JPS59200285A - Printed matter - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention is a method for printing on part or all of a paper surface using an ink containing a coloring agent that can change color by acting on a coloring aid that expires over time in an open state. Regarding the printed matter that was done.

Conventional printed matter has a predetermined standard color during the printing process, and there are very few cases in which the color is intended to change. In particular, there has been very little progress on how to incorporate information that readers do not want to see and information that they need to see in the same page and in a continuous arrangement, and it is necessary for readers to read all parts of the same page. There is no freedom of choice to be able to see it only at the one point in the hour where it occurred.'
-T, for example, for study reference books, explanations of problem sets, hints, explanations, etc., even if it is beneficial for the user to have it in a place that is continuous with the problem or in the problem text, that place should be left blank. It is printed in a separate volume or outside the book. The problem with such conventional reference livestock is that it takes time and effort to compare and contrast all the answers, deciphering, etc., and it is difficult to remember them.

One way to deal with this problem is to fill in the printed text with a red marker and pass it through a green filter.The red part also becomes black, making the text invisible. There are some parts that were used, but with this method, you can only use those that are printed in normal letters from the beginning, so there is a problem that the answer comes into view at first, and furthermore, when using it, you always follow the green filter. There are some inconveniences that you have to deal with, and your ability to do so decreases.

In contrast to the above-mentioned conventional printed matter and memorization cents, the present invention prints with ink containing a coloring agent, and the user can apply a bath liquid containing a coloring aid to the printed area when necessary. By applying it, it is possible to noticeably fade the color after it has developed. This can be repeated. In the above case, the printed area is usually colorless, but if it is colored at the time of printing and is used, it is decolored by applying a coloring aid liquid, and then the same coloring aid is applied. Color development and natural decolorization can also be carried out by applying a coloring agent or another coloring auxiliary liquid. In the former case, it is very convenient to use it in the M valley of a normal question book, etc., and in the latter case, for example, when used in subnotes, it is very convenient for the user to select the word or phrase that he or she wants to erase. L:l] The color or non-color at the time of printing can be arbitrarily selected depending on the combination of the hardness of the coloring agent and the coloring auxiliary agent. The above is a case where the coloration aid is applied in the form of a solution, but it is also possible to use a gas or a solid.

In the present invention, discoloration refers to all forms of discoloration, including color development, discoloration, and discoloration in a narrow sense.
The same applies to I], which refers to coloration that does not fade but only changes color in a narrow sense.

In addition, areas other than those to be printed with the ink of the present invention can be printed with ordinary ink, and there are no restrictions on the dyes and pigments used.

Table 1 shows representative examples of colored rhinoceros that can be used in the present invention.
Color-changing dyes whose typical coloring pH ranges are shown in
In addition to pH changes, flavonoid color threads that change color depending on the presence or absence of ferric chloride and methoxyl groups,
Furthermore, in addition to Q-1 changes such as andonanine and betacyanine color charts, castinoid pigments, chlorophyll pigments, and quinone pigments, there are specific color changes depending on each pigment, such as specific effects, redox, and the presence or absence of metal ions. Contains unique pigments that can change color upon processing.

Further, it is also possible to add a coloring aid described later to the coloring agent ink.

Next, the coloring aid used in the present invention is such that the coloring agent has a pH of
For indicators or color-changing dyes, p I-1 is iN MM
Acidic, alkaline or neutral compounds or other solutions and gases. For u2 compounds, one salt, one il
Strong enemies such as acids, strong enemies such as acids, carbon dioxide, sulfur, etc., citric acid, tartaric acids, strong enemies such as phosphoric acid, ammonium sulfate, fIIHW copper, ammonium chloride, etc., and salts of weak bases, etc. It is a water bath solution with a pH in the range of 1 to 7.Alkaline compounds include strong bases such as sodium hydroxide and potassium hydroxide, salts such as sodium urate and potassium carbonate, ammonia R1 liquid and gas, There are organic products containing ethanolamine and ingropanone groups.As neutral coloring aids, in addition to baba, alkali neutralization salts and bath numbers, hydroalcohols, ketones, and other good sea bath agents and their vapors. , or gas and smoke components generated by burning them.If the coloring agent is a flavonoid colorant, in addition to the above, a reducing agent of magnenium salt,
Metal ions such as iron and copper tin can be used. Method i-1 for natural decolorization after coloring: There are various methods, but one method is to apply a volatile coloring agent, apply a gas, or apply a liquid or gas-rich solid thereof. Another method is to take advantage of the property of decoloring upon drying. For example, when using a pH finger indicator sound, a coloring agent is appropriately selected and the pH value is
The color is removed by washing the conditioner, and the color is erased by drying, and the color develops by spraying with water, alcohol, ketone, etc. It can also be colored (changed).

