bisdiethoxyfluorane, which exhibits a yellow color, and 4,4,6' tris(dimethylamino)triphenylmethane, 2' lactone (blue) are used to make green, and 3, diethylamino, 7 It can be used as desired to obtain a desired color, such as mixing chlorofluorane (red) and 3,6 bisdiethoxyfluorane to produce orange. Next, components 1, 2, and 3 that characterize the present invention
Examples of triazole compounds include 1, 2,
3 triazole, 1, 2, 3 triazole 4 methyl 5 ethyl carboxylate, 4(5) hydroxy 1, 2,
3 triazole, 5(6) methyl 1, 2, 3 benzotriazole, 1, 2, 3 benzotriazole, 5
(6) Chlor 1, 2, 3 benzotriazole, 5(6) Methoxy 1, 2, 3 benzotriazole, 4(7) Nitro 1, 2, 3 benzotriazole, 5(6) Carboethoxy 1, 2, 3 benzo Triazole, 5 methoxy 7 nitro 1, 2, 3 benzotriazole, 4 amino 1, 2, 3 benzotriazole, 4 benzoylamino 1, 2, 3 benzotriazole, 4.
5, 6, 7 tetrachlor 1, 2, 3 benzotriazole, 4 hydroxy 1, 2, 3 benzotriazole, naphtho 1, 2, 3 triazole, 5, 5' bis 1, 2, 3 benzotriazole, 4(7) sulfoanilino 1, 2, 3 benzotriazole, 1.
Examples include diethyl 2,3 triazoledicarboxylate, and one or more of these can be used. The triazole compounds used in the present invention all have a structure having a hydrogen atom at the nitrogen atom at the 1st or 3rd position, and when the hydrogen is substituted with another organic group, etc., they do not show a discoloration phenomenon. It's inconvenient. The 1, 2, 3 triazole compound, like phenols, is not easily oxidized in the atmosphere or under sunlight, or in the presence of heavy metal salts, etc.
It is extremely stable and does not color, and therefore, the ink or its printed matter can withstand long-term storage and always exhibit stable performance. Next, constituting the third component of the present invention,
Alcohols or amides with a boiling point of 150°C or higher at room temperature include saturated monohydric alcohols such as octyl alcohol, nonyl alcohol, decyl alcohol, dodecyl alcohol, tetradecyl alcohol, cetyl alcohol, octadecyl alcohol, ceryl alcohol, myricyl alcohol, etc. unsaturated alcohols such as geraniol, nerol, linalool, oleyl alcohol, etc., as well as acetamide, caprylic acid amide, lauric acid amide, myristic acid amide, stearic acid amide, oxystearic acid amide, bisstearic acid amide, ayato Acetylamide, ayatoanilide, paratoluenesulfamide, benzoic acid amide, salicylic acid amide, oxalic acid amide, phthalic acid amide,
Examples include phthalimide, diethyl urea, thiourea, diphenyl urea, benzimidazole, etc.
In the present invention, it is desirable to use any one of the above because the color change temperature becomes sharper. The reason why the solvent for the triazole compound in the present invention is limited to alcohols or amides is that these solvents, like other solvents such as esters and ketones, have an unnecessarily strong dissolving power and cannot dissolve one dye. It does not impede the required discoloration properties when dissolved, nor does it have poor solubility like hydrocarbon solvents. The reason is that the gender can be easily predicted. Next, the reason why the boiling point of these alcohols and amides is set to 150℃ or higher is that those below this temperature generally tend to volatilize easily and are difficult to coexist with other components, and their dissolving power is large, which is inconvenient. It is from. By the way, among the alcohols and amides that have a boiling point of 150°C or higher at room temperature and are used in the present invention, those at a higher level are commonly in a solid state, and the higher the boiling point, melting point, or freezing point of the solid, the more discoloration occurs at high temperatures. It has certain properties, and those with lower levels are effective in low temperature ranges. In this way, the thermochromic temperature range of the present invention can be set to any desired temperature ranging from approximately -40°C to approximately 150°C, and significant discoloration is observed above and below the set temperature, which is reversible. It is something that is repeatedly repeated. The thermoreversible color-changing ink composition of the present invention comprises the above-mentioned three components, electron-donating color pigments 1, 2, and 3.
