JPS6345083A - Light-transmitting recording material and image-forming method using the same - Google Patents

Abstract

PURPOSE:To ensure excellent transparency and make it possible to obtain clear high-quality images even in the case of using the title recording material on an optical apparatus, by providing a coating layer having a surface electric resistance not higher than a specified value and trapping a recording agent capable of being dissolved and/or dispersed in an aqueous medium. CONSTITUTION:This light-transmitting recording material has a surface electric resistance of not higher than 10<14>OMEGA/square, and can trap a recording agent capable of being dissolved and/or dispersed in an aqueous medium. A base for a coating layer may be any one which has a heat resistance of at least 100 deg.C and is light-transmitting. The recording material for use with a recording agent of felt-tip pens, fluorescent markers, fountain pens or the like preferably has a pH of 4-10 and is substantially resistant to water. With this arrangement, migration or bleeding of the recording agent will not occur even when a recorded matter is placed in a wet condition.

Description

Detailed Description of the Invention (Industrial Application Field) The present invention relates to a recording material and an image forming method that provide recorded images with excellent translucency in an image forming method using an electrostatic recording method. Furthermore, the present invention can produce high-quality, clear images even in image forming methods using recording instruments such as felt-tip pens, highlighters, and fountain pens that use aqueous media, and recording devices such as pen plotters and inkjet recording systems. The present invention relates to a recording material and an image forming method.

The present invention also relates to a recording material and an image forming method that can provide high-quality images even in a thermal transfer recording method or an impact type recording method.

(Prior art) The image forming method using the electrostatic recording method is Inana's method.
A method of forming an image by selectively applying an electric charge to the surface of the recording material and attaching particulate recording agent (toner) to the charged part, and is used in copying machines, facsimiles, etc. In particular, electrophotographic copying machines that utilize electrostatic processes are widely used.

The image forming method using the electrostatic recording method consists of a process of forming an image by electric charge on the recording material and attaching the recording agent, and a process of thermally fixing the attached recording agent.For example, it is suitable for electrophotography. Performances required of the recording material include conductivity, smoothness, whiteness, gloss, non-curling, homogeneity, etc. Among these, the electrical properties of the surface of the recording material are particularly important. For this reason, it is common that the material to be recorded for electrophotography is subjected to conductive processing so that it has a suitable surface resistance.

In addition, there is also a demand for a recording material that has translucency and can be used in optical equipment (e.g., overhead projectors) to observe transmitted images. Strongly, such recording materials are
In addition to the performance required in F, it is essential to have excellent translucency.

The recording material for the above purpose is generally a translucent sheet material such as a resin film whose surface is conductive, but in this case, in addition to the Oη performance, the recording material itself It is also required that the surface of the recording material has partial heat resistance.

Furthermore, in the above-mentioned applications, there is a high demand for color images.

Conventionally, to form a color image on a translucent sheet material, for example, silver halide photoprinting or electrophotography has been used, but in either case, a large-sized device is required.

The easiest way to form a color image is to directly color with a so-called water-based pen that uses water-based ink, such as a sign pen, highlighter pen, or fountain pen, or to use a pen plotter that uses these. However, in this case, it is necessary that the recording material in the ink be fixed on the light-transmitting sheet material quickly.

Other methods of forming a color image include using a printer or pen plotter using a color hard copy device, a wire tod method, an inkjet recording method, a thermal recording method, or the like.

In this case, the following performance is particularly required of the transparent recording material.

For example, in an inkjet recording method using water-based ink, the rapid fixation of the recording agent in the ink is particularly important, as is the case with water-based pens, and in a thermal transfer method, the smoothness and heat resistance of the surface of the recording material are particularly important. be.

As mentioned above, each recording method requires different performance from the recording material, and all of the above recording methods (electrophotographic copying machine, water-based pen, ink jet recording method, wire tod method, thermal transfer method) There is still no known translucent recording material that can be used for this purpose.

For example, the OHP film 11 for electrophotography described in JP-A No. 56-38056 provides a plastic film 7 with an F coating layer having a surface resistance of 1.0x10' to 9.0x109Ω, and then Surface resistance 1.0X10ゝ0
A toner receiving layer of ~1.0×10 13 Ω is provided.

This film has heat resistance and surface conductivity of l=min, but since the surface of the film itself is non-porous, it is difficult to use felt-tip pens or highlighters on images obtained using a 7E F photocopy machine. When coloring is carried out with a fountain pen or the like, there is a problem that water-based components remain on the surface and drying is slow, resulting in damage to the recorded image if the surface is touched by an object after recording.

Therefore, an object of the present invention is to provide a translucent recording material that is suitably used in the electrostatic recording method described above, has particularly excellent translucency, and can provide clear, high-quality images even when used in optical equipment. It is to provide.

