JPS62269135A - Silver based electrostatic printing master - Google Patents

Abstract

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

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to electrostatic printing, and more particularly to electrostatic printing, and more particularly, in preparing a master for printing, a conventional silver monolide copy': JL
The invention relates to an improved electrostatic printing master suitable for use with the technology.

BACKGROUND OF THE INVENTION Electrostatic printing methods are well known in the art;
It has been proposed as an alternative to other printing techniques. In one method of electrostatic printing, static 1! is used to create the desired image! A "master" that can selectively retain charge is first prepared.

The master is exposed to a corona discharge to create an electrostatic latent image and then contacted with a dry or liquid toner of opposite electrostatic charge to develop the image.

The toner image is then transferred to a substrate, typically paper, where the toner is fused to fix the image and the master is replaced for the next printing cycle.

In U.S. Pat. No. 4,069,759, by dispersing a conventional photographic silver halide salt in an insulating polymer (e.g. gelatin) and coating this dispersion onto a conductive substrate. , it was proposed that an improved electrostatic printing master be created. This coating is imagewise decomposed and developed so that the degenerated silver halide is reduced to metallic steel. Not yet! The original silver halide is then dissolved and removed from the coating to fix the image. This master, proposed in U.S. Pat. No. 4,069,759, offers many advantages and allows the use of conventional aqueous-silver halide photographic chemistry, but with gelatin as an insulating, 451J mer. When selected, gelatin has been found to be too sensitive to humidity when used in the workplace. Gelatin quickly absorbs moisture from the air,
At moderate to high humidity it no longer functions as an insulating medium, yet creates a conductive path through which a ground surface charge can build up on the master during electrostatic printing.

Therefore, based on the usual aqueous silver halide photographic chemistry,
The relative humidity conditions commonly encountered during single printing create a need for improved electrostatic printing masters that provide benefits such as superior insulation.゛The present invention provides g suitable for use in the preparation of electrostatic printing masters.
4, the composition is capable of swelling in an aqueous photographic processing layer with a μ value greater than about a5, and is notable for its ability to swell under relative humidity conditions commonly encountered during printing processes. It consists essentially of a photographic silver halide salt dispersed in an insulative polymeric binder that retains good insulating properties. This composition equilibrates for 1 hour at 20°C and 50% relative humidity! The skein surface has an insulating value such that it retains an apparent macroscopic electric field of at least 5 V/μm, as measured by an electrostatic surface voltage probe 2 seconds after being fully charged. Ordinary photographic gelatin, which is practically the only medium that can be processed by wet processing, is
Under these test conditions, after equilibration, approximately I
Just keep it at V/μm or less. Since this binder can be wetted to about A5 and pf3 under one condition, conventional aqueous silver halide developing solutions can be used to process masters used in electrostatic printing.

Acrylic acid or methacrylic acid co/IJ polymers with acid numbers ranging from 70 to 160 are preferred binders for selection in the practice of this invention. - the silver rhodanide/binder composition is typically applied onto an electrically conductive substrate;
It can also be mounted on a flexible support for use as an electrostatic master. After the master has been imaged by actinic light, this master is processed using conventional aqueous silver halide developing chemicals and fixing chemicals. is used and developed to contain a silver image.

In a second embodiment, a diffusion transfer film is prepared by t-coating a polymeric binder containing development nuclei on a conductive support and overcoating this binder with a conventional silver halide photographic emulsion. This photographic W& original element is fully exposed and then developed using conventional diffusion transfer techniques to reveal an imaged electrostatic master.

As used herein, the term "electrostatic master" refers to a master that contains silver particles in the form of an image that can be used in a printing process, or that can be exposed and/or developed. - Refers to film elements such as those used for electrostatic printing, which are film elements containing all silver halide grains.

The use of conventional aqueous silver halide photographic chemistry meets various requirements for the preparation of electrostatic printing masters, especially high quality halftone dots (h
It is ideally suited when high resolution is required for continuous full moons (alf-ton θ) or continuous full moons. Sharp image resolution can be obtained due to the fine grain size of silver, which can be obtained when using aqueous photographic chemistry well known in the industry.

The insulating binder selected for carrying out the present invention is typically in the range of 9 to 14 greater than about &5, which is common with common aqueous developers used in silver halide photography. - "swellable" in an aqueous solution with a value of - "Swellable" (meaning that the binder readily takes up water and thus swells in the same way as gelatin in this range. When using the preferred polymers described below, the swelling is about &5 This property is achieved by ionizing acidic groups (usually calgexylic acid groups chemically bonded to an insulating binder) by basic solutions with μ values of When silver halide emulsions are used, the exposed halide steel is reduced to metallic silver by the developer, and the unused metal is reduced to metallic silver by the developer. The n-element silver halide is dissolved by the complexing agent.

When a silver halide emulsion is used (made by well-known techniques such as solarization or chemical fogging), the unexposed silver halide is reduced to metallic silver, and The exposed silver halide is removed.

In an example described in more detail below, silver halide for negative printing is dispersed in an insulating binder as defined in this invention, a developer of about -A5 or higher swells the binder, and is exposed to light. The silver halide is reduced to metallic silver, and a complexing agent, usually in the fixer, removes the unexposed silver halide. In the diffusion transfer embodiment, the photosensitive silver halide for negative printing is in an emulsion layer (usually gelatin) that is separate from the insulating binder containing the fine dispersion of development nuclei. , a developer having a μ value of about &5 or greater swells both the emulsion layer and the insulating binder layer defined by the invention, thereby developing the exposed silver halide in the emulsion layer to metallic silver. , and the unexposed silver halide is dissolved by a complexing agent (silver solvent). The complexed unexposed silver halide then diffuses into the swollen binder layer where the silver ions are selectively reduced to metallic silver on the development nuclei.

