JPS5942639B2 - energized recording paper - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to an energized recording paper that produces different colors depending on the magnitude of applied power and that enables clear recording to be obtained.

As a conventional recording method for obtaining two-color recording by energization, there is a method that combines an energization recording method and a discharge recording method. This method takes advantage of the fact that when recording at low voltage, the heat-sensitive material develops color due to current recording, while when recording at high voltage, the conductive layer is destroyed and becomes similar to discharge recording. This method exposed the color of the colored layer. This two-color coloring method has a simple device configuration and is capable of recording two colors just by changing the magnitude of the voltage.However, in actual recording, the color produced when recording at a low voltage is different from the color produced at a high voltage. Since it remains even when recorded at high voltage, the color becomes muddy and clear recording cannot be obtained when recording at high voltage.
FIG. 1 is a diagram for explaining a multicolor recording method using a combination of current recording and discharge recording.

In this figure, 1 is a support such as paper, on which a colored layer 2 and a conductive layer 3 are provided, and further on which a conductive coloring layer 4 containing a heat-sensitive coloring material is provided. 5 are configured. 6 is a recording needle, □ is a return electrode, and 8 is a power source.

Now, in the state shown in FIG. 1, the current from the power source 8 is transmitted from the recording needle 6 to the conductive coloring layer 4 - the conductive layer 3 - the conductive coloring layer 4 -
It flows to the return electrode T.

Joule heat is generated in the conductive coloring layer 4, which has a higher resistance value than the conductive layer 3. At this time, since the area of the recording needle 6 is smaller than that of the return path electrode 7, the conductive coloring layer 4 in contact with the recording needle 6
The amount of Vegure heat generated is greater than in other parts. Due to this heat generation, the heat-sensitive coloring material present therein develops color, and energization recording is performed. On the other hand, if the voltage of the power source 8 is increased, heat generation becomes too large in the vicinity where the recording needle 6 contacts, and the conductive coloring layer 4 and the conductive layer 3 are destroyed. As a result, the colored layer 2, which has been covered up to now, is exposed, and an image formed by the colored layer 2 is recorded by so-called discharge. At this time, by making the color of the colored layer 2 and the color of the conductive coloring layer 4 different, recording in two colors becomes possible. FIG. 2 is a schematic diagram of the energized recording paper 5 showing the state after recording, in which the recording section 9 is a recording section based on energization recording, and the recording section 10 is a recording section based on discharge recording.

By the way, the recording unit 10 using discharge recording is actually the second
Instead of a hole having a simple shape as shown in the figure, a part of the conductive coloring layer 4 and a part of the conductive layer 3 remain. Furthermore, since the conductive coloring layer 4 is colored, the color of the colored layer 2 mixes with the color of the conductive coloring layer 4 in this state, resulting in a drawback that the image is not very clear. This invention has been made in order to eliminate the above-mentioned drawbacks, and an object of the present invention is to provide a current-carrying recording paper that can erase the coloring of the conductive color-forming layer and obtain a clear image when recording is performed using discharge recording. This is the purpose.

This invention will be explained below. FIG. 3 shows an embodiment of the present invention, in which the heat-sensitive coloring material contained in the conductive coloring layer 4 is decolored in order to erase the coloring of the conductive coloring layer 4 during discharge recording. This is because the agent 11 is contained in the colored layer 2.

The other configurations are the same as those shown in FIG. Since the decoloring agent 11 is normally separated from the conductive coloring layer 4 by the conductive layer 3, it does not perform any decoloring action, but when recording is performed by discharge recording, a part of it is colored during recording. As the layer 2 is colored, it moves and adheres to the conductive coloring layer 4 remaining in the recording section 10 (FIG. 2). As a result, the colored material in that area disappears, and the color of the colored layer 2 becomes clearly visible. At this time, the color erasing agent 11, which is colored in the same way as the colored layer 2, moves to the surface, erasing the coloring of the heat-sensitive coloring material, and at the same time moves the colored material in the colored layer 2 to the surface, A clearer image can be formed. FIG. 4 shows another embodiment of the present invention. In this embodiment, a layer 12 containing a colored layer 2 and a decoloring agent 11 and colored in the same color as the colored layer 2 is shown in FIG.
It is separated into.

The recording principle is the same as that of the embodiment shown in FIG. 3, so its explanation will be omitted. Next, the composition contained in each layer will be explained.

The heat-sensitive coloring material contained in the conductive coloring layer 4 consists of a leuco dye and a color developer. As the leuco dye, leuco forms of triphenylmethane dyes, leuco forms of fluoran dyes, etc. are used.

Specific examples include 3,3-bis(P-dimethylaminophenyl)-6-nitroptalade, 3,3-
Bis(P-dibutylaminophenyl)-putalade, 3
,3-pis(P-dimethylaminophenyl)-4,5,
6,7-tetrachloroptalade, 3,3-bis(P-
dimethylaminophenyl)-putalade, 3,3-bis(P-dimethylaminophenyl)-6-dimethylaminoptalade (crystal violet lactone), 3,
3-bis(P-dimethylaminophenyl)-6-aminoptalade, 3-dimethylamino-6-methoxyfluoran 7)-acetamino-3-dimethylaminofluoran 3-dimethylamino-5,7-dimethylfluoran , 3-diethylamino-5,7-dimethylfluorane,
3,6-bis-β-methoxyethoxyfluorane, 3,
6-bis-β-cyanoethoxyfluorane, 9-P-nitroanilino-3,6-bis(diethylamino)-9-
lactam of xanthenyl-10-benzoitukaside (rhodamine B lactam), 9-P-nitroanilino-3,
Examples include lactams of 6-bis(dimethylamino)-9-thioxanthenyl-10-benzoic acid.