Another object of the present invention is to enable image formation using recording instruments such as sign pens, highlighters, fountain pens, and other recording devices using aqueous media, and to produce clear, high-quality color images. An object of the present invention is to provide a translucent recording material that can be used.

Another object of the present invention is to provide a translucent recording material that can provide high-quality images even in thermal transfer recording systems and impact recording systems.

Another object of the present invention is to provide a novel image forming method in which a high-quality translucent image can be formed using any one of an electrostatic recording method, a recording method using an aqueous medium, and a thermal recording method. It is in.

(L stage for solving problems) The above object is achieved by the present invention as follows.

That is, the present invention consists of two inventions. A second invention is a transparent recording material characterized by having a coating layer shown in FIG. This image forming method is characterized in that image formation is performed using at least one of the methods.

(Function) The translucent recording material of the present invention has disadvantages when used in electrostatic recording methods, namely, the surface resistance increases at low humidity, and as a result, image fogging due to triboelectric charging, etc. In order to avoid problems, the surface electrical resistance value is set to 101.
It is essential that the resistance is 4Ω/□ or less, preferably 10
Range of 8 to 1014Ω/□, more preferably 1010 to
J in the range of 1014Ω/□! It is desirable to adjust it.

The surface electrical resistance value of the recording material as described above corresponds to the composition of the recording material of the present invention, and the hydrophilic material and additives used in forming the coating layer from a hydrophilic material as described later. This can be easily adjusted by changing the types and combinations of , and the surface electrical resistance value can be maintained within the above range even under low humidity conditions.

In the present invention, "captability" means that after a predetermined period of time (numerically (C5 minutes or more)) after recording is performed on a recording material with a recording liquid, the surface of the recording material recorded with the recording liquid is This refers to the ability of the recording agent in the recording liquid to be captured on the recording material to such an extent that the recording agent does not adhere to the filter paper even when the filter paper is pressed.

In the present invention, based on the fact that the recording material is translucent, it is essential that the surface be non-porous, so it is necessary that the recording material be made of a specific material. It is.

When the surface is porous, such as paper, capillary action causes
The aqueous recording medium is absorbed and the recording agent is also captured, but in the case of a non-porous recording material, the following methods of capturing the recording agent can be cited, for example.

(I) As a constituent material of the recording material, a material that electrically adsorbs recording agent molecules or is reactive with recording agent molecules and generates bonds such as ionic, hydrogen bonding, or covalent bonding. What it contains.

For example, if a water-soluble dye is used as a recording material, the recording material contains a cationic resin with respect to the acidic dye.

(11) Contains a material that has expansion Δ゛J1 property or solubility with respect to the medium of the recording agent as a constituent material of the recording material, and also captures recording sound by trapping the medium in the recording material. thing.

To give a specific example, when a water-based recording liquid is used with a water-soluble dye, the recording material contains a water-soluble polymer or a wood-philic polymer.

With the recording material of the present invention configured as described above, it is possible to form an image even by a recording method using an aqueous medium, and the image will not be damaged by touching the recording surface with an object or a finger after recording.

Furthermore, according to the findings of the present inventors, the recording material of the present invention has the following characteristics:
In order to obtain a clearer recorded image, it is preferable that the recording material absorbs an aqueous medium, and therefore the embodiment (n) is preferred.

In the present invention, since the recording material may be heated during recording, such as in a thermal transfer method, the recording material has a thermal softening temperature of 100°C or higher, preferably 120°C or higher, and more preferably 140°C or higher. It is desirable to hit the surface. Therefore, in applications where heating may be required, the material constituting the recording material of the present invention is selected from materials whose thermal softening temperature falls within the above range.

To explain by giving a specific example, as a material that has a heat softening temperature of 1, for example, polyvinyl alcohol (hereinafter referred to as P
VA), acrylic acid-based polymers, etc., but the recording material of the present invention generally also uses PVA or PVA with an appropriate degree of saponification that is swellable or soluble in an aqueous medium. It is composed of an acrylic polymer, etc., which is a copolymerization of a hydrophobic monomer and a wood-philic monomer.

The recording material of the present invention having the above-mentioned characteristics provides a clear and high-quality image even when recorded using an electrophotographic method, for example. On the other hand, the thermal softening temperature is 1
If the temperature is lower than 00°C, the recording surface may become cloudy, making it impossible to obtain an image with sufficient translucency, which is not preferable.

Here, the thermal softening temperature refers to the temperature at which the resistance to external stress on the surface of a recording material due to heating exceeds a certain value. They discovered that there is a correlation between F and the electrostatic recording characteristics that govern the heat fixing mechanism.

Therefore, the thermal softening temperature referred to in the present invention is defined as the temperature at which the scratch resistance of the surface of the recording material reaches a certain value or more. The temperature is below.