Although the P3 marginal binder can swell in the developer, its insulating properties are not compromised as severely as gelatin does under typical humidity conditions encountered in the workroom; This binder retains the electrical charge during electrostatic printing, eliminating the need for special humidity control or drying the master before each printing cycle, which is required when using gelatin binders. .

Typically, the binder is left at 20°C and 50°C relative humidity to allow its surface to equilibrate and thus absorb moisture.
capable of maintaining an apparent macroscopic electric field of at least 5 V/μm, preferably at least 30 V/μm, as measured with an electrostatic surface voltage probe 2 seconds after the surface is fully charged. It is characterized by certain things. Equilibrium for the test will normally occur within about 60 minutes; in contrast, gelatin is significantly inferior, and under this test method has an apparent The macroscopic electric field was shown.

Synthetic polymers having acid numbers of about 70 to 160 have been found to be particularly useful in the practice of this invention. Preferred classes of polymers to provide swelling properties include:
Typical polymers containing 10-25% by weight of acrylic or methacrylic acid contain styrene, which is water-incompatible, or other aromatic atoms, which make the polymer resistant to atmospheric moisture. to make it less hydrophilic. Typically, the polymer also includes monomers such as suitable acrylic or methacrylic esters, which improve the film's transparency, flexibility, toughness, and
It depends on processing performance etc. Other copolymers, such as alkenes with 2 to 12 carbon atoms, /% OOL
/ Fins, vinyl acetate, vinyl ethers with 3 to 12 + 7) carbon atoms, methacrylamide and the like are also useful.

Preferred polymers are copolymers containing styrene and acrylic acid or methacrylic acid monomers, and preferably also acrylic ester or methacrylic ester monomers. 25-30 1 ton of styrene,
10-25 weight acrylic acid or methacrylic acid,
Particularly preferred are polymers containing those in which the balance consists of acrylic esters or methacrylic esters. The molecules ik of preferred copolymers are typically 2
It ranges from 5,000 to 150,000. These polymers are compatible with silver halide dispersions, produce transparent and durable films, are readily available commercially, and are susceptible to free radical polymerization in cloudy or emulsified states. using ordinary techniques such as .

You can also make it with Equivalent polymers useful in the practice of this invention will be apparent to those skilled in the art, including polymers and copolymers of acrylic acid and methacrylic acid, and those described by B.F. Good. Lynch's Cal? Set ■525 and Cal set [
F] 526, and those available on the market such as Soyeon Kryl [F] 67 from P.

Preferred classes of polymers include (1) styrene-type monomers, (2) acrylate-type monomers, and (3) styrene-type monomers.
) Unsaturated Cal? It consists of a xyl-containing heptamer terpolymer 2 and a tetrapolymer. The first component provides hardness and moisture resistance to the polymer, the second component provides flexibility and plasticity to the polymer body, and the third component provides alkali swellability. Styrenic monomers typically include styrene, alpha-substituted styrene with an alkyl group of 1 to 6 carbon atoms, and active substituents such as nitro, alkoxy, acyl, carboxy, sulfo or halo, etc. on the benzene nucleus. Simple compounds such as styrene, alpha methyl styrene, tert-methyl styrene, and t-zotylstyrene are preferred. Acrylate-type components include alkyl and hydroxyalkyl acrylates and methacrylates, where the alkyl group has 1 to 12, preferably 1 to 6 carbon atoms, such as methyl methacrylate. , ethyl methacrylate,
These include ethyl acrylate, hydroxyzolobyl methacrylate, hyP-roxymethyl methacrylate, hyP-oxyethyl acrylate, and mixtures thereof. The unsaturated carboxylic acid content is typically 3 to 1.
Heptamines with 5 carbon atoms, preferably 3 to 6, such as cinnamic acid, crotonic acid, sorbic acid, itaconic acid, maleic acid, fumaric acid, and even more preferably L < t
'! Included are acrylic or methacrylic acid, their corresponding half esters or corresponding anhydrides, and the like.

When this class of polymers is selected in the practice of the present invention, the proportions of the three heptamer components are selected such that the 114-conducting film element has the following properties: - The halogenated scissors can be processed by common aqueous photographic techniques; the electrostatic master made from it retains the deep charge in the silver-free area under ambient conditions of relative humidity:
And this electrostatic master is flexible; durable and non-tacky. Representative kitamotos used to achieve these results are shown in Table 1.

Carboxylic Acid Type 5-50 10-25 This class of polymers has the advantage of not being sensitive to the common carrier IMPA used in liquid toners.

The insulating polymeric binders described above, rather than those shown in the examples, are made by conventional free radical polymerization techniques. These polymers are soluble in basic solutions;
It can be applied from an aqueous solution such as triethanolamine, ammonia, or potassium. These polymers are compatible with silver halide dispersions and form transparent durable films. It is preferable to modify the binder (crosslinking, curing, plasticization, adjusting acidity, etc.) prior to aqueous photographic processing, thereby adjusting swelling properties or improving durability. Various modifiers can be added for this purpose. Typical modifiers include aldehydes, multifunctional azidinones, and epoxides. For this class of polymers in the practice of this invention, diglycidyl ether of 1.4=butanediol is the preferred modifier.

Equivalent polymers that achieve the balance of properties described above will be apparent to those skilled in the art and may be selected in the practice of this invention.

The photosensitive silver halide selected for dispersion in the paint goo can be any of the well-known salts used in photographic applications. Representative useful salts include silver chloride,
Silver bromide, silver iodide, silver chlorobromide, silver iodobromide, silver chloroiodobromide, etc. are included, and they may be used singly or as a mixture. - Precipitation of silver halogenide is carried out in a conventional manner in flea gelatin.To avoid defeating the purpose of the invention, the amount of gelatin present should be limited;
Or it should be washed away afterwards to reduce it. Typically, at most 3 to 15 mol of silver per mole. of gelatin can be tolerated in electrostatic printing masters without exhibiting any detrimental effects.