Color developing agents include phenol compounds and organic substances.

Examples include 3,5-xylenol, thymol, 4-tert-butylphenol, 4-hydroxyphenoxide, methyl-4-hydroxybenzoate, 4-hydroxyacetophenone, α-naphthol, β - Naphthol, catechol, resorcinol, hydroquinone, 4-tertiary octylcatechol, 4,
4-Secondary butylidenedienol, 2,2'-dihydroxydiphenyl, 2,2'-methylenebis(4-
methyl-6-tert-butylphenol), 2,2
/-bis(4'-oxyphenyl)propane, 4,4'
-isopropylidene bis(2-tertiarybutylphenol), 4,4'-secondary butylidene diphenol, birogallol, phloroglycin, phloroglucinic acid, boric acid, oxalic acid, maleic acid, tartaric acid,
Examples include citric acid, succinic acid, benzoic acid, stearic acid, gallic acid, salicylic acid, 1-oxy-2-naphthoic acid, 2-oxy-P-toluic acid, 0-oxybenzoic acid, and 4-oxyphthalic acid.

As the substance that imparts conductivity to the conductive coloring layer 4, fine powders of conductive substances such as zinc oxide, tin oxide, indium oxide, copper iodide, and titanium oxide, and conductive agents such as polymer electrolytes and oligomers are used for heat-sensitive coloring. It is carried out by including it in the layer.

Examples of the binding material for binding the conductive coloring layer 4 include an ammonia aqueous solution of isobutene maleic anhydride, hydroxyethylcellulose, carboxymethylcellulose, methoxycellulose, polyvinyl alcohol, polyvinylpyrrolidone, polyacrylamide, polyacrylic acid, gelatin, starch, and the like. Use an aqueous solution of

As the decoloring agent, polyethers, glycols, and organic titanium compounds can be used.

Examples of polyethers include polyoxymethylene, polyethylene oxide, polyoxydecamethylene, and derivatives thereof.

Glycols include polyethylene glycol monolaurate, polyethylene glycol monostearate, polyethylene glycol monooleate, polyethylene glycol tallow, fatty acid ester, sorbitan monolaurate, sorbitan monopalmitate, sorbitan monostearate, polyoxyethylene. Zorbitan monolaurate, polyoxyethylene alkylamine, polyoxyethylene oleyl ether, polyoxyethylene cetyl ether, polyoxyethylene alkyl allyl ether, polyoxyethylene sorbitan monooleate, polyoxyethylene alkylamide, polyoxyethylene dodecyl mer Examples include cabtan ether and polyalkylene glycol derivatives.

Examples of organic nitrogen compounds include NN-(diphenyl)guanidine, guanoline, and N-acetylguanidine.

In addition, the support 1 can be paper made from wood pulp, hemp pulp, bast fiber, linter, rayon, synthetic pulp, or other raw materials alone or mixed together, synthetic paper such as nonwoven fabric, or synthetic resin film. be.

Next, a specific example will be explained.

Specific Example 1 Polyethylene glycol monolaurate containing 3% by weight of rose bengal was melted and applied onto a red-colored high-quality paper so that the coating amount was approximately 89/m''.

Aluminum was vacuum-deposited onto this. Next, the coating liquids consisting of A, B, and C were separately dispersed in a ball mill for 24 hours, and then mixed in the ratio of A/B/C = 1/2/5. Furthermore, 30 parts of isoptylene-maleic anhydride copolymer aqueous solution (15%) was added to 80 parts by weight of the mixed liquid.
The coloring layer coating solution obtained by adding parts by weight and mixing well was coated on the support 1 so that the coated amount after drying was 8 g/771'', and when it dried, a background with a whiteness very close to natural color was obtained. A colored recording paper was obtained.

The above recording paper was scanned at a stylus force of 10 g and a scanning speed of 1.2 m/Sec.
When recording was performed using a cylindrical scanning recording tester with a recording voltage of 45 V, a blue recorded image was obtained.

On the other hand, when recording was performed under the same conditions except that the recording voltage was increased to 70 V, a red recorded image was obtained.

This red image had greater red clarity than a similar recording paper without a decolorizing agent layer, and blue and red could be clearly distinguished.
Specific Example 2 A 10% aqueous solution of polyethylene oxide (molecular weight 10,000) containing 3% by weight of rose bengal was coated on white high-quality paper at a coating weight of 89/I after drying.

Aluminum was vapor-deposited thereon, and a recording paper was obtained in the same manner as in Example 1. This recording paper also produced a blue image at 45V and a red image at 75V using the above-mentioned tester. As explained above, in the present invention, since the current-carrying recording paper is constructed by containing a decoloring agent, even in the case of so-called discharge recording where the recording voltage is high, the coloring caused by the current-carrying recording where the recording voltage is low is not mixed, so that the recording It has the advantage that clear recorded images can be obtained simply by changing the voltage.

[Brief explanation of the drawing]

FIG. 1 is a cross-sectional view for explaining the principle of current-carrying recording using a conventional current-carrying recording paper, FIG. 2 is a cross-sectional view showing the state of the current-carrying paper after recording, and FIG. 3 is a cross-sectional view showing an embodiment of the present invention. FIG. 4 is a sectional view of a recording paper showing another embodiment of the present invention.

Claims (1)

[Claims] 1. In a current-carrying recording paper in which at least a colored layer, a conductive layer, and a conductive coloring layer are sequentially provided on a support, the coloring state of the heat-sensitive coloring material in the conductive coloring layer is erased, and the coloring state of the heat-sensitive coloring material in the conductive coloring layer is erased. A current-carrying recording paper characterized in that a decoloring agent is mixed into the colored layer, or a layer containing the decoloring agent is provided between the conductive layer and the colored layer.