In the present invention, the scratch test was conducted under a load of 50 g, and the scratch resistance was judged based on the absence of scratches and ridges on the surface.

With the recording material of the present invention having the above configuration, the object of the present invention described in I) η is achieved, but more preferred embodiments for making the present invention more effective are described above. do.

The liquid fertilizer 21 material of the present invention has a base material and a surface on the base material that has a practical heat softening temperature of 100°C or higher, and (1) a coating that has a recording agent capturing property that can be dissolved and/or dispersed in an aqueous medium. It is preferable that the recording material is a light-transmitting recording material characterized by being provided with a layer, and preferably the coating layer is water-resistant.

As the base material used as the support for the coating layer in the present invention, any base material that has a heat resistance of 100° C. or higher and is transparent can be used.

Suitable examples include films or plates made of polyester resin, polysulfone resin, diacetate resin, triacetate resin, acrylic resin, polycarbonate resin, polyvinyl chloride resin, polyimide resin, etc. . The thickness of these base materials is preferably in the range of l to s, ooo μm.

"Water resistance" as used in the present invention refers to practical F water resistance, which is such that the coating layer does not dissolve when immersed in still water for 1 minute.

In other words, if the coating layer is not water resistant, the surface of the recording material will become tacky when water passes through or adheres to the surface under high humidity conditions, and for example, when used in an electrophotographic copying machine, it may become heavy. This is undesirable because it causes problems such as the recording material becoming stuck to the conveyance system of the apparatus.

Furthermore, when recording using an aqueous medium, the strength of the recording section may become weak, the recording section may become blocked, or when recording directly onto the surface of the recording material with a recording device, the surface of the recording material may be damaged. '4-ru.

■The recording devices mentioned above, such as sign pens, highlighters, fountain pens, etc., have a pH value in the recording medium due to the stability and color development of the recording agent.
: Contains A trimming, etc., and usually has a pH in the range of 4 to 10. Therefore, for the above reasons, the recording material of the present invention has a pH of 4.
It is desirable to have substantially water resistance in the range of 10 to 10.

Specifically, the aspect of water resistance and recording agent capture property is as follows:
In the embodiment (1) or the embodiment (n) above, in which the coating layer is water resistant, the coating layer is water resistant and exhibits swelling and/or solubility in an aqueous medium, and has recording agent capture properties even during wet ablation. Even if the recorded material is placed in a wet state, the recording material will not migrate or run out.

As a specific example of forming the latter type of S layer, the following example may be given.

(a) Example of blending and using a water-resistant polymer and a hydrophilic polymer.

(b) An example in which a hydrophobic segment and a hydrophilic segment are present in the molecule, and the polymer itself is water resistant and hydrophilic.

(c) An example in which a water-soluble polymer is crosslinked with a well-known crosslinking agent to suppress excessive hydrophilicity.

(d) Creates a certain persimmon-like bond between water-soluble polymers,
An example of using a blend of polymers that are water-soluble but become water-resistant when blended.

In the present invention, it is further preferable that the wet friction fastness to water droplets on the surface of the -π-covered layer is JIS L-085:l of grade 2 or higher.

If the abrasion fastness is less than 2, when using a recording device that directly contacts the surface of the recording material, such as a pen, a highlighter, or a fountain pen, the surface that received the aqueous medium will be affected.
Problems arise such as the shape cannot be maintained and images are likely to be damaged.

A more preferred embodiment of the recording material of the present invention having such a structure is one in which the coating layer contains a crosslinkable compound (or crosslinkable polymer) and a cationically modified PVA.

The cationic modified PVA that characterizes the present invention is the first
-pvA having a cationic group such as a tertiary amino group or a quaternary ammonium base in its main chain or side chain.

Generally, PVA is obtained by saponifying polyvinyl acetate using an acid saponification method or an alkali saponification method.
The cationic modified products of PvA preferably used in the present invention are vinyloxyethyltrimethylammonium chlorite, 2,3-dimethyl-1-vinylimidazolinium chloride, trimethyl-( 3-acrylamido-3,3-dimethylpropyl)ammonium chloride, trimethyl-(3
-methacrylamidopropyl)ammonium chloride, N-<1.1-dimethyl-3-dimethylaminopropyl)acrylamide, N-(3-dimethylaminopropyl)methacrylamide, trimethyl(3-acrylamido)ammonium chloride, 1-vinyl- 2-methyl (or ethyl, phenyl) imidazole, 1-vinyl-2,4,5-trimethylimidazole, etc., quaternary ammonium salts (or
or 0-lm- or p-aminostyrene or monoalkyl, dialkyl, 5<q-isomers thereof; or their quaternary ammonium salts: 0-lm- or ρ-vinylhensylamine or their stiff monoalkyl, dialkyl derivatives or quaternary ammonium salts thereof;
class ammonium salts: N-(vinylhensyl)dololysine: N-(vinylhensyl)piperidine.