Grain size distribution and silver halide sensitization are defined as grain size distribution and silver halide sensitization suitable for selected classes of photographic processes such as general continuous tone, X-ray, phosphorography, microphotography, direct blurring, etc. It can be adjusted as you like. Generally, silver halide dispersions include sulfur, gold, lotum,
Conventional compounds such as selenium and others or cyanine, 1,1'-diethyl-4,4'-cyanine iodide, methine and ? Sensitized by organic sensitizing dyes such as rimethine cyanine dye, cryptocyanine, merocyanine, and others. Other additives commonly used in silver halide photographic materials can also be added, if desired.

To prepare a 9-silver norogenide dispersion in an ffl-resistant polymeric binder, the binder is generally dissolved in an aqueous solution containing an amine such as ammonia or triethylamine. If necessary, an alcohol such as methanol, ethanol or inpropatol is added to help dissolve the polymer. Ketones such as methyl ethyl ketone can also be added as co-solvents. - An aqueous dispersion of silver halide salt is then added to the dissolved binder in the required quantity. The amount of silver halide to binder depends on the specifics of the application, but is generally such that the master surface immediately above the developed silver discharges significantly more rapidly than the areas without silver.

Ratio of silver to polymer binder to 11, 5~
A 1:3 range will typically give useful results.

The preferred range is 1:1.7 to 1:2.3.

The polymeric binder containing silver halide is applied to the electrically conductive substrate as a dispersion or solution in an aqueous carrier solvent containing basic amines or potassium or sodium as described above. Application may be by any of the conventional methods, including spray, brush, roll or dip applicator application, pouring onto the surface, pick up, spin cord, air knife, wire pull application, and other means. . The thickness of the film is typically about 0.02 to about 0.3 mil (about 0.5 to about 7.5 mils) after drying.
5 μm) preferably about c1.04 to about α20 mil (
from about 1.0 to about 5.0 μm) and adjusted accordingly. Depending on the intended use, the conductive substrate can be a metal plate such as aluminum, copper, zinc, silver, etc.
? +7mer film: substrates such as paper, glass, synthetic resins, etc., coated with metals, metal oxides or metal halides by vapor deposition or chemical deposition: substrates coated with conductive polymers: or metals, gold #i The substrate may be coated with a polymeric binder containing all oxides, metal halides, conductive polymers, carzenes or other conductive fillers.

In addition to the various components mentioned above, common photographic additives such as developers, superadditives, antifoggants, coating aids such as saponins, alkylarylsulfonic acids or sulfoalkylsuccinic acids: glycerol or 1. Appropriate additions to the master include a benabilizer such as 5-pentanol; an antistatic agent; an agent to prevent the formation of organic matter; an antihalation dye; an undercoat, undercoat, or backing layer; and others. be able to. Bonotizo images can be obtained by reversal processing of silver halide, either by photofogging or by chemical fogging agents; or by giving a direct positive m using prefogging techniques. It can be obtained by silver halide emulsion.

The direct positive emulsion is described in Lielsmarker's U.S. Patent No. 2,
No. 184,013, Illingsworth U.S. Pat. No. 3,501,307, and others.

Referring to the drawings, FIG. 1 shows an electrostatic printing master, the photosensitive layer 1 comprising photosensitive silver halide dispersed in an insulating binder according to the invention. The eyebrows 1 generally have a thickness of 0.5 to 7.5 μm, but the eyebrows can be made thinner or thicker depending on special intentions. An optional adhesion-promoting thin layer 2, such as gelatin, helps the photosensitive layer adhere to a conductive base layer 3, which rests on a supporting substrate 4.

This master is active ft, II! Imagewise exposure is performed by any of the methods commonly used for silver halide photographic materials, such as imaging with a cathode ray tube or laser. The latent image 5, shown in FIG. 2, is developed using a conventional aqueous developer solution by reducing the exposed silver halide to metallic silver. A conventional aqueous fixing solution such as sodium thiosulfate is
As shown, it is then used to remove unexposed silver halide grains. This developed master is now ready for electrostatic printing.

FIG. 4 shows the master of FIG. 3 after it has been charged by a corona discharge, depositing a ponotive charge 6 on the master surface. The area 5 of the silver-containing film provides a path for the charge on the surface to escape to ground, thus creating a latent image of charge that remains on the master surface. Alternatively, charging can be accomplished using a negative corona discharge, a shielded corotron, a scorotron, a radioactive source, a contact electrode such as an electrically biased semiconducting rubber roller, or the like.

This latent image is then developed with liquid or dry toner 7 of opposite polarity, as shown in FIG. Suitable methods include cascade, magnetic brush, cloud method, liquid development, Magne-Dry 2, and wet development. Typical dry toners used include Kodak's Ektaprint toner, Hitachi's Hi-Toner HMT-414, and Canon's N.
P-350F) toner, and Toshiba's T-5UP toner. Suitable liquid toners include Sabin's 24 toner, Canon's LBP) toner, and James River Graphics' T1818) toner. The thus developed (toned) latent image is transferred to a conventional substrate, typically paper, where it is fused in a conventional manner.