These methods can also be used in combination. Even if the color does not naturally fade (discolor), it is also possible to achieve the same changes as above using a writing instrument, etc. that separately contains a coloration aid for color development and a coloration aid for erasure. .

Solvents for preparing the above coloring agents as ink, 6811 preservatives include water, alcohol, ketones, polyhydric alcohols, Ether Asahi, Ester 'JA, Yoshi 47F N,
Nitrogen compounds, 1llt: yellow compounds, organic bath agents such as hydrocarbons, and each A thickener, rosin, shellac, cellulose plastic, acrylic, epoxy, silicone fit +1
By adding a phenol resin or the like, it can be prepared as either a water-based ink or an oil-based ink. Solutions for adjusting the coloration aid include water, alcohols, and the various Nantsuki solvents mentioned above. Moreover, various thickeners, preservatives, etc. can be mixed as additives. Ammonia or various organic compounds having an amine group can also be used as a gas. It is also possible to make coloring or decolorization (change) by hardening the ``Madairosukeoki'' with soap, etc., and making adjustments such as adding moisture at the time of use. Tools for spraying coloring aids include sugley, and felt cotton impregnated with the coloring aid or its solution is placed inside a bag sealed with molecular film, and the coloring agent is marked with coloring agent ink. Color can also be created by inserting a paper surface into it. In this case, the color is erased by removing it from the bag. In addition to brush pens, tools for applying color aids include felt hen and brush pens. In addition to ft.
Tissue paper, a container with a trousers attached to the tip, etc., or any other material may be used.

Next, the printing substrate used for printing of the present invention includes valves,
Paper types include high-quality general-purpose paper, Japanese paper, synthetic paper, and surface-treated paper, and it is desirable to be able to withstand repeated application of the coloring aid solution. In addition to the above-mentioned papers, it can also be applied to printing on polymer films, natural plant films such as lichens, moss boards, wafers, wooden boards, glazes, and three-dimensional objects made of the above materials as well as board-shaped ones. can.

By using the invention with the above structure, for example, if you apply it to the above-mentioned character 2 reference document, you can practice continuously without having to compare and contrast the answers and 1,000 words with the answers in the separate volume. I can continue.

Also, if you apply it to rote learning such as English, you won't need to use a dictionary to look up the meaning of ``tansho'', and you will not need to use a dictionary to look up the meaning of ``tansho''. You can read a wide variety of English texts without the disadvantage of being too busy and unable to be effective.

The above are characters and graphics printed with coloring agent ink; it is the same whether it is originally colorless or colored, and in the case of color, a method such as erasing it from a known singleton can be used.

Referring to the present invention in this way, -! When applied to J: Power, it is possible to create a reference book with a very high ratio and with a lot of choice in how to use it.In addition, it can be used not only for Sanpoki, but also for various reading materials such as mystery novels, quizzes, games, and Go. , it can be interestingly applied to various games such as shogi.

Application example Printing inks enriched with the following coloring agents were prepared.

Ethanol 100 parts Globylene glycol 20 parts Surfactant 3 parts Shellac 2 parts Thymol phthalein 0.5 parts or more of printing indigo was used to print only the page on a letterpress printing machine, and other questions were printed using normal N-table ink. We used high-quality paper for the "Monday" paper, and created a problem set. A part of this is shown in FIG. 1(a).

Next, a coloring aid bath liquid was prepared with the following composition and impregnated into a brush pen.

5% ammonia aqueous solution 100 parts Ethyl alcohol 60 @ ethylene glycol 20 parts When the above (6) is applied to the answer area, red letters appear as shown in Figure 1 (b), and the color disappears after a few seconds. As a result of testing by selecting 20 people at a time, comparing the case where it was created in a separate volume and the case where it was used directly, and the case where it was used directly, the present invention was tested. When using the automatic method, the efficiency is about 2.3 times lower than that of the side-by-side method.