N-vinylpyrrolidone: α- or β-vinylpyridine or their quaternary ammonium salts: α- or β-piperidine or their quaternary ammonium salts: 2- or 4-vinylquinoline or their quaternary ammonium salts Salts, etc.: Copolymerize vinyl acetate with other nitrogen-containing heterocyclic vinyl compounds or vinyl compound molecules that can be easily converted into cationic groups, such as nitro derivatives thereof, and process the resulting copolymer using a conventional method. Obtained by saponification.

In addition, vinyl acetate and other polymers having reactive groups are copolymerized, and after saponification, such reactive groups are used to react with a cationic group-containing compound to cationically modify PVA. It's okay. Furthermore, by utilizing the hydroxyl group in PVA, a compound having a group capable of reacting with the hydroxyl group and a primary to tertiary amino group or a quaternary ammonium salt, such as glycidyltrimethylammonium chlorite, is used to form PVA. may be directly cationized.

The amount of cationic groups present in such a cationically modified PVA is expressed as a molar fraction at the 1,000-j11° position in the polymer, where the cationic groups account for 2 to 100% of the total monomer units.
A range in which it accounts for 20 mol% is suitable. When the amount of cationic modifying groups is less than 2 mol%, the recording agent adsorption of the coating layer decreases.
The recording properties such as water resistance, resolution, and color development of images or the storage stability of images under high humidity conditions are not sufficiently effective compared to those of unmodified ones. This is not preferable because the adhesive strength and film formability of the IU layer to the base material become poor. Although the degree of saponification of PVA, which is the backbone polymer, should be selected depending on the intended use of the recording material, it is preferable to use a degree of saponification of about 70 to 93 mol %. In addition, the degree of polymerization of the cationic modified PVA is 500 to s,
ooo is preferable, and 800 to 3,000 is more preferable. Furthermore, in any case, the higher degrees of polymerization and saponification may be used in combination.

Further, in the recording material of the present invention, it is preferable that the coating layer contains a compound having crosslinking properties.

A compound having crosslinking properties is a compound having crosslinking properties with a cationic modified product of PVA, and examples of such compounds include aldehyde compounds, carboxy compounds, activated vinyl compounds, polyvalent metal-containing compounds, and methylol compounds. , acid anhydrides, and the like. In the recording material of the present invention, it is more desirable and effective that the coating layer contains an isocyanate compound and/or a water-soluble melamine tree.

Particularly suitable as the isocyanate compound is a hydrophilic bourethane resin having an isocyanate group at the end obtained by reacting an isocyanate compound with a polyether polyol or a polyester polyol,
Also, suitable water-soluble melamine resins are methylolmelamine, particularly methylated methylolmelamine resins. Such resins are manufactured by methods well known in the T industry.

The cationically modified PVA used in the liquid fertilizer material of the present invention is a water-soluble polymer, so the π layer formed only from the cationically modified PVA is substantially water-soluble, The surface of the coating layer becomes tacky when water droplets adhere to it or when it is left under high humidity conditions, resulting in blocking when recording materials are placed on top of each other, and damage to the conveyance system of the recording device. This may cause problems due to adhesion or double feeding when feeding paper with the nails.

In a more preferred embodiment of the present invention, the coating layer of the recording material is composed of a cationically modified PVA crosslinked to suppress excessive hydrophilicity and have appropriate hydrophobicity (water resistance) by a well-known method. Therefore, the above-mentioned troubles will not occur.

The mixing ratio of the cationic modified PVA and the crosslinking compound is:
Although it varies depending on the type of crosslinking compound, 100/1 to
A suitable ratio of Ii'I is approximately 2/l<PVA0')fJfon-modified product/crosslinkable compound).

That is, a crosslinking compound or a thione-modified product of PVA
If it exceeds 2/1, the hydrophilicity of the coating layer formed will be low, resulting in no absorption of water-based ink. This is not preferred for recording systems that use water-based inks, such as water-based pen systems, pen plotter one-way systems, and ink sheet systems.

As crosslinking of the cationic modified PVA progresses, the water resistance, heat resistance, and surface hardness of the coating layer become better, but the absorbency of water-based ink decreases; however, according to the findings of the present inventors, crosslinking When a hydrophilic isocyanate compound and/or water-soluble melamine resin is used as the compound, there is little decrease in water-based ink receptivity even after crosslinking. This embodiment is composed of a cationically modified PVA crosslinked with an isocyanate compound and/or a water-soluble melamine resin.