A second embodiment is shown in FIGS. 3-9, and is illustrated in U.S. Pat.
Conventional diffusion transfer techniques, such as those described in No. 3.606, were used to create an electrostatic printing master with an image of silver dispersed in the previously described insulating synthetic binder. . In this example, the insulating synthetic binder 9 contains dispersed development nuclei with a thickness of about 0.25 to 3 μm, and the g-element layer 8 contains a silver monohalide salt dispersed in a hydrophilic colloid. Overlying the binder, the ratio of silver to binder 9 is between 1:1 and 5:1. A conductive layer 3 and a substrate 4 are used as previously explained. Suitable development nuclei are well known to those skilled in the art and typically include (1) metals such as silver, gold and rhodium; (2) silver, zinc, chromium, gallium, iron, cadmium, cobalt, nickel; manganese, lead, antimony, bismuth,
Sulfides, selenides, tellurides of metals such as arsenic, copper, rhodium, palladium, platinum, lanthanum and titanium,
Polysulfides or polyselenides: (3) Easily reducible silver salts that form silver nuclei during processing, such as silver nitrate or silver citrate; (4) Inorganic substances that react with incoming diffusing silver salts to form nuclei. and (5) organic compounds, which are (a
containing active sulfur atoms, such as l mercaptans, xanthates, thioacetamides P1 dithiooxamides and notothiobiurets, which generate sulfide nuclei during processing, or with reducing agents such as tb+hydranone derivatives or silanes; It produces silver nuclei when deposited on silicic acid or barium sulfate. Furthermore, the hydrophilic colloids can be any of those commonly used in diffusion transfer methods, such as gelatin, heptalated gelatin, cellulose derivatives such as carboxymethyl cellulose and hydroxymethyl cellulose, and dextrins, Soluble starch, polyvinyl alcohol, or other hydrophilic polymeric colloidal materials such as polystyrene sulfonic acid.

Referring to FIG. 7, photosensitive layer 8 is exposed in a conventional manner to create a photosensitive silver halide layer 911. For negative emulsions, the light-sensitive Ifihx is then treated with a developer to reduce the exposed silver halide in areas 10 to metallic silver, and treated with an aqueous solvent composition to reduce the - halogen in the unexposed areas. converting the silver oxide to form a soluble monohalide scissor complex which diffuses into the layer 9 of synthetic binder where it is reduced to insoluble silver particles 11 in contact with development nuclei;
The a-layer 8, which produces the silver image, is then removed as shown in FIG. 9, yielding an electrostatic master ready for printing in the usual manner. Developers for this diffusion transfer process are well known and are described, for example, in Andrelot and Edtwide (Focal Press 1972) and Grant Ha (Wiley Publishing 1979).

Numerous other alternatives will be apparent to those skilled in the art. For example, silver halide emulsions for ponotibs may be used in conjunction with the diffusion transfer coatings 8 shown in FIGS. 3-9. Is it possible that the exposed silver monohalide is converted into a complex salt in an aqueous solution to form a layer of insulating binder? and is reduced by development nuclei to form the desired silver image.

Similarly, another photosensitive film can be used instead of the photosensitive layer 80 and acted with the insulating binder 9 before or after imaging. Photosensitive silver halide emulsion NI'! The insulating polymeric binder layer 8 and the insulating polymeric binder layer 9 may contain a variety of compounds commonly used in diffusion transfer systems, such as the insulating binder or silver-containing areas 11 of the electrostatic printing master.
It can be contained as long as it does not impair the conductivity of the material. Therefore, suitable antifogging agents such as tetraazoindene and mercaptotetrazole, dispersion aids such as saponin and polyalkylene oxy-P, hardeners and plasticizers such as formaldehyde and chromium chloride, etc. It can be used as needed. The supporting substrate 4 can be used if the master is used as a photographic tool or for photolithography.
It can be made transparent.

Various methods can be chosen for ioning the electrostatic print master.

If the toner particles are conductive and essentially neutral, or are oppositely charged to the housing or latent image, they will adhere to the charged latent image. If the toner is charged with the same polarity as the charged latent image, the toner will stick to the uncharged areas. To aid in uniform toning of areas and to prevent background toning of uncharged image areas, a developer electrode can be used. Transfer of the colored image to the desired substrate, typically paper, is facilitated by the use of a corona discharge of opposite polarity on the grave side of the substrate. Alternatively, toner transfer can be accomplished with electrically biased rollers, adhesive films, paper, and the like. The toner image thus transferred is fixed by conventional methods known to those skilled in the art. Normal heat fixing, solvent fixing,
Pressure fixing and other methods are used. When necessary, the surface of the master is cleaned using a brush, rag, blade, vacuum knife, or other cleaning means to remove residual toner images.

This electrostatic printing master offers several advantages over those previously stated. Conventional aqueous development and fixing methods are required to remove soluble by-products in the solutions used for these purposes; It is free of biological material and does not suffer from the conditions encountered using the dry silver monohalide development process described in US Pat. No. 4,069,759. Also, the insulating properties of the binder selected in accordance with the present invention are less sensitive to moisture which can interfere with electrostatic printing processes, thus requiring the use of heating the master to remove moisture or special humidity adjustments. The master can be used repeatedly or after storage. Using the electrostatic printing master provided by the present invention, high resolution can be obtained and the results obtained are high grade phosphor,
Comparable to those obtained with flexographic and letterpress printing methods. Halftone imaging is usually employed for this purpose, but this master method is useful because the density of the developed silver varies with the original intensity used in the image on the film, as in conventional photography. can also be used for the inverse successive gradation method.

The following examples are illustrative of each type of the invention and should not be construed as limiting the invention. Other applications will be apparent to those skilled in the art.

In the examples all parts and cents are by weight and all temperatures are in degrees Celsius unless otherwise indicated.

Unless otherwise stated, the silver halide emulsions are negative and sensitized with gold and sulfur-containing compounds in the conventional manner. Silver chloride has cL13 mmol of P per mole of silver.
It is primed with hC15.

A general method for polymer preparation is as follows: Polymer A (styrene/methyl methacrylate/ethyl acrylate/methacrylic acid, 30/10 by weight)
/40/20).