[Brief explanation of the drawing]

Figure 1 (a) is one group of problem sets applied to this book, (b)
) is colored to indicate the state of the problem when using the question book. Tomo '3t' ni -1 bow 1 l) ノ, 川 Ｇａｎｔ ｄｅｒ ｔｅ:) Box side Figure 1 (a) No. 3, person making the amendment 4, attorney's specification 1, title of the invention in printed matter 2, claims (11-By acting on a coloring aid that expires over time, the color naturally fades after coloring) A printed matter printed on a part or all of 7Ω using a ζ1 ink containing a coloring agent. (2) The coloring agent is a pH indicator having a colorless pH range, according to claim 1. Printed matter. Printed matter. (4) The coloring aid is a volatile pH adjuster 3
6 DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a printed matter using a color former ink which can develop color by the action of a coloring aid and which can be discolored over time. Conventionally, printed matter is printed on a printing medium such as a paper surface using visible ink, and it is hardly intended that the printed color change after printing. Furthermore, there has been no proposal for a system in which the invisible printed content can be changed to become visible depending on the reader's wishes or choices. Therefore, for example, study guides, answers to problem sets, hints, etc.
Even though it may be beneficial for users to write explanations along with the questions or in the question text, in conventional printed materials that use only visible ink, they are placed at the end of the book to prevent answers and other information from being read immediately. It is printed in a separate volume or in the margin. With such conventional reference documents, it takes time to compare and contrast questions, answers, explanations, etc. As a solution to some of these problems, there is a method that camouflages printed characters using colored dots and makes them visible by passing them through a filter of a predetermined color, but this method requires a filter when reading, and It is difficult to display fine or complicated characters, and it is also not easy to use.Furthermore, there are colored parts other than black on the paper surface, which makes it look bad, and it takes time to print. There is. As a result of various studies regarding the convenience of the readers and users in handling the above-mentioned annotation columns for answers, etc., the present invention has been developed to make the colorless and invisible annotation columns visible at any time as desired, and to erase the color over time. The present invention has been completed by finding a way to solve the above-mentioned problems, and the printed matter of the present invention naturally fades after coloring by interacting with a coloring aid that expires over time. It is characterized by printed matter printed on part or all of a printing medium using a colorless ink containing a coloring agent. The notes section is printed with a colorless ink containing a coloring agent, and the user can color it by applying a time-resistant coloring aid to this printed area when necessary. After that, the color can be naturally faded, and this can be done repeatedly. Here, a pH indicator having a colorless pH range can be used as a coloring agent. Examples of such I)H indicators include γ-dinitrophenol, m-nitrophenol, O-dil-lophenol, p-nitrophenol, cyanine, α-naphtholphthalein, phenolphthalein, cresolphthalein, and thymolphthalein. rhein, ethylbisacetic acid,
Bromophenol purple, hexano] xylend,
There are varieties such as heptamethoxy red, which are used depending on the color to be expressed. In addition to one type, a mixture of a plurality of types may be used. In addition, as a coloring aid, an acidic, alkaline, or neutral compound or a solution thereof that can adjust pH-t,
It is possible to use a drug that loses its effectiveness over time and expires over time. Expiration over time is caused by drying due to volatilization or evaporation of water, and due to expiration, the coloring agent loses its coloring ability. Among pH adjusters that expire due to volatilization, those with alkaline pH in the range of pH 7 to 14 include ammonia, monoethanolamine, ethylamines, propylamines, 2-ethylhexyloxypropylamine, Examples include -ethoxybutylamine, 3-methoxypropylamine, diisobutylamine, 5eC-butylamine, isopropanolamines, ethanolamines, 2-ethylhexylamine, and ethyleneamines. Volatile coloring aid pH 1~
Examples of those having a pH in the range of 7 include acetic acid, formic acid, etc. The loss of ion dissociation ability of the coloration auxiliary agent due to drying of water is utilized. Although there are many pH adjusters that have such properties, it is difficult in practice to completely dry water, so use one that loses ionic dissociation ability when the concentration exceeds a certain value. Examples of such pHi adjusters include diisopropanolamine, triisopropanolamine, jetanolamine, sulfur and lithium hydroxide, and potassium hydroxide. Water, alcohols, and polyhydric alcohols can be used as solvents for mixing these coloration aids. In addition, coloring aids can be used in combination of multiple types, and those with a pH of 1 to 7 and those with a pH of 7 to 14 can be used in combination, and some of them are nonvolatile or do not expire even when dried. It can also contain. in this case,
