JPH06316152A - Printed matter - Google Patents

Abstract

PURPOSE:To provide a printed matter capable of developing a color forming layer printed in a colorless state at any place without requiring the coating work of a color forming aid. CONSTITUTION:A color forming aid layer 7 consisting of a color forming aid 5 and a size 9 and preventing the contact of the color forming aid 5 with a color former 4 by the size 9 is formed on the upper surface of a color forming layer 6 printed using ink 3 containing the colorless color former 4 forming a color by the reaction with the color forming aid 5. The color former 4 is an electron donating color forming compd. selected from crystal violet lactone, malachite green lactone, 1,3-dimethyl-6-diethylaminofluorane, 6-diethylamino- benzo [3a]-fluorane, 3-cyclohexylmethylamino-6-methyl-7-anilinofluorane, benzoylleucomethylene blue and ethylleucomethylene blue and the color forming aid 5 is an electron acceptive coupling compd. selected from zinc salicylate, bisphenol A, an inorg. acid and an org. acid.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention allows a color-printed layer printed in colorless to be colored at any place without requiring a coating operation of a color-forming aid, and its handling is convenient. The present invention relates to a printed matter that can be suitably used for drawing lots and the like.

[0002]

2. Description of the Related Art It is widely known that, for example, PH indicators such as phenolphthalein change from substantially invisible colorless to visible colored by the action of acids and alkalis, and in recent years, such PH indicators have been known. There is proposed a printed matter in which a coloring area such as a hidden character or a hidden picture is printed by using as a coloring agent. In addition to the effect of concealing the coloring area, this one can give the user a high degree of interest and amusement by impressing the printed contents with a change in appearance when the coloring area is colored, surprisingness, etc. In addition to coloring, coloring books, and reference books, it is hoped that it will be used in various fields such as omikuji, bunsui, and lottery.

[0003]

However, conventional coloring of printed matter requires inconvenience such as the need to separately prepare a coloring aid which is an acid or alkaline substance, and as a result, the place of use is limited. The scope of its use was reduced. In addition, although there are various colors of PH indicators, since each has a unique coloring PH area, it is extremely difficult to develop a large number of PH indicators at the same time by using one color-forming auxiliary agent. Difficult, so these P
In the printed matter using the H indicator, there were few kinds of colors to be colored, and the appearance was monotonous.

Therefore, in view of such a situation, the inventor of the present invention has conducted extensive research on various dyes, pigments and the like. As a result, some of the electron-donating color-developing compounds known as dyes react with specific electron-accepting color-developing compounds to develop from colorless to their own unique color; The decolored state can be maintained by bringing the color compound and the color-developing compound out of contact with each other by using a sizing agent such as PVA (polyvinyl alcohol), and the color can be developed by bringing them into contact with each other by pressing or the like. In particular, when zinc salicylate and bisphenol A are used as the color developing compound, the effect of the color developing compound is lost due to the presence of water, the color-developing state returns to a colorless state, and this colorless / color-changing change is repeated. I have found that it can be returned.

That is, the present invention provides a color-forming aid in which a color-developing compound is brought into non-contact with the color-forming compound of the color-developing layer on the upper surface of the color-developing layer printed with an ink containing a specific color-developing compound. It is an object of the present invention to provide a printed matter that can form a colorful colorful hidden picture or the like based on the formation of layers and at the same time can develop the hidden picture or the like by a pressure contact work or the like to solve the above problems.

[0006]

In order to achieve the above-mentioned object, the printed matter of the present invention uses an ink containing a color-forming agent which forms a substantially invisible colorless to visible color by a reaction with a color-forming auxiliary. On the upper surface of the printed color forming layer, while forming a color forming auxiliary agent layer comprising the color forming auxiliary agent and the sizing agent and making the color forming auxiliary agent and the color forming agent non-contact with each other, the color forming agent is formed. Crystal violet lactone (blue); malachite green lactone (green); 1.3 dimethyl-6-
Diethylaminofluorane (orange); 6-diethylamino-benzo [α] -fluorane (red); 3-cyclohexylmethylamino-6-methyl-7-anilinofluorane (black); benzoylleuco methylene blue (blue); ethylleuco Methylene blue (blue); methoxybenzoyl leuco methylene blue (blue); 2- (phenyliminoethanedilidene) -3.3-trimethyl-indoline (red); 1.3.3-trimethyl-indolino-
7'-chlor-β-naphthospiropyran (purple); di-β
-Naphthospiropyran (purple); N-acetyl auramine (yellow); N-phenyl auramine (yellow); rhodamine B
Lactam (red); one or more electron-donating color compounds selected from the group A, and the color-forming aid is an electron selected from the group B consisting of zinc salicylate, bisphanol A, an inorganic acid, and an organic acid. It is characterized in that it is a receptive color developing compound.

[0007]

The above-mentioned electron-donating color-forming compound selected from the group A makes a color unique to each color-forming compound by making molecular contact with the electron-accepting color-developing compound selected from the group B.