A high speed stirrer, reflux condenser, dropping tube, p and thermometer were installed!5! flask contains 788 t deionized water, 5 t Duponol WAQg (sodium lauryl sulfate), 35.2 F styrene, 11.7 t methyl methacrylate, 4 & 92 ethyl acrylate, 25.49 methacrylic acid, and 0.5F octyl mercaptan was charged. The flask was flushed with nitrogen gas and heated to 60°C for 15 minutes.

(LO2f of ferrous ammonium sulfate, 0.28F ammonium persulfate, and 128P of ferrous ammonium sulfate were added to a sodium bisulfite flask, while the mixture was heated at 69°-7
Emulsification is continued at 4°C.

316,! M styrene, 105.5y methyl methacrylate, 422f ethyl acrylate, 211t
of methacrylic acid, and 5.1 Of octyl mercaptan were added to the flask over a period of 140 minutes, while simultaneously adding 2.061 Of ammonium persulfate, 0.
L52t of sodium bisulfite and 19.49g of Duponol WAQETh 100CI in deionized water were added at 140 minutes. Polymerization was continued for an additional hour and the emulsion was slowly cooled to ambient temperature for 1 h. A solution of Part 5 calcium acetate was added, at which time the trimer agglomerated. The excess water was removed, the solution was washed repeatedly with deionized water until the P solution became clear, and the solution was vacuum dried. Polymers B~ were made in a similar manner. The polymer composition and acid value are shown in Table 2 below. The acid value is the η number of potassium potassium necessary to neutralize the polymer'-1rM, and was determined by potentiometric titration.

Table 2 7-a Polymer S MMA EA EMA
AA MAA ANA 30 10 4o
20 124B 25 40 2
0 15 94C27601380 D 30 53 17100g
25 21 30 24 151F
35 13 28 24 152G
254020 15 81H51
2920135 I 45 40 15 97S=
Styrene MMA = Methyl methacrylate EA = Ethyl acrylate AA = Acrylic acid MAA = Methacrylic acid AN = Acid value Examples 1-11 show various polymers used with different silver halides and different) It shows the charge retention in case of polymer ratio.

Examples 1-6 Solutions were made from each of the following ingredients. . That is, polymer 1a
l Q, 5 g triethylamine
Example 1 = Polymer A Example 2 = Polymer B Example 3 = Polymer C Example 4 = Polymer D Example 5 = Polymer E Example 6 = Polymer F For this solution, silver chloride 1 Silver chloride emulsion containing 5.3F gelatin per mole (silver chloride grains are CL13 per mole)
Doped with mmol RhCl3, median edge length
0.13-0.17 μm) 15.11 Liquid 12
．． 5P was added with stirring. This dispersion was applied with a doctor knife onto a copper-coated polyester substrate. The dried film has a thickness of 2.4 μm and a size of 10.

It had 90 m9 of silver chloride per cWL2 and the ratio of silver ions to polymer was 2.8:1. The unexposed film was pan processed according to the following procedure:
Commercially available glue sogel rough developer (CUFD, E, I, manufactured by DuPont, manufactured by Nemo Earth), 3 for 30 seconds
0 ts sodium thiosulfate fixer, then 2 ts acetic acid stop solution for 15 seconds at 25°C, then washed with cold water and 15 seconds at 125°C.
Dry for 0 minutes.

The treated film is mounted on a flat plate,
The copper layer was connected to ground and equilibrated for 1 hour at 24° C. and relative humidity. These were then subjected to a corona band i! (by a double line corotron) at a 2 kV. The charge was stopped (time 20) and the charge was then allowed to decay. The results obtained are summarized in Table 3 below at 773 m.

TABLE 3 EXAMPLES R) I=23 RE=50% Examples 7-10 Solutions were made from the following ingredients. i.e. polymer (al 32.7f triethanolamine 11.!M water
131 t(a) Example 7 = Polymer 〇 Example 8 = Polymer H Example 9 = Polymer I (vinyl acetate) acid value 67 74.2 t of silver chloride from Examples 1 to 6 was stirred into this solution. I added it while doing so. However, it contained 35.39' gelatin per mole of silver chloride. This dispersion was applied to a copper-coated polyester base as in the previous example. The dried film was 4 μm thick and contained 100 :I
I had a silver plate 1tk of rL2 v80W9. The silver ion to binder ratio was 1.15:1. The film was prepared using commercially available X-ray film developers (MXD, E, I,
DuPont) and a fixer (thiosulfate) at ambient temperature. These were treated with acetic acid, washed with water, and dried at 125° C. for 10 minutes.

After equilibration at 24°C and 37°C relative humidity, the treated film was corona charged as described in the previous example. The results are summarized in Table 4 below in voltage per μm. Emulsion (silver bromide 9a 5 mol, silver iodide 1.5 mol, average grain volume α0 185 μm
Example 9 was repeated using 3). The thickness of the dried film was 4 μm, and the concentration was 80119 per 100 cIIL2.
It contained silver monohalide. The ratio of silver ions to polymer is 1.15:1. The films were treated and charged in the same manner as in Examples 7-11. At 24°C and relative humidity of 37°C, the static tit pressure maintained per μm in the polymer zone is:
2.30.80. at 60 and 120 seconds respectively.
It was 56.47 and 40v/μm.

Examples 12-17 demonstrate the use of various conductive substrates with two different insulating polymers.

Example 12 Polymer J (methacrylamide/methyl methacrylate/ethyl acrylate/methacrylic acid, 4.2/4
2.8/43/10) was created as follows.

That is, 4.22 methacrylic acid mir, azar methyl methacrylate, 43t ethyl acrylate,
10t methacrylic acid and 0.1f VAZC! 6
4. The mixture of initiator (azobisisobutyronitrile) added in t-t-sitanol 6662 was heated under nitrogen atmosphere.
Heated at reflux for an hour. Separately once [VA of 1L1t
ZO was added and reflux was continued for 2 hours, and α1 was added twice more.
t of VAZO was added and reflux was continued for a total of 8 hours.

