JPS5935355B2 - Conductive composition for electrically sensitive recording material - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to conductive compositions for electrically sensitive recording materials, and more particularly to conductive compositions with synergistically improved conductivity, low humidity dependence, stickiness resistance, whiteness and low cost. The present invention relates to a conductive composition for an electrically sensitive recording material having a combination thereof.

In this specification, an electrically sensitive recording medium refers to any recording medium that can perform recording in response to electrical signals, or can perform recording in combination with electricity and other energy such as light, heat, etc. For example, it is defined as a concept covering energized recording media, discharge breakdown recording media, electrostatic recording media, electrophotographic photosensitive recording media, etc.

Regardless of the image forming mechanism used by these electrosensitive recording materials, it is important from the standpoint of rapidly forming clear images that they have a layer with appropriate conductivity under the conditions of use. Conventionally, conductive agents for imparting conductivity to these recording materials include various substances such as metal powder, carbon black, water-soluble or hygroscopic inorganic or organic salts, various surfactants, Wetting agents such as polyhydric alcohols, polymer electrolytes, etc. are well known and are actually used.

However, all of these known conductive agents have drawbacks in one of the following respects, and are still not fully satisfactory. For example, conductive agents such as metal powder and carbon black are themselves good conductors and have the advantage of not being affected by humidity, but they generally have a unique color or opacity. This is a fatal flaw.

In other words, it is most important for the recording medium to have excellent whiteness from the viewpoint of the sharpness and contrast of the image formed, and furthermore, the recording medium on which the image is formed can be processed by diazo copying method, electrophotographic copying method, etc. It is hoped that it can also be used as a manuscript for conventional copying methods. The above-mentioned metals and carbons are still unsatisfactory in that not only do they lack these special properties, but the recording bodies are heavy and relatively expensive. In addition, salts, activating agents, organic wetting agents,
Other conductive agents such as polymer electrolytes exhibit conductivity only in the presence of moisture, and therefore suffer from various drawbacks.

For example, in the case of electrolytic recording materials that contain salts or the like as a conductive agent, it is necessary to use this recording material in a moist state (wet state), and special consideration must be taken to preserve the recording material before use. Furthermore, in connection with wet recording, disadvantages such as image smearing are likely to occur. In addition, electrostatic recording media and electrophotographic recording media equipped with a conductive layer made of a polymer electrolyte, such as a cationic conductive resin or a γ-ionic conductive curved resin, have the trouble of using the recording media in a humid state. Even if this is not the case, the effect of humidity on conductivity is still significant, and if a recording medium is left in a low-humidity atmosphere for a long time, the sharpness of the image will be lost due to a decrease in conductivity. On the other hand, in a high humidity atmosphere,
In connection with the fact that the polymer electrolyte is water-soluble, there is a drawback that the paper tends to stick to each other (tackiness).
The present inventors have discovered that a composition in which a proton conductive compound and an inorganic solid acid fine powder are combined in a fixed quantity ratio and dispersed in a binder in a fixed quantity ratio is a composition in which a proton conductive compound is used alone. The electrical conductivity increases synergistically compared to a composition in which the inorganic solid acid fine powder is dispersed in the binder or a composition in which the inorganic solid acid fine powder alone is dispersed in the binder. The thing is
It has been found that it is extremely useful for use as a conductive layer in electrically sensitive recording materials.

The present inventors further found that this conductive composition exhibits constant conductivity even under low humidity conditions, does not have a tendency to stick even under high humidity conditions, and has low humidity dependence and stickiness resistance. It has been found that it has excellent combination properties.

According to the present invention, the proton conductive compound contains a proton conductive compound, an inorganic solid acid fine powder, and a binder, and the proton conductive compound satisfies the following conditions: (j) the ratio of the number of carbon atoms/the number of nitrogen atoms ( C/N) is in the range of 0 to 8, especially 1 to 4, or (il) the first stage base dissociation constant (PKb.
Temperature 20℃) is 0.