Therefore, in the present invention, for example, the color-developing compound of the color-developing layer printed on the paper surface and the color-developing compound of the color-forming auxiliary layer formed on the upper surface of the color-developing layer are not brought into contact with each other by using a sizing agent. Since it is in the state, the color forming layer can be kept colorless.
Further, in this product, the color-forming layer and the color-forming auxiliary agent layer are brought into pressure contact with each other to bring the compounds into contact with each other, whereby the color-forming layer can be easily colored. Such pressure contact can be performed by rubbing or pressing a familiar hard object such as the surface of a nail and a coin, a writing instrument, or the like on the surface of the color-forming auxiliary agent layer. Therefore, it is possible to develop the color of the color-forming layer at any place by subjecting the printed matter to pressure contact without separately preparing a color-forming aid, which is convenient for handling.

Further, since these color changes are not based on the conventional PH changes, it becomes possible to simultaneously develop various coloring compounds into unique colors by using one color auxiliary agent, and a rich color hiding picture or the like. Can be printed. The colors after development are shown in parentheses. Group A includes the three primary colors, and these colors can be mixed, making it possible to create complex and profound colors such as photographs and paintings. Printing is also possible.

Moreover, when zinc salicylate and bisphanol A are used as the color developing compounds, after color development,
The color of the product can be instantly decolored by the presence of water adhesion, and the product value can be greatly enhanced by repeating this coloring / decoloring.

[0011]

DESCRIPTION OF THE PREFERRED EMBODIMENTS An embodiment of the present invention will be described below with reference to the drawings. In the figure, a printed matter 1 has a coloring layer 6 such as a hidden picture printed on the paper surface 2 using an ink 3 containing a coloring agent 4 that changes from colorless to colored, and the upper surface of the coloring layer 6 In this, a color-forming assistant layer 7 including a color-forming assistant 5 and a sizing agent 9 is formed.

In this case, the ink 3 is an anhydrous liquid in this example, which is formed by kneading the color former 4 with the vehicle. The color former 4 includes crystal violet lactone; malachite green lactone; 1.3 dimethyl-
6-diethylaminofluorane; 6-diethylamino-
Benzo [α] -fluorane; 3-cyclohexylmethylamino-6-methyl-7-anilinofluorane; benzoylleucomethylene blue; ethylleucomethylene blue; methoxybenzoylleucomethylene blue; 2-
(Phenyliminoethanedilidene) -3.3-trimethyl-indoline; 1.3.3-trimethyl-indolino-7'-chloro-β-naphthospiropyran;di-β-naphthospiropyran;N-acetylauramine; N -One or more electron-donating color compounds selected from the group A consisting of: phenyl auramine; rhodamine B lactam; As the vehicle, for example, a mixture of styrene resin, acrylic resin and the like with a solvent such as dioctyl phthalate and dimethyl phthalate can be used. A colorless ink can be obtained by stirring the vehicle and the color former for about 20 minutes. Can be obtained. The components of these vehicles and their blending ratios can be changed depending on the type of printing. For example, in the case of permeation drying such as high-speed printing, it is preferable to eliminate the resin material as a vehicle to reduce the viscosity. Further, in the color-forming compounds of group A, the colors can be mixed at the time of color development by combining them, and printing with a complicated and heavy color tone is possible.

The color-forming assistant layer 7 is a colorless and transparent thin layer covering the entire surface of the color-forming layer 6, and in this example, as shown in FIG. It has a single layer structure dispersed in.

The sizing agent 9 is an adhesive which is substantially colorless and transparent and fixes the color forming aid 5 on the color forming layer 6 in a non-contact state with the color forming agent 4, and is, for example, water-soluble carboxymethyl cellulose. (CMC), polyvinyl alcohol (PVA), sodium alginate, polyacrylic acid and the like can be preferably used. In particular, polyvinyl alcohol is more preferable because it has excellent transparency. In addition, those soluble in alcohol and general organic solvents can also be used.

Further, as the coloring aid 5, zinc salicylate,
In addition to bisphenol A, an electron-accepting color-developing compound selected from the group B consisting of inorganic acids such as hydrochloric acid, nitric acid, acetic acid and sulfuric acid, and organic acids such as citric acid, tartaric acid, malic acid and succinic acid is used. Then, the color developing compound and the sizing agent 9 are mixed and stirred to form a mixed liquid, and then these are coated to form the color-forming auxiliary agent layer 7 having a one-layer structure on the upper surface of the color-forming layer 6. At this time, since the molecules of the color-developing compound dispersed in the paste agent 9 are covered with the paste agent 9, the color-developing compound is not in contact with the color-forming compound in the color-developing layer 6 and the ink 3 is not colored and is in a colorless state. Can be maintained at.

In the printed matter 1 as described above, for example, the surface of the nail of a fingertip, a familiar hard material such as a coin or a pen is strongly rubbed or pressed against the surface of the color development aid layer 7 to form the color development aid layer 7. When the color developing compound and the color forming layer 6 are brought into pressure contact with each other, the separated color developing compound and the color developing compound come close to each other and are brought into a substantial contact state, so that the color development can be performed.