In order to coexist simultaneously with the triazole compound and either alcohols or amides with a boiling point of 150°C or higher at room temperature, basically a eutectic mixture or solvent solution of the three components, and further treatment of the capsule inclusions, etc. It is prepared by applying the printing ink, or by separately compounding it as a dispersion and mixing it with synthetic resins, natural resins, pastes, etc. to form a vehicle for the printing ink. It goes without saying that the above-mentioned capsule inclusion is the best method for such coexistence, and there are no particular restrictions on the type of resin used in combination, and it can be used for ordinary printing, textile printing, etc. Most of them are applicable. In short, these film-forming substances contain the three essential components without separating them from each other, and are more preferably those that have strong film-forming properties. In addition, in the capsule encapsulation consisting of the three components or the printing ink containing the three components used in the present invention, various chemicals such as surfactants, anti-drying agents, resin crosslinking agents, catalysts, viscosity Regulators, solvents, fragrances, colored pigments, fluorescent whitening agents, ultraviolet absorbers, oils and fats, metal soaps, waxes, extender pigments, pigment analogues, electrolytes, acids, alkalis, phenols, amines, antireduction agents , a rust preventive agent, etc. may be appropriately added, and such cases do not depart from the gist of the present invention. The thermoreversible color-changing ink composition of the present invention is obtained as described above, and then printed by gravure, letterpress, offset, silk screen, etc., or by roller, flat automatic screen, rotary screen, hand screen, etc. A desired pattern is applied to the substrate by printing, spraying, transfer, etc., unnecessary solvents are removed, and heat treatment is applied if necessary. In this way, printed matter is obtained which exhibits extremely stable thermoreversible color change. Next, the effects of the present invention will be listed. (1) If the thermoreversible color-changing ink composition of the present invention is used, it will not deteriorate in sunlight or the atmosphere for a long period of time;
It is possible to obtain thermoreversible color-changing printed matter that always exhibits stable performance. (2) The thermoreversible color-changing ink composition of the present invention does not require delicate or complicated operations unlike ink compositions containing liquid crystals, and it does not require 1, 2, or 1, which are the main components in the composition.
The 3-triazole compound is an extremely stable substance with little risk of toxicity such as heavy metals and phenols, and moreover, the chelation and anti-ultraviolet absorbing abilities of the compound can be expected to have even more advantageous effects. (3) The thermoreversible color-changing ink composition of the present invention is about -
Sensitive over a wide range of temperatures from 40℃ to 150℃
Moreover, it can be arbitrarily adjusted to change color in a variety of ways, making it extremely versatile. Example 1 10 parts by weight of ethyl cellulose (hereinafter, parts by weight are simply referred to as "parts"), Eslec BM-2 (trade name)
5 parts of Solgen #30 (trade name), 5 parts of finely powdered silica, 15 parts of methyl alcohol and 45 parts of isobutyl alcohol were made into a homogeneous viscous liquid, and then 15 parts of myristyl alcohol and 1, 2, 3 benzene A molten mixture consisting of 1 part of triazole and 3 parts of 4,4,6'tris(dimethylamino)triphenylmethane/2'lactone was poured into the viscous liquid under high speed stirring to form a homogeneous slurry. A color-changing blue printing ink was obtained. In addition, 4.
4.6′ Tris(dimethylamino)triphenylmethane・2′lactone, 3diethylamino・
A thermoreversibly color-changing red printing ink and a yellow printing ink were prepared using 7-chlorofluorane and 3,6-bisdiethoxyfluorane. Next, using the three colors of printing ink, continuous gravure printing of each color was performed on white high-quality paper (140 g/m ² ) using a floral pattern gravure plate (200ι, 30μ) separated into three primary colors, and methanol and isobutyl alcohol were added. After drying and removal, the entire surface was gravure overcoated (5 g/m ² ) with a transparent lacquer solution consisting of 16 parts of polystyrene resin pellets, 4 parts of SBR resin, and 80 parts of xylene using the same plate, and dried. In this way, a photo-like floral pattern was printed on the white high-quality paper, and the pattern suddenly disappeared when the room temperature rose above 35°C, and reappeared clearly below 34°C. It could be repeated any number of times. For comparison, paraphenylphenol, which is a phenol, was used instead of the 1, 2, and 3 benzotriazole blended in the blue printing ink of this example.