Furthermore, a preferable embodiment of the present invention is an embodiment in which the coating layer contains a crosslinkable compound having 2 or more F atoms. According to the imagination of the present inventors, when two or more types of compounds are used together, in addition to the crosslinking reaction between the crosslinking compound and the cationic modified product of PVA, a reaction between the crosslinking compounds also occurs, and both Although the reactivity ratio of 1! is not determined, the cationic modified product of pvA is retained in the network of the water-resistant crosslinkable compound, resulting in the formation of 1! This is thought to be because the layer has moderate water resistance and also maintains affinity for water-based inks.

In the above embodiment as well, the mixing ratio of the cationic modified PVA and the crosslinking compound (total) is preferably about 100/1 to 2/1 by weight, and the mixing ratio of the crosslinking compounds used together is as follows: One type of compound does not exceed 90% by weight of the total amount. If they are not used in combination outside the range specified in F, no significant effect will be obtained.

Preferred examples of other polymers that can be used in combination with the cationically modified PVA in the above method include albumin, gelatin, casein, starch, cationic starch, gum arabic, natural resins such as alginate sorta, and polyamides. , polyacrylamide, polyvinylpyrrolidone, quaternized polyvinylpyrrolidone, polyethyleneimine, polyvinylpyridinium halide, melamine resin, polyurethane, carboxydimethylcellulose,
PVA, polynisdel, polysodium acrylate, SBR
Synthetic resins such as latex, N[111 latex, polyvinyl formal, polymethyl methacrylate, polyvinyl butyral, polyacrylonitrile, vinyl chloride, polyvinyl acetate, phenolic resin, alkyd resin, and epoxy resin are mentioned, and one type of these materials The above may be used as desired. When such a translucent polymer is used in combination with the cationic modified PVA,
The cationic modified PVA and other polymers are used in an IR weight ratio of 20:1 to 1:20, preferably 15:1 to 1:10.

In addition, in order to improve the blocking resistance of the coating layer in the above method, for example, wrinkle strength, clay, talc, diatomaceous material, calcium carbonate, sulfuric acid, etc. may be added to the extent that does not impair the transparency of the recording material. Coated with fillers such as calcium, barium sulfate, aluminum silicate, synthetic theolite, alumina, oxide 1, lead, lithopone, sachin white, etc.
It can also be dispersed in the π layer.

The recording material of the present invention is formed using the above-mentioned main materials, and this recording material has particularly excellent translucency.
It is used as 1 in the case of HP, etc., and is useful as a recording material for forming an image for transmitted light observation.

Such a light-transmitting recording material is prepared by coating the above-mentioned cation-modified PVA alone or using PVA on the above-mentioned light-transmitting base material.
A light-transparent coating layer is prepared by forming a light-transparent coating layer from a mixture of a cationically modified product of 1 and another light-transmitting polymer, preferably a polymer to which a crosslinkable compound is added.

As a method for forming such a V layer, the above-mentioned P layer can be formed.
A coating solution is prepared by dissolving or dispersing a cationic modified product of VA (P-only or a mixture of this and other polymers, preferably one containing 4F containing a crosslinking compound) in a suitable solvent. It is preferable to apply the coating liquid to the transparent substrate Murakami by a known method such as a roll coating method, a Rottbarcoach ink iL spray coating method, or an air knife coating method, and then quickly dry it. A method of hot-melt coating a PVA0 cation-modified product alone or a mixture with other polymers, preferably with the addition of a crosslinking compound, or a method of hot-melt coating the above-mentioned material once a sheet for a coating layer is formed; Other methods such as laminating the sheet to the substrate described above may also be used.

In the above recording materials, the thickness of the coating layer formed on the base material is usually about 1 to 200 um, preferably about 5 um.
It is about 100 μm.

The recording material formed as described above is a translucent recording material that has sufficient translucency.

In the present invention, sufficient light transmittance means that the recording material exhibits a linear transmittance of at least 2% or more, and preferably a linear transmittance of 10% or more.

If the linear transmittance is 2% or more, for example, 0) It is desirable that the ratio is 10% or more.

The linear transmittance T (%) here refers to the incident perpendicular to the sample, transmitted through the sample, and at least 8
The spectral transmittance of the straight light that passes through the light-receiving side slit on the extension line of the incident optical path north of 7 cm or more and is received by the detector is measured using, for example, a 323-type Hitachi self-recording spectrophotometer (manufactured by Hitachi, Ltd.), etc. The Y value of the color tristimulus value is determined from the measured spectral transmittance using the following formula.

T=Y/Y, xloo (I) T: Linear transmittance Y: Y value of sample Yo; Y value of blank Therefore, the linear transmittance referred to in the present invention is for straight light, and is for diffused light. Light transmittance (place an integrating sphere behind the sample to determine the light transmittance including diffused light), and Futsumachi salt (place white and black backings on the back of the sample and compare them) This is different from the method of determining the translucency using diffused light, such as 49-valued.

The problem with devices that use optical technology is the behavior of straight-line light, so when evaluating the translucency of the recording material to be used in those devices by 3f, Determining the ratio is particularly important.