The polymer was precipitated in cold water, washed with water, and dried to a white powder. Solutions of each of the following components were made.

That is, polymer J aof triethanolamine α5f water 5 5.
Of this polymer solution, 99 V of the ortho-sensitized silver iodobromide emulsion of Example 11 was added with stirring. This emulsion contains gelatin fl silver halide 1
139 molar gelatin and - silver chloride content
0 dispersion was 6.0 m after drying using a wire bar on aluminum under a red safelight.
It was applied to give a coating of .mu.m.

The application was handled and processed under a red safelight. The image shows a tungsten lamp at a distance of 56 inches (1,42 m) (lamp output is 12 inches (30,5 m) from the bulb).
Using a 10 foot candela (107.6 lux) at
lf tone) and a resolution plate by contact printing. In this example the exposure was given for 1 second and plate developed for less than 1 minute under a nitrogen atmosphere with the following developer: 0.01 Part Potassium Bromide 105 Part Sodium Sulfite 1.00% Hydroxylamine Hydrochloride in Deionized Water 0.01 LIJ
Dimaison-8 1,004 Hydroquinone 5.40% Potassium carbonate 5.40% Potassium bicarbonate, then fixed for 2 minutes, stopped in dithiacetic acid for 2 minutes,
They were washed in distilled water for 2 minutes, both at 26°C, and then dried in air heated to 125°C for 1 minute.

The image consists of a black silver image in the exposed areas of the coating and a white background in the unexposed areas. Resolution is 1■
There were at least 101 wire pairs per line. Charge amount and dark decay were measured using a Monroe model 276A electrostatic analyzer. The initial charge amount of the exposed area was 8V, which was the same as that of the aluminum blank, and did not attenuate even after 60 seconds. The initial charge of the unexposed area -1 is 153V, which increases to 1 after 10 seconds.
00■, attenuated to 92V after 20 seconds and 75V after 60 seconds. This difference in charge between exposed and unexposed areas is useful for electrostatic toning.

This electrostatic master is charged with a positive corona to a maximum charge, while the aluminum substrate is electrically grounded. After a few seconds of decay, the ground is removed and the plate is filled with a non-polar hydrocarbon liquid Isopar 0 with a cowriebutanol value of approximately 27.
The sample is immersed in a negatively charged black toner particle dispersion manufactured by Exxon. The toner will stick to the white parts of the image without silver, making the entire master appear black. This is gently rinsed in a dish containing Isonor 0, drained, wetted again with Isonor [F], stacked with paper, and passed under a positive corona to help transfer the toner to the paper. Picture gl! transfers normally (toner transfers where there is no silver on the master), and when the master is wetted with isobars, a resolution of 6 line pairs per penalty is obtained.

Example 13 The method of Example 120 was repeated with the following changes. That is, the emulsion was coated with copper to a thickness of 5.7 μm.

Polyimide film manufactured by DuPont de Nemo Earth)
The overcoated and treated film was heated at 125°C for 5
heated for minutes. The electrostatic master thus finished was mounted on the drum of a Sabin 770 copier, charged and toned, and the image was transferred to paper as in Example 12. Between 100 and 150 copies of black toner images with a resolution of 201s were obtained.

Example 14 A polymer solution of 992 was used, the resulting silver ion to polymer ratio was Cu2S:1, and the dispersion was coated on copper-coated Kapton [F] to a coating thickness of 5.7 μmK. 12 I completely turned around. The subsequent processing is the same as in Example 13. This master seems to have good charging and gradation due to its high f-remarch (Example 14), but the image coating tends to peel off easily.

Example 15 Aluminum evaporated Mylar 1'81 (E.

Example 12 was repeated using a polyester film (manufactured by A.I., Depont). A perfect image was obtained with no problems with adhesion or image quality.

Actual flow example 16 Same process as Polymer J, 4.2f methacrylamide, 21.8t methylmethacrylate, 64t
Polymer K was made using 3 t of ethyl acrylate and 10 t of gold methacrylate. A film was made, exposed, processed, charged and toned as in Example 12. Initial charging it'! 55V, 10
The charging i/ after seconds was 16V.

Example 17 The same coating and treatment as Example 16 was used in this smudge example, but the image was heated to 125° C. for 10 minutes. The image area (A), which was air dried before heating, was somewhat cloudy; the area CB), which was wet when placed in the oven, became clear after heating.

The black silver image had a resolution of 228 line pairs per fl. The charge and decay of the images were measured with a Monroe model 276A static analyzer under the relative humidity of each strain and are shown in Table 5. Data are in V per μm.

Table 5 B So 40 34 32 201A 70 50 43 38 E 48 32 27 24 35th Section A 54 29 23 19 B 36 17 13 11 49th A 53 24 18 15 B 35 13 9 7 63th A 18 5 2 - B 11 2 - - 72 A 21 - + B 9 - The copper layer of the electrostatic master in this example was electrically grounded and the image was positively charged by the corona under ambient conditions. After a few seconds, the grounded image is immersed in a toner bath consisting of negatively charged toner particles in iso/4-[F], gently shaken with iso-[F], and this The wet image is transferred to the paper with the help of a negative corona on the paperback side. This toner image is positive with respect to the original image, negative with respect to the master,
The resolution was 916 line pairs. The electrostatic master is recharged, toner is applied, and the toner image is allowed to dry. The transparent adhesive tape removes toner from the master and is positive for the original and zonal.
Provides a transparent image with zero-line pair resolution.