Inks were prepared using three types of β-naphthol and phenol resin powders, and the blue pattern plate was replaced with each ink to produce printed matter similar to the example. Observing the color change properties, it was found that all of the inks were at almost the same temperature. However, after 20 hours of irradiation with a carbon arc fade meter, the blue patterned areas of these prints turned yellowish brown to dark brown, thus changing to an olive color. , the density decreased significantly, the decoloring property deteriorated, and a brown pattern remained firmly at temperatures above 35°C, and the printed matter of this example was hardly affected by the irradiation, but the color was not affected by the irradiation. It showed a huge difference. Example 2 Table 1 shows the discoloration temperatures when several other alcohols were used in place of the myristyl alcohol used in Example 1.

[Table] Example 3 40.5 parts of 20% polyvinyl alcohol aqueous solution,
Add 2 parts of 4,5,6'tris(dimethylamino)triphenylmethane/2'lactone, 12 parts of myristyl alcohol fine powder, and 1 part of 5-ethyl, 1,2,3-benzotriazole, and finely disperse with a sand mill. Ta. Next, 30 parts of a 10% carboxymethyl cellulose aqueous solution was added as an incompatible aqueous glue solution to the aqueous polyvinyl alcohol solution, and the mixture was stirred for about 5 minutes to separate into two phases having a sea-island structure. 10 parts of a 20% aqueous solution of industrial tannic acid was added to the two phases and stirred, and after about 1 minute, 4 parts of anhydrous sodium sulfate and 0.5 parts of borax were immediately added and stirred to solidify the blue colored particles, and the next day,
Dilute with saturated saline solution 5, separate only the colored particles by decantation etc., then suspend the particles again in saturated saline solution 1, uniformly dissolve 5 g of glutaraldehyde in the liquid, I left it for a week. Thereafter, the granules were separated and thoroughly washed with water to obtain short columnar capsules with an average particle diameter of 0.1 mm (26.5 mm).
Department). Add 10 parts of the blue particles to Matsuminzole MR-500 (trade name, polyacrylic acid ester copolymer emulsion) 25
A yellow-green printing paste was obtained by mixing with 64 parts of an oil-in-water emulsion containing 1% of methyl cellulose and 1 part of Neocolor Yellow M3G (trade name, aqueous dispersion of organic pigments). Next, using the printing paste, rotary screen printing was performed on the cotton sateen fabric using a plain cylinder (40 meshes) on the entire surface, dried, and dried at 100°C for 3
Heated for a minute. Thus, when this printed fabric is viewed from a distance of approximately 0.4 m, it can be observed as a pointillist pattern consisting of small blue dots (0.1 to 0.2 mm in diameter) on a pale yellow background. Moreover, when observed from a distance of about 1 m or more, it appeared like a pale green marbled plain color that could be mixed with the ground color. When the temperature of the printed fabric reaches 35 degrees Celsius or above, the initially green color rapidly turns yellow and becomes just a plain yellow dyed fabric, and when the temperature falls below 34 degrees Celsius, blue spots appear again and the entire fabric is restored to green. Moreover, this change was observed over and over again. The printed fabric has good washing fastness and light fastness, but is slightly inferior in rubbing fastness. However, the discoloration and the stippled speckled pattern, which are the commercial values, are extremely effective, so there is no problem at all. Example 4 In advance, 2 parts of Coronate HL (trade name, polyisocyanate), 21 parts of cetyl alcohol,
Heat and dissolve 4 parts of 4,4,6'tris(dimethylamino)triphenylmethane/2' lactone and 3 parts of 1,2,3 benzotriazole/4-sulfooctylamide (described in Japanese Patent Publication No. 49-08778). ,
Add this to Poval #205 (trade name) 6.5% aqueous solution 200
A solution of 4 parts of Nitsuporan #125 (trade name, polyol) in 4 parts of methyl glycol acetate was gradually added dropwise to the solution of 4 parts of Nitsuporan #125 (trade name, polyol). After stirring at ℃ for 8 hours and leaving it until the next day, blue capsule-containing spherical particles were collected at room temperature so that they could settle (average particle size 0.012 mm,
Yield: approximately 35.6 copies). Similarly, instead of the cetyl alcohol and the blue coloring dye, a combination of myristyl alcohol and 3,6 bisdiethoxyfluorane, and a combination of lauryl alcohol and 3, diethylamino, 7