3 to 8, especially an organic base satisfying at least one of 2 to 6, and the first stage acid dissociation constant (P
Ka, temperature at 25°C) is 6.5 or less, especially 5 or less, and the proton conductive compound and the inorganic solid acid fine powder are 0.5:100 to 0.
The weight ratio is 0:100, and the binder is 10 to 50% based on the total amount of the proton conductive compound and the inorganic solid acid fine powder.
0 weight? There is provided a conductive composition for an electrically sensitive recording material, characterized in that the composition is present in an amount of .

In addition to the advantages and features described above, the conductive compositions of the present invention have many other advantages and useful features.

First, the use of this conductive composition achieves the advantage that an electrically sensitive recording material that is outstandingly superior to white materials can be obtained. That is, the inorganic solid acid fine powder used in the present invention is generally a fine powder with excellent whiteness and pigment properties, and the proton conductive compound is also a solid with significantly less coloration than ordinary organic bases. By incorporating this proton conductive compound in a binder together with a solid acid fine powder, the whiteness of the conductive layer can be significantly improved. Furthermore, the conductive layer composition of the present invention not only can be provided at a significantly lower cost than cationic conductive resins, etc., which are conventionally the best conductive agents, but also can reduce the weight of the conductive layer of the recording medium or reduce the thickness of the conductive layer. Significant economic advantages are achieved in conjunction with the ability to Furthermore, while conventional conductive agents decrease in conductivity as the operating temperature rises, the conductive composition of the present invention exhibits properties that improve on the contrary, making it possible to perform recording operations under high temperature and low humidity conditions. It has the advantage that

The invention will be explained in detail below. Proton Conductive Compound In the present invention, a proton conductive compound is defined as a solid electrolyte whose mobile ions are protons.

This solid electrolyte has protons as mobile ions even in an extremely dry state, and therefore exhibits ionic conductivity even in an extremely dry state, which is an important point different from ordinary solid electrolytes. be. Here, the term "absolutely dry state" used in the present invention refers to a state in which a sample to be measured is left to dry at 25° C. for 24 hours in a desiccator using diphosphorus pentoxide as a desiccant. In addition, the W value of diphosphorus pentoxide, that is, the amount of water remaining in 1 ton of air (~
number) is 2×10-51r! It is y. The proton conductive compound is 1×1013Ω-α or less in an absolutely dry state, especially 2,
5XI012Ω-? It is desirable to have the following volume resistivity. From the viewpoints of easy availability and low electrical resistance, acidic monosalts of organic bases are preferred, but other known proton conductive compounds can also be used as long as they satisfy the above conditions. . The proton conductive compound consisting of an acid addition salt of an organic base used in the present invention has significant advantages over the low-molecular or high-molecular quaternary gamma monium salts commonly used as conductive agents. .

That is, the mobile ions in the quaternary ammonium salt type conductive agent are anions that exist as ions, but the mobile ions in the conductive agent used in the present invention are protons (hydrogen ions), and the present invention The conductive agent used for this purpose has excellent ion mobility; in the former case, conductivity can only be obtained in the presence of moisture, and in the latter case, the conductive material is It does not require the presence of water to obtain it. Examples of the organic base constituting the proton conductive compound include l-class, secondary or tertiary aliphatic, alicyclic, aromatic or heterocyclic amines, hydrazine or its derivatives, guanidine or its derivatives, and imine. These bases may be low molecular weight compounds or high molecular weight compounds.

Suitable examples of these organic bases are shown in Table 1 below, but the present invention is not limited to the exemplified organic bases. The base used in the conductive agent of the present invention generally satisfies the following conditions: (1) the ratio of the number of carbon atoms to the number of nitrogen atoms (C/N) is in the range of 0 to 8, particularly 1 to 4; :
l) The first stage base dissociation constant (PKb. temperature 20°C) is within the range of 0.3 to 8, particularly 2 to 6, and preferably satisfies at least one of the following, particularly preferably both. is desirable.