It is best to exclude substances that react and form salts upon mixing. The type and concentration of the coloring aid are determined by the pH value at which the coloring agent develops color. In addition, for coloring agents such as nitrophenols whose pH range for color development is close to neutral, the coloring agent ink vehicle may be pre-mixed with a nonvolatile pH adjuster such as dilute sulfuric acid, tartaric acid, or citric acid. pH of
Adjust lower. This helps prevent color development after printing. The time it takes for the color to disappear after it develops can be changed by adjusting the evaporation rate and drying rate of the color change aid, but when applied to the notes section of teaching materials, etc., it is best to leave the color for 1 to 10 minutes, and for a long time. It is undesirable for the color to continue to develop until the next exercise. Color former ink contains a color former and is usually adjusted to a colorless state. It is also possible to prepare the composition so that it becomes colorless by drying after printing. To prepare a color former ink, a solvent for the color former, such as alcohol, is used, and polyhydric alcohols, surfactants, various resins, etc. are added. Note that when coloring is performed using a coloring aid such as water or alcohol after printing, it is preferable to use an aqueous coloring agent ink vehicle as the coloring agent ink. Dimethyl sulfamide, dimethyl sulfoxide, alcohols, polyhydric alcohols can be used as additives to prepare the aqueous color former ink vehicle, and rosin, shellac, guar gum, methyl cellulose, and ethyl cellulose can be used as thickeners. can. Coloring agent inks can also be prepared by grinding the coloring agent into fine particles and then kneading it into various ink vehicles, or by adsorbing the coloring agent dissolved in a solvent to an appropriate inorganic or organic powder. Afterwards, it can be kneaded into various ink vehicles, and the color former ink can be prepared by any method. Table 1 shows examples of combinations of coloring agents and coloring aids that can be used in the printed matter of the present invention, the flH value at which the coloring agent develops color, that is, the coloring pH, the pH value at which the coloring agent disappears, that is, the coloring pH1, the type of color, The approximate value of the time required from color development to natural discoloration by adding a color development aid is shown. The coloring pH is a value at which the printed portion has a density that can be easily recognized or read by the human eye due to the action of the coloring aid. Further, the decoloring pH is a value at which the color is almost undetectable to the naked eye, and the range of discoloration and decolorization can be freely selected by adjusting the difference between the two values. The time from color development to discoloration can be adjusted by adjusting the concentration of the pH adjuster of the coloring agent, the type of additives, etc. The coloring agent ink contains denatured alcohol as its vehicle structure.
75 parts, water 15 parts, surfactant 10 parts, tartaric acid 0
Add ~10 parts. The time values shown at the end of Table 1 exemplify the case where the vehicle is printed with a coloring agent ink containing the amount of coloring agent added in Table 1, and the time values are as follows. The concentration of the pH adjuster in the coloring agent ink can be adjusted within the stated time range depending on the concentration of the pH adjuster in the coloring aid, additives, liquids, and gases (vapors). It is. In addition to the so-called felt ben, tools for applying the coloring aid to the printed matter include ben type markers such as underline markers having an acrylic tip or a polyester tip at the tip. It may also be applied using containers with a sponge-like application tool at the tip, a spray, or a brush, rubber, sponge roller, etc. after being stored in a container. Furthermore, an impregnated material such as felt, sponge, cotton, or polymer filter impregnated with a volatile coloring aid liquid may be placed in the container and the vapor may be applied. A separate chamber 7 communicating with the impregnating material 4 through a pore 5 is provided in the transparent container 3, and by inserting a piece of paper, a card 9, etc. containing a portion printed with coloring agent ink into the separate chamber 7, the vapor is made to act. It's okay. Note that the printed portion of pieces of paper, cards, etc. can be visually recognized through the container 3, and the color can also be naturally erased by taking them out. Alternatively, the container can be formed into a felt-ben shape with chips removed, and only the steam can be applied thereto. The printing material can be used for various shapes and purposes, including books such as books, newspapers, weekly publications, etc., papers such as pamphlets and catalogs, and three-dimensional objects such as packaging boxes and globes. The material of the printing medium includes wood-free paper, medium-quality paper, Western paper such as historical paper, Japanese paper, surface-treated paper, synthetic paper, and the like. For the purpose of increasing the number of times of repeated use, high-quality paper, medium-quality paper, etc. are preferable, but they are selected depending on the purpose of use and considering profitability. In the same sense, it is possible to print not only on paper but also on starchy materials such as fibers, wood, rubber, synthetic polymers, and wafers by subjecting them to appropriate surface treatments. Printing can be performed using various printing methods such as letterpress, gravure, and stencil printing, and can be printed on a part or all of the paper surface, for example, along with the visible part using black ink. In addition, the suggestion columns for questions, points requiring notes, etc. are made visible, and the spaces between notes for answers, etc. are printed with the coloring agent ink according to the present invention to make them invisible. As mentioned above, these invisible parts are colored