In combination with chlorofluorane, red capsule encapsulates were produced by an interfacial polymerization method similar to that described above. Next, 8 parts of each of the three types of granules were added and a self-crosslinking acrylic resin, butyl acrylate-acrylonitrile-butoxymethylacrylamide terpolymer (butyl acrylate 69.1%, acrylonitrile 23.1%, and butoxymethylacrylamide) 8.8% composition, melting point 80℃)
50 parts of a 46% by weight ethyl acetate/toluene (1:1) mixed solution, 20 parts of ethylene glycol butyl ether
1 part, 4 parts of talc, and 2 parts of stearylamide were uniformly mixed to prepare a brown printing ink at room temperature of 15°C. Using the printing ink, on parchment paper,
A mixed solution consisting of 5 parts of silicone resin, 5 parts of Amide Wax (trade name), and 90 parts of xylene is applied over the entire surface (8 g/m ² ) using a roll coater.One-point manga-like figures and inverted characters are applied to the peelable sheet surface. A pattern consisting of the following was screen printed (90 meshes) and then air-dried to obtain a thermal transfer sheet. The pattern layer forming side of the transfer sheet is brought into contact with the surface of the polyurethane synthetic leather sheet, and the pattern layer is formed by applying pressure and heating at 170°C for 5 seconds using a hot press machine, and then peeling off the paper. Transferred onto synthetic leather. In this way, the transferred synthetic leather was left to cool for a while, and by the time it reached room temperature, a one-point manga-like printed pattern of blue, green, and finally brownish color appeared. Actual measurement of the color change temperature of the printed pattern shows that it becomes brownish at temperatures below about 16°C, becomes green as it reaches 17°C, then becomes blue when it reaches 35°C, and then
At temperatures above 45°C, it became colorless and lost its color, and the above change was repeatable. The thermal transfer printed sheet of this example and the resulting polyurethane printed product both have excellent stability, and their color change performance does not deteriorate even after long-term storage, and their commercial value is extremely high. Example 5 Orthotoluenesulfuramide 200 parts, 4.
20 parts of 4/6'tris(dimethylamino)triphenylmethane/2' lactone, 4 hydroxy 1, 2, 3
10 parts of benzotriazole and 760 parts of 2% sodium alginate aqueous solution were made into a finely dispersed mixture in a ball mill, and then Permanent Red E5B (trade name)
A bluish-purple printing paste was obtained by blending 10 parts of an aqueous dispersion containing 25%. The paste was applied to the entire surface of aluminum foil (0.1 mm) using a knife coater at a coating amount of 2 mil,
A film was formed by drying. Next, add 1.5% to the entire surface of the coating film.
A 5% aqueous solution of hydroxypropyl cellulose containing barium chloride (isopropyl alcohol: water = 7:3) was applied at 2 ml using the same coater, and after air drying, heat treatment was performed at 180°C for 30 seconds. . In this way, a product with a structure in which color-changing dyes, etc. were encapsulated in barium alginate on the aluminum foil, and the surface was covered with hydroxypropylcellulose was obtained, and the colored foil was cut into strips with a width of 50 mm. Moreover, the adhesive was evenly applied to the back surface. Next, the adhesive back side of the foil was attached at right angles to the 36-inch width of a cotton broadcloth, and the cloth was passed over the cylinder of a steam cylinder dryer whose surface temperature had been adjusted to 150°C. Ta. In this way, the band-shaped foil on the cotton broadcloth, which is bluish-purple at room temperature, exhibits a band-like discoloration with red in the center and purplish-red at both ends, confirming the accuracy of the setting temperature of the cylinder, and also confirming the discoloration. When the cloth was separated from the cylinder, the color changed from purple to bluish-purple almost simultaneously. Incidentally, the same result was always obtained even when the color change and color restoration operations were repeated 500 times. Example 6 There are nearly infinite combinations of various amides and 1, 2, and 3 triazoles, each with different melting temperature and discoloration, but Table 2 shows that myristyl alcohol in Example 1 The figure shows the discoloration temperature when various amides are used instead of , and it is known that it is effective in producing discoloration effects at considerably high temperatures.

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Claims (1)

[Claims] 1. A thermoreversible color-changing ink composition containing in the coexistence of three components: an electron-donating coloring pigment, a 1-2-3 triazole compound, and either an alcohol or an amide having a boiling point of 150°C or higher at room temperature. thing.