That is, in a preferred embodiment of the present invention, the above C/N value or P
By selecting an organic base with a Kb value within the above range, the conductive range when used as a conductive agent can be significantly increased compared to when the C/N value or PKb value is outside the above range. I can do it. The exact reason for this is unclear, but C
If /N or PKb is smaller than the above range, the bond of the acid addition salt becomes too strong, making it difficult for protons to dissociate even in an electric field. It is presumed that if the acid-adding force is large, the bond itself of the salt becomes weaker, making it difficult to form protons themselves, and this is also associated with a decrease in the proton concentration. As the acid constituting the proton conductive compound of the present invention, any inorganic acid or organic acid can be used, but from the viewpoint of the conductivity of the final conductive agent, the first stage acid dissociation constant (PKa .Temperature at 25° C.) is desirably in the range of 6.5 or less, particularly 5 or less.

Suitable examples of inorganic acids are hydrohalic acids, such as hydrochloric acid; sulfuric acid, such as sulfuric acid, sulfurous acid; nitrogenous acidic acid, such as nitric acid, nitrite; orthophosphoric acid, metaphosphoric acid, pyrophosphoric acid. Examples of suitable organic acids include formic acid, acetic acid, triacetic acid, crotonic acid, glycolic acid, salicylic acid, p-hydroxybenzoic acid, oxalic acid, malonic acid, and succinic acid. , tartaric acid, azelaic acid, maleic acid, citric acid, pyromellitic acid, glutamic acid, and other carboxylic acids; methanesulfonic acid, benzenesulfonic acid, p
- Sulfonic acids such as toluenesulfonic acid; phosphonic acids, phosphinic acids, etc. can be mentioned. Preferred acids are, in order of importance, sulfuric acid, hydrochloric acid, phosphoric acid, nitric acid, sulfonic acid.
The acid addition salt of the organic base used may be a neutral salt, an acid salt, or a base salt, depending on the valency of the base and acid.

These salts may be easily obtained by varying the reaction molar ratio of organic base and acid. Inorganic Solid Acid Fine Powder In the present invention, the inorganic solid acid fine powder is defined as an inorganic solid fine powder exhibiting the characteristics of Brønsted acid or Lewis acid.

The inorganic solid acids include silicic acid, alumina, and γ.
Any natural, synthetic, by-product, regenerated or activated inorganic solid acid containing luminosilicic acid or the like can be used. A suitable example is: Natural clay minerals or their activated products; montmorillonite group clay minerals such as bentonite, acid clay, frass gamma, subbentonite; kaolin group clay minerals such as kaolin; or activated products obtained by acid treatment of these. Matter of white earth.

(B) Dry process amorphous silicic acid fine powder available under the trade name of amorphous Aerosil silicate (Nippon Aerosil).

Mizukasil (Mizusawa Chemical Industry), Tokusil (Tokuyama Soda),
Wet-method amorphous silicic acid fine powder available under trade names such as Cyroid (Fuji Davison Chemical). (C) Active γ-lumina Amorphous γ-lumina or alumina hydrate.

Width Composite oxide silica/alumina, silica/magnetic γ, silica/poria.

(g) Zeolite Natural or synthetic zeolite, especially hydrogen ion or ammonium ion substituted zeolite.

(g) A fired product of a composition of solid phosphoric acid type silica or γ-lumina and phosphoric acid.

(G Other inorganic chemicals Amorphous titanium dioxide, titanium phosphate, zircon phosphate.

These inorganic solid acids are desirably as finely powdered as possible from the standpoint of being able to be uniformly dispersed in the binder and improving the conductivity and whiteness of the composition, and from this standpoint, generally 20μ Hereinafter, it is particularly desirable to have a particle size of 10 μm or less.

Furthermore, from the viewpoint of synergistically improving the conductivity of the conductivity composition, the inorganic solid acids used in the present invention generally have adsorption properties, that is, those with a relatively large specific surface area, especially those with a BET specific surface area. is preferably 50 i/9 or more, more preferably 100 i/9 or more. Particularly suitable solid acid fine powders for the purpose of the present invention include various clays, their acid-treated products, finely powdered silicic acid, hydrogen, ionic zeolite, and the like.

Binder: As the binder for dispersing the proton conductive compound and the inorganic solid acid fine powder, various polymeric organic binders, which are water-soluble, water-dispersible, or organic solvent-soluble, are used. Ru.