For example, when observing a projected image on an OHP, in order to obtain a clear and easy-to-see image with high contrast between recorded and non-recorded areas, it is important that the non-recorded areas of the image are bright, that is, the straight line of the recording material. It is required that the light transmittance be at a certain level or higher. In OHP tests using test charts, in order to obtain images that meet the above objectives,
The in-line transmittance of the recording material is required to be 2% or more, preferably 10% or more in order to obtain a clearer image. Therefore, recording materials suitable for this purpose are:
It is necessary that the in-line transmittance is 2% or more.

Although typical aspects of the recording material of the present invention have been illustrated above,
Of course, the recording material of the present invention is not limited to these embodiments. In any embodiment, the coating layer may contain various known additives such as dispersants, fluorescent dyes, pH adjusters, antifoaming agents, lubricants, preservatives, and surfactants. can.

Note that the recording material of the present invention does not necessarily have to be colorless, and may be a colored recording material.

(Effects) According to the translucent image forming method of the present invention using a translucent recording material having the above structure, a high-quality and clear image can be formed on a recording material having excellent translucency. (ii) It is possible to provide a high-quality and clear projection image.

Translucent recording materials with the following configurations include electrophotographic recording systems, water-based pens, pen plotters (one-way systems), thermal transfer systems (7),
It is possible to form high-quality and clear images even with conventional recording methods such as the ink sheet method, and the image formation of the present invention involves recording on the liquid fertilizer 3E material by a recording method selected from the group F. According to the method, translucent image formation is faster, more precise, more colored, and lower cost than the conventional image forming method that used a special pen and color film on plastic sheets.

Furthermore, the recording material described above is capable of forming high-quality, clear, translucent images even when used in any of the recording methods in the first group.
It is possible to use a combination of one group of recording methods, and for example, by using the image forming method of the present invention using an electrophotographic recording method and a water-based pen, dense color images can be formed at high speed and at low cost. It is now possible to do so. A method of forming such a translucent image is hitherto unknown.

Furthermore, the image forming method of the present invention allows the formation of translucent images in the same manner as paper, and there is no selectivity regarding the recording method, so it is necessary to prepare a +7 recording material for each recording method. There is no need to do this, and it is excellent in terms of operability and cost.

(Example) Hereinafter, the present invention will be explained in more detail by giving Examples and Comparative Examples. In the text, parts or percentages are based on weight unless otherwise specified.

Example 1 A polyethylene terephthalate film (manufactured by Toshi) with a length of 11λ and 100 μm was used as a translucent base material, and a coating liquid having the composition shown in F was applied onto this film so that the thickness after drying was 5 μm.
Coat using a bar coater method and heat at 120°C.
The film was dried for 10 minutes to obtain a translucent recording material of the present invention. The surface electrical resistance of this recording material is 6.2×10”Ω
/ It was □.

Soil”jυOld-Cation modified PVA (PVA-C-318-2A
(manufactured by Kuraray) 100 parts of a 10% aqueous solution of comb polymer (manufactured by Soken Chemical) 2.5 parts of a 25% methyl cellosolve solution
20 parts of MMA macromonomer was graft copolymerized to 80 parts of a copolymer of 56 parts of diacetone acrylamide and 24 parts of diacetone acrylamide.

In addition, the surface electrical resistance is YIIP4:129A 1lG
11 nEsl5T-ANCE METER, YIIP
Measured using +6008A RESISTIVITY CELL.

Examples 2 to 5 The polyester film used in Example 1 was used as a translucent base material, and a coating solution with the following composition was applied onto this film so that the thickness of the wL coating layer after drying was 6 μm. The paper was coated with a bar coater and dried by heat treatment at 140° C. for 10 minutes to obtain a translucent recording material of the present invention.

m (Surface electrical resistance: 2.2 x 1012 Ω/□) Coating liquid composition: Cation-modified PVA (PVA-C-318-28, manufactured by Kuraray) 10% aqueous solution 100 parts incyanate compound (Elastron C-9 Part-T) Pharmaceutical products)
10% aqueous solution 7 parts Water-soluble melamine resin (Sumimar M-501, manufactured by Sumimaru Kagaku) 10% aqueous solution
Part 15 proof of failure (surface electrical resistance; 1.7x 1
(112Ω/□) Coating 11/i composition; Cation modified PVA (PVA-C-: 118-2
A, manufactured by Kuraray) 10% aqueous solution 50 parts Water-soluble polyester polyurethane resin containing isocyanate groups (Elastron E-37, manufactured by Kogyo Seiyaku) 2
5% water-soluble M 2.5 parts Catalyst (Elastron Catalyst 32, Dai-Kogyo Seiyaku Co., Ltd.) 0.2 parts Mojo Roku 1 (Surface electrical resistance; 2.8 x 1012 Ω/
□) Coating liquid composition: Cation modified PVA (PVA-C-318-2A
, Coo 7L/manufactured) 10% aqueous solution ioo
10% aqueous solution of 20 parts styrene/acrylic acid copolymer (Oxirac 511-2100, ``Hon Catalyst Chemical!!A'') 10% aqueous solution
10 copies combined record and 5 (Surface electrical resistance: 3
．． 5x 101207) Coating liquid composition.