Examples 18-24 This example demonstrates the properties of a film made by dispersing a silver salt in a gelatin binder, but also by dispersing the same silver salt in the improved insulating medium of the present invention. It contrasts with the nature of things. The silver salt used in all examples was silver chloride grains, with 0.0.
It is doped with 13 mmol RhCl3 and has a central edge length of 0.13-0.17 μm. Charge retention was measured after developing the unexposed film.

■ Film with gelatin binder Tin chloride curds containing 1i3f' of gelatin per mole of silver chloride
) (The particles contain 113 mmol of Rh per mole of silver chloride.
Doped with Cl3, median edge length 0.13-0
．． Add 361C1 (with 17ttm f) to 3045r of water, and add 130t of IJum solution to 3045r of water.
H was set to 6.7, heated and stirred at 45°C for 1 hour, and then 214 tf of a solution made from a mixture of 165.2 f of 0.1N sodium hydroxide, 32.1 t of tetraazoindene and 16.7 f of water was added. Additionally, a silver chloride dispersion was prepared.

The pyrimidine gelatin was swollen in water at 20°C and dissolved by adding additional water at 50°C to give a 15 weight solution. Add 295 t of gelatin solution to 7052 of AgCl dispersion to make a net 1
I made an emulsion of 763 Jukei AgC1. Add formaldehyde hardener to 5 tons of formaldehyde per 10,002 emulsions.
was added to a concentration of

This emulsion was coated with indium oxide using a laboratory coater.
Coated onto a tin-coated polyester substrate (surface resistance approximately 500 ohms/square, Q, 127 m thick polyester paste). The film was processed using standard g with the following procedure: develop, stop, set, stop, wash, dry. The gelatin used and the coating thickness after treatment are summarized in Table 3.

(11) Film with improved 4-remer binder A solution was made from each of the following components, i.e. polymer
2.00f water
IQ, 44f isopro/9-nor! L2Cl caustic potassium
0.30f potassium bicarbonate 0.
062 Acid Violet 520 Dye 0.1
0f AgCt Cars 549 containing 10 tons of gelatin per mole of silver chloride was added to this solution while stirring. The 0 dispersion was prepared using a wire-wound rod to form an indium oxide-tin oxide coated polyester substrate (surface resistance) subbed with gelatin. The film was coated on a 0.127 m thick polyester film (approximately 500 ohms/square). This film was processed according to the method described for the gelatin film; the polymers used and coating weights are summarized in Table 3.

6 Table 18 2688 Deionized Gelatin 5,21
9 268B deionized gelatin 1.820
Lucero-I LLS non-deionized 5.8
gelatin 21 Lucero-ILLS non-deionized 2
．． 8 gelatin 22 Polymer A1.6 23 Polymer EO99 24 Polymer E1.4 0 After treatment (iiD Measurement of charge retention power) The above film sample was mounted on an aluminum plate,
Electrical connections to the conductive indium-tin oxide substrate and ground were made using conductive copper tape. The film is my Omega hygrometer (Ft)! -201 model) under a predetermined relative humidity at the edge, the sample was allowed to equilibrate in a covered box for 1 hour, and then a double-wire corotron was charged with a voltage of 6 kV with a deep corona. The voltage is the electrostatic surface voltage
It was measured by using Pe. The result is 7 in Table 7.
It is summarized in terms of 7 μm.

@7 Table implementation Example time (seconds) 18 19 20 21 22 2
3 24T=24℃ RH=11 Example T=23℃ R) 1=30% Example Time (seconds) 18 19 20 71 22
23 T=22° C. RH=48 Films with a gelatin binder were heated to determine the effect on electrostatic properties. Example 18~
No. 21 films were dried at 100° C. for 10 minutes, then conditioned at 48° relative humidity for 1"! or 10 minutes, after which electrostatic data were measured. These V/μm data are They are summarized in 8 tables.

Table 8 Example 0V) Toning Results The films of Examples 18 to 24 were heated at a temperature of 19°C and a relative humidity of 48°C.
6 developed with a liquid electrostatographic toner containing Kagen black pigment in a modified Serpin model 870 copier under identical conditions as described above, with a corona charge-to-toning time of 15 seconds.

The double line corotron was biased at 6 kV and the development electrode was held at ground potential. Transfer of the toner from the film surface to the offset enamel paper was accomplished using a biased transfer roll. The toner transferred to paper is heated to 100℃ in a furnace.
It was heated and melted. Reflection optical density measurements were made using a Macbeth M918 densitometer and are shown in Table 9 below.

Table 9 Example Ambient conditions After heating 1 1B 0.02 Q, 5619
0.02 Q, 3020
α02 0.20 21 0.02 0.27 22 1.51 23 1.34 24 1.11 8 Heated for 10 minutes at 100°C and conditioned for 1 minute at ambient conditions prior to toning.

Examples 25 and 26 demonstrate the use of commercially available resins as insulating polymer binders.

Example 25 Cal in 35f of water? Setsu) @526 (ethyl acrylate/methyl methacrylate/acrylic acid 17/71
/12 ratio copolymer, B.

2.5f (manufactured by F., Gudrich) and triethanolamine 0-599 were dissolved. A mixture of this polymer solution and the silver halide emulsion of Example 12 was coated on Kapton [F], which had been coated with 1 copper, to give a thickness of 100 cr and 60 cm. Exposure and development were carried out according to the procedure of Example 120 to obtain good resolution. A silver image with a black background without any fog was obtained. Test of charge 2 and charge decay as a function of relative humidity! tIl was performed on pure Carbocet [F] 526 coating at 36.901 W per 100 crIL2 on copper under the same conditions as Example 17. At a relative humidity of 4 to 72 degrees, Cal? 526 retained charge at least as well as or better than Polymer J of Example 12.