Water-soluble binders include various starches, cyanoethylated starch, methylcellulose, ethylcellulose, hydroxyethylcellulose, carbo S) 1,000 dimethylcellulose (CMC), gum tragacanth, gum arabic, glue casein, gelatin, SlSS, sodium alginate, polyvinyl alcohol, partially saponified Examples include type I or a combination of two or more of polyvinyl acetate, partially acetalized polyvinyl alcohol, polyvinyl methyl ether, polyvinylpyrrolidone, polygamma acrylamide, water-soluble acrylic resin, and the like.

Examples of water-dispersible binders include various water emulsion and latex binders, polyvinyl acetate, polyvinyl chloride, polyvinylidene chloride, vinyl chloride monovinyl acetate copolymer, and styrene-butadiene copolymer. , methyl methacrylate-butadiene copolymer, acrylic ester-styrene copolymer, polyethylene, polypropylene, ethylene monovinyl acetate copolymer, vinyl acetate-acrylic ester copolymer, acrylonitrile-styrene copolymer, acrylonitrile-butadiene Water bending emulsions or latexes such as copolymers, gamma acrylonitrile-styrene-butadiene copolymers, etc. may be used.

As the organic solvent-soluble binder, various natural, synthetic or semi-synthetic thermoplastic or thermosetting binders such as silica, copal, rosin, dry-cured oil-modified rosin, and phenolic resin can be used. Rosin, epoxy resin, phenolic fiber, amino resin, unsaturated polyester resin, silicone resin,
Silen resin, bismaleimide resin, thermosetting gamma acrylic resin, cellulose acetate, polyvinyl acetate, polyvinyl butyral resin, thermoplastic acrylic resin, styrene-butadiene copolymer, vinyl chloride monovinyl acetate copolymer, chloride Vinyl monoacetate-vinyl alcohol copolymer, vinyl chloride vinyl monoacetate-maleic acid copolymer, styrene-acrylic ester copolymer, polygammaide resin, ethylene monovinyl acetate copolymer, ionomer, cyclized rubber One type or a combination of two or more types of these are used.

Composition In the present invention, the proton conductive compound prisoner and the inorganic solid acid fine powder CB) are mixed in a ratio of A:B=0.5:100 to 100:100, particularly 2:100 to 80:1.
It is important to use the combination in a weight ratio of 0.00, most preferably from 5:100 to 50:100.

For example, a composition in which tetramethylgammanidine sulfate alone is dispersed in a binder as a proton conductivity bending compound is 3.
3×】09Ω1? A composition containing kaolin alone as an inorganic solid acid fine powder dispersed in a binder has a volume resistivity of 2.0 x 1011 Ω. On the other hand, a composition in which both of these are dispersed in a binder exhibits a volume resistivity of 1.0×10 8 Ω-? It shows a significantly small volume resistivity.

That is, according to the present invention, by using a proton conductive compound prisoner and an inorganic solid acid fine powder (B) in combination,
This results in an improvement in the conductivity curve of approximately 33 times compared to the case of (B) alone and approximately 2000 times compared to the case of (B) alone, which is due to the fact that the conductivity curve is improved by approximately 2000 times compared to the case of (B) alone. This shows that the conductive solid and the inorganic solid acid do not act independently as conductive agents, but that they work together to synergistically improve the conductivity. . If the ratio of the amount of the proton conductive compound to the inorganic solid acid fine powder (B) is outside the above-mentioned range, no improvement in the conductivity curve due to the synergistic effect of the two can be expected.

Furthermore, when the amount of the compound is greater than the above range, the conductivity of the composition becomes saturated, the binding properties of the composition are lost, or the coating film of the composition tends to become sticky. Cases often arise. On the other hand, if the amount of the solid acid powder is larger than the above range, the volume resistivity of the composition becomes too high or the humidity dependence of the conductive curve becomes too large, which is not preferable for the purpose of the present invention. do not have. The amount of the binder used varies depending on whether the conductive composition is used only as a conductive substrate layer or as a conductive recording layer of an electrically sensitive recording material, but generally speaking, , the binder (C) is added in an amount of 10 to 500 weight per total amount (A+B) of the proton conductive compound and the inorganic solid acid fine powder (B). It is best to use an amount of 10 to 500% by weight in the case of the former conductive substrate. In the case of the later conductive curved recording layer, it is used in an amount of 20 to 100% by weight.
good.