Cation modified PVA (PVA-C-:118-2
^, manufactured by Kuraray) 10% aqueous solution 100 parts Water-soluble melamine resin (Sumimar M-100, manufactured by Sumimaru Chemical) 10% aqueous solution 4 parts Styrene/acrylic acid copolymer (Oxilac 511-2100, manufactured by Nippon Shokubai Chemical) 10% 2 parts of aqueous solution The thus obtained recording materials 1 to 5 of the present invention were slightly transparent.

Gon 2 Rokuj (Surface electrical resistance; 3.OX 1013Ω
/□) A commercially available OHP film (NP-Dry Transparency, manufactured by Canon) for electrophotographic copying machines was used as a recording material for comparison.

Expanded material 1- (Surface electrical resistance: 101SΩ/□F)
As a recording material for comparison, Ichi! An untreated polyester film (manufactured by Toshi) was used for the wings.

Next, recording was performed on the transparent recording materials (1 to 7) using the following recording methods A to E as representative examples of recording methods for forming images.

(Recording method A) A typical example of an electrophotographic recording method is a copying machine (NP-5
00Rε, manufactured by Canon), and the adhesion of toner in the formed image, scratches on the surface of the recording material,
Examine the presence or absence of cloudiness, toner scattering, ghosting, etc., and combine the obtained projected images by marking an image that is excellent in all as ○, an image that is poor in any of them as △, and an image that is inferior in all of them as ×. evaluated.

(Recording method B) A typical example of water-based pen recording is a highlighter pen (COl, 0
R5TA11: ] 665TAEDTLER) was used for three recordings, and the ink fixability and the presence or absence of changes in the shape of the coating layer surface during recording were evaluated.
The obtained projection images were evaluated as ``1'' as a whole, with a score of △ for a score inferior to even one, and a "x" for a score inferior to all of them.

(Recording method〇) A typical example of a pen plotter is a pen plotter.
(Myplot II MP-100OA, manufactured by Graphic Co., Ltd.), recording was performed with the attached water-based fiber pen, and evaluation was made in the same manner as in recording method B.

(Recording method D) A typical example of the inkjet method is the on-demand inkjet printer PJ-1080, which uses four colors of water-based ink and ejects ink using piezo vibration f.
A (manufactured by Canon) was used to record and check whether the ink piled up on the surface, the fixation of the ink, etc.
An overall evaluation was made of the projected images, with an score of 0 for those that were excellent in all, △ for those that were poor in all, and a × for those that were poor in all.

(Recording method E) As a typical example of the thermal transfer recording method, recording is performed using a word processor (PW-10, manufactured by Canon) that uses the thermal transfer recording method, and the transferability of the ink to the recording material and the recording material are evaluated. The shape change due to heat on the surface of the material was examined, and the obtained projection images were evaluated comprehensively, with those that were excellent in all of them as O1, those that were inferior in even one as △, and those that were inferior in all of them as X.

Table 1 shows the evaluation results using the following recording methods A to E.

In addition, in-line transmittance, OHP permeability, recording material h in Table 1
Li capture ability and water resistance were based on the following evaluations.

(6) Linear transmittance is measured using a 323-type Hitachi self-recording spectrophotometer (u
The distance from the sample to the window on the light receiving side was kept at 9 cm, and the spectral transmittance was measured. 1) η
It was determined by the following formula (I).

(7) OHP suitability was measured as a typical example of optical equipment, and was determined by displaying a recorded image on a screen using OHP and observing it with J-vision. The OD (optical density) is high, the projection image is clear and easy to see with high contrast. If it is a 0.25mm line or cannot be clearly distinguished, it is △, and if it is a non-recorded area, it is quite 11.
Goods <, OD of recorded image is quite low, pitch width is 1mm,
A case where a line with a thickness of 0.3 mm could not be clearly distinguished or a case where a non-recorded area and a recorded image could not be distinguished were rated as "×".

(8) Recording agent capture property was measured by performing a recording experiment on a recording material with a fluorescent pen at room temperature, and after 5 minutes, pressing a filter paper against the surface of the recording material. can be)
Colored filter paper was rated x (no capture ability).

(9) Water resistance is determined by whether the recorded image obtained using recording method C is immersed in still water for 1 minute, and whether traces of the recorded image can be discerned and whether tack occurs due to partial dissolution of the coating layer. We judged whether the results were correct or not, and made an integrated evaluation using ○ and X.