In the coating of the mixed solution, a water-soluble agent such as polyvinyl alcohol is used as the sizing agent 9 in order to prevent a part of the color-developing compound from being partially colored in the vicinity of the color-developing compound. It is preferable to use zinc salicylate and bisphenol A of Group B as the color-developing compound. That is, the mixed solution is composed of, for example, 2 to 16 parts by weight of polyvinyl alcohol, preferably 4 to 8 parts by weight, 5 to 20 parts by weight of zinc salicylate, preferably 8 to 12 parts by weight, and the balance of water. This is because the zinc salicylate or the like reacts with the color-forming agent 4 to cause the color-forming layer 6 to develop color, while the effect is lost due to the interposition of water, and the coloration is changed to a colorless state. Therefore, when the mixed solution is configured as described above, it is possible to reliably prevent false color development during coating,
It can improve productivity and quality.

Further, FIG. 3 discloses another example of the color forming auxiliary layer 7. In the figure, the color-forming assistant layer 7 includes a base layer portion 7A made of the paste 9 and a color-forming assistant layer portion 7 made of the color-forming assistant 5.
B has a two-layer structure, and the base layer portion 7A keeps the color forming agent 4 and the color forming auxiliary agent 5 out of contact with each other. In this case, it is preferable to set the thickness of the base layer portion 7A to be extremely small.

Further, the color-forming auxiliary agent layer portion 7B is formed only by the color-forming auxiliary agent 5, and in order to fix the color-forming auxiliary agent 5, for example, a small amount of a paste agent of the same kind as the paste agent 9 is mixed. Alternatively, the outer surface formed only of the color-forming aid 5 may be coated with a sizing agent that is the same as or different from the sizing agent 9. In this way, the underlayer portion 7
When the multi-layer structure having A is used, erroneous color development at the time of production can be avoided, and therefore, a free color developing compound belonging to the group B can be used as the color developing aid, and a sizing agent can be used. It is possible to use as the solvent 9 an alcohol and an organic solvent.

[0020]

INDUSTRIAL APPLICABILITY As described above, the printed matter of the present invention has a color-forming aid layer comprising a color-developing compound and a sizing agent formed on the upper surface of the color-developing layer printed with an ink containing a specific color-developing compound. Therefore, it is possible to develop the color of the color-forming layer at any place without separately preparing a color-forming aid, which facilitates the handling thereof and can greatly expand the range of utilization of hidden pictures and the like.

[Brief description of drawings]

FIG. 1 is a front view showing an embodiment of the present invention.

FIG. 2 is a cross-sectional view showing an example of a color forming auxiliary agent layer.

FIG. 3 is a cross-sectional view showing another example of a color-forming auxiliary layer.

[Explanation of symbols]

 3 Ink 4 Coloring agent 5 Coloring aid 6 Coloring layer 7 Coloring aid layer 7A Underlayer 7B Coloring aid layer 9 Paste

Claims (3)

[Claims] 1. A color-developing layer printed with an ink containing a color-developing agent that is substantially invisible from colorless to visible when reacted with a color-developing agent, and is coated with the color-developing agent and a sizing agent. And forming a color-forming auxiliary agent layer in which the color-forming auxiliary agent and the color-forming agent are not in contact with each other,
Crystal violet lactone; malachite green lactone; 1.3 dimethyl-6-diethylaminofluorane; 6-diethylamino-benzo [α] -fluorane; 3-cyclohexylmethylamino-6-methyl-7
-Anilinofluorane; benzoylleucomethylene blue; ethylleucomethylene blue; methoxybenzoylleucomethylene blue; 2- (phenyliminoethanedilidene) -3.3-trimethyl-indoline; 1.3.
One or more selected from the group A consisting of 3-trimethyl-indolino-7'-chloro-β-naphthospiropyran;di-β-naphthospiropyran; N-acetyl auramine; N-phenyl auramine; rhodamine B lactam. A printed matter, which is an electron-donating color-forming compound and the color-forming auxiliary is an electron-accepting color-developing compound selected from the group B consisting of zinc salicylate, bisphanol A, an inorganic acid, and an organic acid. 2. The color-forming assistant layer has a one-layer structure in which the color-forming assistant is dispersed in the sizing agent, and the sizing agent covers the color-forming assistant to form a color-forming assistant and a color-forming agent. The printed matter according to claim 1, characterized in that and are not in contact with each other. 3. The color-forming auxiliary agent layer has a multi-layer structure including a base layer portion made of the sizing agent and a color-forming auxiliary agent layer portion made of the color-forming auxiliary agent, and the base layer portion is the color-forming auxiliary portion. The printed matter according to claim 1, wherein the color-forming aid and the color-forming agent are not in contact with each other by being interposed between the agent layer portion and the color-forming layer.