That is, if the amount of the binder (○) used is less than the above range, the conductivity will be saturated and the binding properties of the composition will be significantly reduced.
On the other hand, if the amount exceeds the above range, the conductivity will drop significantly and its humidity dependence will also tend to increase, so it is important to use it within the above range. Although generally not required, the conductive compositions of the present invention include:
If desired, various conductive agents or auxiliary agents known per se,
For example, polyvalent γ alcohol, water-soluble inorganic salts, etc. can be used.

Conductive Substrate The conductive coating composition of the present invention can be advantageously used for preparing conductive substrates for electrostatic recording paper, electrophotographic paper, and the like.

This electrically conductive substrate is easily manufactured by coating or self-immersing the composition of the present invention onto at least one surface of a paper substrate, or by incorporating it into the paper during manufacturing.

The coating amount of the conductive coating composition varies depending on the degree of conductivity required, but is generally 3 to 509/M3, particularly 509/M3.
It is desirable that the range is from 309/Rrl to 309/Rrl. The coating solution of the conductive composition of the present invention can be prepared, for example, by dissolving a proton conductive compound in water, and then adding solid acid fine powder (C
) is uniformly dispersed, and finally a solution of the water-soluble binder (C) or an emulsion or latex of the water-dispersed binder (C) is added and mixed.

When the binder used is an organic solvent solution, a proton conductive compound and solid acid fine powder are added to this solution, and these are uniformly dispersed by milling using a ball mill or the like to obtain a coating composition. . The solid content concentration of these coating liquids is 10 to 60%, especially 25 to 50% in terms of working conditions.
It is preferable to set it in the range of %. A dielectric layer or a photoconductive layer, which is known per se, is provided on the conductive curved substrate to be used as electrostatic recording paper or electrophotographic photosensitive paper.

Conductive Recording Layer The conductive composition of the present invention can also be advantageously used as a conductive recording layer of current-carrying recording paper.

Current-carrying recording paper having the following coloring mechanism is known, and the conductive composition of the present invention can be used for any of these.

(a) Introduction of foreign ions into the recording layer; (b) Discharge of ions at an electrode in contact with the recording layer;
(C), Oxidation or reduction on the electrode surface in contact with the recording layer, (d), Increase in concentration of specific ions 7V1 (PH change) on the electrode surface in contact with the recording layer, (e), Occurrence in the recording layer. Juur heat (heat-sensitive coloring).

In the coloring mechanism (a) above, the metal needle as an anode is eluted into the conductive substrate in the form of cations due to an electrode reaction, and the coloring is caused by a coloring agent retained in the conductive substrate. A substance that reacts with the agent to form a colored image of the electroconductive compound: 11 A metal needle serving as an anode is eluted into the conductive curved substrate in the form of a cation by an electrode reaction, and the reduction inherent in the conductive substrate is Coloring agents used in these mechanisms can be roughly divided into three types: those that form an image made of fine metal particles when reduced by a chemical agent, and those that form an image that consists of a metal needle as a cathode such as 111 tellurium. Examples include those listed in Table 2 below.

Furthermore, the following can be cited as examples of combinations other than those listed in Table 1.

A suitable example of the coloring mechanism (b) above is as follows.