Go Σ1-j dyeing 1) Recording method AOOOOOO○ × 2) Recording method BOOOO○ × × 3) Recording method C○ ○ ooo xx4) Recording method D 000 00 × ×5) Recording method EOOOO
OO△ 6) Linear transmittance 82% 82'J 809 & 79! k
80! k 81* 84! 7) OHP11! sex
○ ○ ○ OO○ 8) Recording agent capture property OO○ ○ ○
× ×9) Water resistance 00000 x x
As shown in Table 1, using recording materials 1 to 5 of the present invention,
In addition, according to the translucent image forming method of the present invention using recording methods A-E, clear and high-quality images were obtained. If the water-based ink remains on the recording material for a long time, the ink may flow on the surface, or the ink may not be fixed even after - days have passed after recording, and the recorded area may be touched with a finger. The image was damaged and a clear translucent image could not be obtained. Further, when recording method E was used, ink was not transferred from the ink printer to the recording material in one minute, and a high-quality and clear projected image could not be obtained.

Furthermore, the recording materials 1 to 5 are stored at particularly high humidity (30°C, 85%R).
11) Smooth recording was possible even in the following environments.

When recording material 7 was used in recording method A, toner scattering and toner transfer failure occurred, and good images could not be obtained. Further, when used in the BE test method, similarly to recording material 6, high-quality images could not be obtained.

According to the recording material and method of the present invention configured as described above, the following effects can be achieved as already mentioned.

For example, in the case of a recording method using an aqueous medium, the fixing properties of the recording agent were excellent, and clear, high-quality translucent images, especially translucent color images, were obtained.

Also, methods that directly contact the surface for recording, such as using a sign marker, highlighter pen, fountain pen, etc., can also be used.
The recording portion sufficiently maintained a proper shape during recording, and no image damage occurred even when overlapping.

Furthermore, in the electrostatic recording method, one surface has excellent heat resistance,
Even after the toner was heat-fixed, there was no problem with the surface becoming cloudy, and an image with excellent translucency was obtained. Furthermore, high-quality images with excellent toner adhesion and no fogging caused by electrostatic charging or the like were obtained.

Furthermore, the recording material of the present invention can provide high-quality and clear images even in thermal transfer and impact recording methods, and the recording material and the recorded image are not deformed or damaged by heat during recording. Never happened. Furthermore, the transferability of the ink wax and the adhesion of the transferred ink wax were good.

As described below, in the recording material and image forming method of the til+ of the present invention, in the recording method using an aqueous recording medium, for example, the inkjet method and the method using the Pen Block-1 water-based writing instrument, etc. It is possible to obtain recorded images with excellent translucency to an extent that cannot be obtained, and furthermore, good results can be obtained even in systems that require heating, such as electrostatic recording systems and thermosensitive recording systems.

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Claims (14)

[Claims] (1) It is characterized by having a surface electrical resistance that does not exceed 10^1^4 Ω/□ and a coating layer that exhibits trapping properties for a recording agent that can be dissolved and/or dispersed in an aqueous medium. Translucent recording material. (2) The surface electrical resistance is 10^8 to 10^1^4Ω
The recording material according to claim 1 falling within the range of /□. (3) The surface electrical resistance is 10^1^0 to 10^1^
The recording material according to claim 1, which has a resistance of 4Ω/□. (4) The recording material according to claim 1, wherein the coating layer exhibits absorbency to an aqueous medium. (5) The recording material according to claim 1, wherein the recording material has a linear transmittance of 10% or more. (6) The recording material according to claim 1, wherein the recording material has a linear transmittance of 30% or more. (7) The recording material according to claim 1, wherein the thermal softening temperature of the surface of the coating layer is 100° C. or higher. (8) The recording material according to claim 1, wherein the coating layer has substantially water resistance. (9) The recording material according to claim 1, wherein the coating layer has substantially water resistance and has a recording agent trapping property even when wet. (10) The recording material according to claim 8 or 9, wherein the coating layer exhibits water resistance in a pH range of 4 to 10. (11) The recording material according to claim 1, wherein the coating layer has a wet abrasion fastness of grade 2 or higher according to JISL0853. (12) The recording material according to claim 1, wherein the coating layer contains a cationically modified polyvinyl alcohol and a crosslinkable compound. (13) The recording material according to claim 1, wherein the coating layer is non-porous. (14) A translucent recording material having a surface electrical resistance not exceeding 10^4Ω/□ and having a coating layer that exhibits complementary properties to a recording agent that can be dissolved and/or dispersed in an aqueous medium. An image forming method characterized in that image formation is performed using at least one of an electrostatic recording method, a recording method using a water-based pen, a thermal transfer recording method, and an inkjet recording method.