When the coloring aid is applied, the color develops and becomes visible, and the color disappears as the coloring aid expires over time. As mentioned above, when the printed matter of the present invention is used, for example, in various teaching materials, the invisible parts such as between the notes can be colored by applying the coloring aid, thereby making the spaces between the notes visible, which eliminates the trouble of checking answers. can be shortened, and can be carried out without interrupting the flow of the exercise. In addition, the changes in color development and decolorization are more interesting for practitioners,
To prevent learning from becoming a monologue, it greatly improves learning efficiency compared to conventional teaching materials. In addition, for the purpose of language acquisition, foreign language reading material, such as translations of English newspapers and foreign weekly publications, and the annotations between annotations can be made invisible in advance, and the annotations can be made visible if desired, thereby reducing the hassle of looking up a dictionary. It can also be omitted, the amount of reading can be increased dramatically, and it can have many effects, such as helping to improve language skills. Embodiment 1 A case where the printed material is used as a learning reference book shown in FIG. 1(a) will be explained as an example. The question section a is printed with an ordinary ink containing a black pigment, and the furigana, that is, the annotation section for answers, etc., is printed on the right side with the coloring agent ink according to the present invention, which is normally invisible. ing. Note that the same vehicle as described in connection with Table 1 was used for the coloring agent ink. Phenolphthalein was used as a coloring agent, and the coloring aid was adjusted to have the following composition. Ammonia 1 part Caustic soda 0.2 parts Water 100 parts Thickener 0.5 parts Surfactant 9 parts The above solution was impregnated into a core filter for a marquee jigben, in which polyester fibers were wrapped with polyethylene film, and a chisel cut part was attached to the tip. A marking ben was made with a polyester chip attached. Raise the problem statement in Figure 1 (a) on the marking bench tliIa
When tracing the right side of the vertical line, the furigana, that is, the annotation space, turns red as shown in Figure 1 (b), and in the spring, the color disappears after 5 minutes. After drying, the above changes could be repeated again, and the product could be used repeatedly even after a long period of time. Example 2 Using α-naphtholphthalein as a coloring agent, printing was carried out with a coloring agent ink of the same vehicle. In addition, the coloring aid was adjusted to have the following composition. 3-Ethoxypropylamine 15 parts Denatured alcohol 50 parts Tartaric acid
After printing 35 copies, a coloring auxiliary agent is applied to develop a blue color, which then naturally disappears in about 2 minutes. Example 3 After printing with the same coloring agent ink as in Example 2, when vapor of a coloring aid consisting of a 1-10% aqueous solution of ammonia and amine is applied, a blue color is obtained, and when the action is stopped, a blue color is obtained. Discolored naturally. The time required for natural decolorization varied depending on the steam concentration, but was about 1 to 10 minutes. It should be noted that other coloring agents can also be similarly caused to change in color development and natural decolorization. 4. Brief description of the drawings FIG. 1(a) is a plan view showing a part of the contents of the printed matter according to the present invention, and FIG. 1(b) is a plan view showing a state in which color is developed by the action of a coloring aid. , FIG. 2 is a cross-sectional view illustrating a container containing a coloration aid. (a) - Remarks column, (b) - Notes column. Patent applicant Seiji Kawashima Agent Patent attorney Tadashi Naemura Figure 1 (
a) No. 1-56]

Claims (6)

[Claims] (1) Printed matter printed on part or all of the paper surface using ink containing a coloring agent that can change color by acting on a coloring aid that expires over time in an open state. (2) The printed matter according to claim 1, wherein the coloring agent is a pH indicator. (3) The printed matter according to claim 1, wherein the coloring agent is a color-changing dye. (4) The printed matter according to claim 1, wherein the coloring aid is a pI-f adjuster. (5) The printed material described in item 1 of the patent application, wherein the coloration aid is a chemical substance that acts with a coloration agent such as an ion and acts as an element that causes coloration. (6) The m-printing material according to claim 1, wherein the coloring aid is water, alcohol, ketones, or the like.