Further, suitable examples of the coloring mechanism (c) above are as follows. In addition to the above-mentioned oxidized coloring agents, there are many leuco pigments such as leucomalachite green (green), leucoethylnal blue (blue), leucofuscin (red), leucomethylcaprylic blue (blue), and leucotoluimble (blue). (purple) Leucodiphenyl gamma amine (purple) Leuco-N-methyldiphenylamine-p-sulfonic acid (purple red) Leucophenyl gamma lanthranilic acid (purple red) Methyl pyrogen (purple) Leucosafranin T (red) Leucodigosulfonic acid (blue) Leucophenosafranin (red) Leucomethylene blue (blue) Leucodiphenylbenzidine (purple) Leucoolamine (yellow) Benzoylleucomethylene blue (blue) Leucoeryoglucin A (yellow-green → red) Leuco-P-nitrodiphenylamine (Purple) Leucodiphenyl γmine-10,0'-diphenylcarboxylic acid (
blue-purple) can be used.

In addition to 2,3,5-triphenyltetrazolium chloride, examples of reduced coloring agents include tetrazolium blue, tetrazolium purple, tetrazolium violet, 2,5-diphenyl-3-(4-styrylphenyl)tetrazolium chloride, and 2,3,5-triphenyltetrazolium chloride. phosphotungstic acid,
Metal compounds such as phosphomolybdic acid and gamma phosphomolybdic acid can be used.

Further, suitable examples of the color development mechanism described in (d) are shown in Table 3 below.

Examples of diazonium salts include diγzonium salts used in ordinary diazo copying systems, such as P-N,N dimethylaminobenzenediazonium chloride zinc chloride double salt;
4-morpholinobenzenediazonium chloride zinc chloride double salt, P-N,N-diethylamino-2,5-dimethoxybenzenediγzonium chloride zinc chloride double salt, etc. are used.

Furthermore, in the above Table 3, among the latter color forming agent components, the aromatic ] class γ amines include γ amines used in the synthesis of ordinary diazonium compounds for copying, such as aniline, morpholine, N, N-disubstituted baraphenylene range γ
Min, etc. are used in the form of hydrochloride, etc., and as coupling components, phenol derivatives, o-sinaphthalene derivatives, active methylene-based compounds, etc. are used.

Furthermore, as suitable examples of those based on the coloring mechanism (e) above, those shown in Table 4 below can be mentioned.

In this case, it is necessary that the solvent of the binder does not dissolve these color formers and color developers, and a combination of binder, color former, and color developer that satisfies this condition is selected.

In the present invention, the above-mentioned color forming agent or further color developing agent is
An amount sufficient to form an image of sufficient density, that is, generally speaking, 2 to 40%, especially 5%, based on the total amount of proton conductive compound prisoner, solid acid fine powder (B) and binder (C). It is included in the composition in an amount of 35% to 35%.

Furthermore, in order to stabilize the color former or color developer, stabilizers known per se, such as urea-based stabilizers such as thiourea or its gamma chloride derivative; gamma alkali metal chloric acid or perchloric acid may be used. Oxidizing agents such as salts; acidifying agents such as formic acid, oxalic acid, hydrochloric acid, citric acid; or gamma alkali metals or gamma
One or more alkaline buffers such as alkaline earth metals, metal formates, acetates, carbonates, tartrates, bicarbonates, borates, and phosphates can be contained.

These compositions for forming a conductive recording layer can be produced in the same manner as the above-mentioned composition for coating a conductive substrate, except that they contain a color former or a color developer. . This coating composition can be applied onto substrates such as paper substrates, conductively treated paper substrates, metal foils, metal laminated papers, metallized papers, films, etc. from 3 to 509/I, especially from 5 to 259/I.
It can be applied with a coating amount of Trl.

The conductive composition of the present invention can be particularly advantageously used in the reduction type recording layer (c) having a tetrazonium salt as a coloring agent. That is, in the composition of the present invention, since the mobile ions are protons, the color forming agent is extremely effectively reduced at the cathode, resulting in a recorded image with higher density and contrast than in conventional recording layers. It becomes possible to form. The conductive composition of the present invention has an unexpectedly large conductive area compared to the case of solid acid fine powder or pukaton conductive compound alone, and the humidity dependence of this conductive material is different from that of the known inorganic salt conductive material. It has the remarkable advantage that it is significantly smaller than other conductive agents and organic conductive agents, exhibits high conductivity even under low humidity conditions, and shows virtually no tendency to stick even under high humidity conditions. . Furthermore, this conductive composition has the advantage that it is excellent in whiteness and smoothness, and that electrically sensitive recording materials can be supplied at relatively low cost. The invention is illustrated by the following example.

Example 1. Vinyl chloride vinyl monoacetate-vinyl gamma alcohol copolymer (
20? 50 parts by weight of tetrahydrofuran solution (hereinafter referred to as parts), 20 parts by weight of kaolin
1 part, 4 parts of tetramethylgammanidine sulfate, and 30 parts of tetrahydrofuran were milled in a ball mill for 20 hours.

This dispersion was applied onto high-quality paper using a wire bar and dried to produce conductive paper with a coating weight of 109. The prepared conductive paper showed a surface resistance of 6.1 x 107 Ω at 14°C and 54% relative humidity.Incidentally, the samples coated on aluminum foil were tested with and without the addition of kaolin and tetramethylgammanidine sulfate. The volume resistivity was investigated and shown in Table 5. In the table, O means additive I, and X means unadded Calo.

According to the results in Table 5, it can be seen that the conductivity was synergistically improved by the co-addition of kaolin and tetramethylgammanidine sulfate. Example 2. The above composition was milled using a ball mill for 10 hours, and then coated and dried on both sides of 80 μm thick high-quality paper with a wire bar so that the coating weight per side was 59/d to produce electrically conductive treated paper.

This conductive treated paper is 1.5×I at 20℃ and 40% relative humidity.
It showed a surface resistance of O8Ω. Next, add Litopone in an amount equivalent to 10% of the solid content to γ-cryl resin (Diamail LR-297, manufactured by Mitsubishi Rayon), and apply the pulverized and mixed coating solution to one side of the conductive treated paper to a film thickness of about 10 μm. The coating was applied and dried to produce electrostatic recording paper. Linear density on recording paper: 6t/Mm, recording speed: 2m/Sec, pulse width: 20
After applying a DC voltage of -600V in μS and recording operation,
Developed with a positive dry type two-component developer (manufactured by Sanda Kogyo), thermally fixed, and measured the reflection density of the recorded image area with Sakura Microdensitometer PDM-5 (manufactured by Konishiroku Photo Industry) 1 It showed .5. Example 3. 30 parts of hydrogen ion type zeolite, 3 parts of hemethylenetetramine methanesulfonate, 1 part of polyvinyl gamma alcohol
75 parts of a 0% aqueous solution and 50 parts of water were pulverized and mixed in the same manner as in Example 2, and coated on high quality paper to obtain conductive treated paper.

The surface resistance of this paper is 8.9× at 20℃ and 20% Aigari humidity.
It showed 107Ω. When no amethylenetetramine methanesulfonate was added, the resistance was 3.6×10 8 Ω. Next, zinc oxide, sensitizing dye, and binder (SOX-5
An electrophotographic photosensitive paper was prepared by coating a photosensitive layer of 00 Seido Kagaku Co., Ltd., Promphenol Blue, acrylic resin γ Rotapu 3211 Nippon Gamma Co., Ltd.) to a thickness of 8 μm by a conventional method.
When this photosensitive paper was copied using a dry type electronic copying machine 900-D manufactured by Sanda Kogyo, a sharp image with high contrast and no fogging could be obtained. Note that the hydrogen ion type zeolite was prepared by replacing 13X type zeolite with ammonium ions and then heating in vacuum.

Example 4. 50 parts of amorphous silicic acid fine powder (manufactured by Mizusawa Chemical Co., Ltd.), 10 parts of cyclohexyl gamma mintrichloroacetate, 25 parts of styrene-butadiene copolymer (manufactured by Tau Chemical Co., Ltd., 48% solution), and 400 parts of water. The mixture was pulverized and mixed in a ball mill in the same manner as in Example 2, and then applied and dried on high-quality paper to produce conductive paper.

The surface resistance of this paper was as follows. 30℃, relative humidity 20% 1.3 x 108Ω 20℃, relative humidity 80%
6.5X106Ω Example 5. 50 parts of kaolin, 20 parts of tetramethylgammanidine sulfate, 40 parts of methyl methacrylate-styrene copolymer (48% aqueous solution, manufactured by Takeda Pharmaceutical Industries, Ltd.) and 170 parts of water were milled in a ball mill for 10 hours, and then the leuco dye benzoyl leuco 5 parts of methylene bullion was added and milling was continued for an additional 5 hours.

This dispersion was applied to aluminum laminated paper, and after drying, a conductive recording layer having a thickness of 11 μm was obtained. This recording paper was pasted on a metal drum, the γ-luminium layer was used as the negative electrode, and the metal needle (made of tungsten, 150μ diameter) was used as the anode, and the recording speed was 1.2 m/Se.
cl linear density 3.85, stylus pressure 109, recording voltage +200V
Recorded with a reflection density of 0.45 (using a red filter)
A recorded image was obtained. Example 6. In Example 5, 2,3,5-triphenyltetrazolium chloride, instead of benzoylleucomethylene chloride,
Using tetrazolium blue and neotetrazolium chloride, when a voltage of -200 V was applied to the metal needle, red, blue, and purple recorded images were obtained, respectively.

Claims (1)

[Claims] 1 Comprising a proton conductive compound, an inorganic solid acid fine powder, and a binder, the proton conductive compound satisfies the following conditions: (i) the ratio of the number of carbon atoms/the number of nitrogen atoms; (C/N)
is in the range 0 to 8, especially 1 to 4, or (
ii) First stage base dissociation constant (pKb, temperature 20°C)
is in the range of 0.3 to 8, especially 2 to 6, and the first stage acid dissociation constant (pKa, temperature 4.5 ° C.) is 6.5 or less, especially 5 or less, the proton conductive compound and the inorganic solid acid fine powder are in a weight ratio of 0.5:100 to 100:100, and the binder is proton conductive. A conductive composition for an electrically sensitive recording material, characterized in that the conductive composition is present in an amount of 10 to 500% by weight based on the total amount of the compound and the inorganic solid acid fine powder. 2 A proton conductive compound is 1×10^1^ in an absolutely dry state.
The conductive composition according to claim 1, which is an organic base acid addition salt exhibiting an electrical resistance of 3 Ω-cm or less. 3. The conductive composition according to claim 1, wherein the inorganic solid acid fine powder is a solid acid fine powder having adsorption properties with a specific surface area of 50 m^2/g or more. 4. The conductive composition according to claim 1, wherein the inorganic solid acid fine powder is a clay mineral, an acid-treated product thereof, an amorphous silicic acid fine powder, or a hydrogen ion type zeolite. 5. The conductive composition according to claim 1, wherein the binder is a water-soluble organic polymer binder. 6. The conductive composition according to claim 1, wherein the binder is a water-dispersible organic polymer binder. 7. The conductive composition according to claim 1, wherein the binder is an organic polymer binder soluble in an organic solvent. 8 (A) proton conductive compound, (B) inorganic solid acid fine powder, (C) binder, and (D) color development by introduction of different ions, ion discharge, oxidation/reduction, pH change, or Joule heat. Contains a color former or a color developer,
The proton conductive compound meets the following conditions: (i) the ratio of carbon atoms/nitrogen atoms (C/N) is 0 to 8, particularly 1;
or (ii) the first stage base dissociation constant (pKb, temperature 20°C) is in the range of 0.3 to 8, particularly 2 to 6. The base and the first stage acid dissociation constant (pKa, temperature 2
5°C) is 6.5 or less, especially 5 or less, and is an addition salt with an inorganic or organic acid, and the proton conductive compound and the inorganic solid acid fine powder are in a weight ratio of 0.5:100 to 100:100. The binder is present in an amount of 10 to 500% by weight based on the total amount of the proton conductive compound and the inorganic solid acid fine powder, and the color forming agent or color developer is present in an amount of 10 to 500% by weight based on the total amount of the proton conductive compound and the inorganic solid acid fine powder. A composition for a conductive recording layer, characterized in that the composition is present in an amount of 2 to 40% by weight based on the total amount of powder and binder. 9. The composition according to claim 8, wherein the color former is a tetrazolium salt.