Example 26 Cal? Example 25 was repeated using the set o525 (56/67/7 copolymer of ethyl acrylate/methyl methacrylate/acrylic acid, manufactured by B.F. Gutdrich), but no images were produced! 16
It was inferior to that of Example 25.

Example 27 A film was made as in Example 1 using an AgCl emulsion containing 13.3 ri of gelatin per mole of silver chloride and a coating weight of k of 120 cm per 100 cR2.

The film was exposed and processed in an MXD rapid line film developer (manufactured by E.I., DuPont de Nemo Earth) to develop various amounts of silver. The ratio of developed silver was measured using a 4000 (manufactured by Nisterrein Co., Ltd.). The surface resistance value in the silver image area was measured with a Full Cuff Type 7 multimeter (manufactured by John Fulke Mfg.) between two probes 1α apart. band i in silver image area
tt was measured with a Senro 2F 6 person electrostatic test meter. The results are shown in Table 10 below.

Example 28 Mylar [F] (polyester film) coated with indium tin oxide was coated with polyvinyl IJdenchloride resin at a rate of 61'IrL per minute using an air knife applicator at a rate of 1.8 caps per 100 crIL2. and heat set at 170° C. at a speed of 6.1 m/7 min with a residence time of 8 min. Use an air knife for this 6
0.8 to 1.0 per 100 crIL2 at a rate of 1 packet/min.
09 gelatin layer and heat at 145℃ for 157 hours/
Thermal relaxation was performed at a rate of 3.5 minutes with a residence time of 4 minutes.

``A solution of Polymer E was prepared by adding 50 tons of isopropyl alcohol (95%) A and 132 fk of potassium pellets to 23149 water with stirring.To this solution, 600 tons of Polymer TL: 600 tons of polymer TL was added immediately with stirring, and a large amount of Continue stirring at 1 (15 minutes) until the portions dissolve. To this add 54 t of potassium bicarbonate.

The dispersion of silver chloride contains 10 f' of gelatin per mole of silver chloride.
i-containing silver curds (particles! was added to 2300 F of water, and 130 tons of Q, IN sodium hydroxide and 15 tons of Q, IN sulfuric acid were added to adjust the pH to 6.7. This was heated at 45° C. for 1 hour and 2149 of a solution made of 386 t of 0.1 N hydroxide, 759 tetraazoindene stabilizer and 39 F of water was added. This was diluted to 25 g of silver chloride with 614 g of water.

247 t of polymer solution (15%) was gradually added to 25 t of AgC2 dispersion*b 30 t with stirring. EPI-FtEZ5022 (diglycidyl ether of 1,4-butanediol, Celanese M) before application.
6.7 tons of indium tin oxide coated Mylar sheet, treated as described above, was coated with 1a3? using a laboratory coater. Polymer coverage is 10 at FL/min speed.
It was applied to 0crIL2 force 15cm. This was dried at 10°C for 30 seconds, 30°C for 60 seconds and 50°C for 60 seconds. The total dry coating amount is 100 cIrL2 Todoro 103+
It was 19.

After exposure and development as in Examples 18 to 24, the exposed silver image areas had a surface resistance of 50 to 100 ohms and a charge of 1 μm measured 2 seconds after charging. The unexposed, unsilvered areas of the 0 image were charged at a relative temperature of 19 m and measured 2 seconds later to 242 V, 15 seconds to 206 V, and 30 seconds to 190 V (7).
had. Several units described in Examples 18 to 24 8
Toning in 706 camera is 1fi with 5 to 98 dots.
It gave a resolution value of 150 lines per line. The maximum density of the image transferred to paper was 2.4, and the minimum density was 0.03.

Example 29 This example illustrates an example of the invention using a diffusion transfer film. Solution water below 311
6f ammonia water (29 t) 84 t isopropyl alcohol (951) 400 t of powdered polymer A was added to the doof with vigorous stirring. This solution was allowed to stand overnight without stirring until the polymer was dissolved. 600 t of this polymer solution at 1720 rVc and a 21% solution of zinc sulfate were added over 1 minute with vigorous stirring, followed by 1.0621 210 t of sodium sulfide.
Add 2.59 ml of Acid Violet 520 (antihalation dye) for 5 seconds while stirring.
520 t of diluted liquid was added in 30 seconds. Water 1250 for this
With the addition of F, it was reduced to 4 chi. EPI-RE before application
xiy2 of Z 5022 (diglycidyl ether of 1,4-butanediol) was added. This solution was applied under the following conditions: 200 feet/min (61 m 1 min), 4 inches (10
Mites (polyester) with a thickness m-[F] 5 μm on which indium-tin oxide had been previously deposited was applied using an air knife and dried at 85° C. (2 mm) at an air knife pressure. This film was then heated at 145° C. 45 feet/min C15.7 m1
Thermal relaxation was carried out in a separate pass at 145° C., giving a residence time of 5.5 minutes. This was coated with high contrast silver chlorobromoiodide (AgC) at a blue-sensitive camera speed dispersed 2:1 in gelatin using a Par coater at a speed of 24.4 m/min.
The emulsion was overcoated. The final amount of binder applied was 100 cI! 9.31Hi per L2, emulsion layer 75.6 per 100cIIL2
■It was. The silver ion to polymer ratio was 50:1. This film was exposed to Agfa CP297
B in diffusion transfer developer (Agfargewald) at 28°C.
H1 was developed for 1 minute with little stirring, stirred for 1 minute at 28 °C in a 10-euacetic acid stop solution to remove most of the gelatin in the upper layer, rinsed with water at 15 °C, and transferred at room temperature.

The unexposed areas developed into the polymer binder layer and had a surface resistance of 20-35 ohms Ov.

The exposed areas are free of silver in the polymer binder layer;
After charging, the charging amount is 150V in 2 seconds at a relative humidity of 38%.
, 104V for 15 seconds and 91V for 30 seconds. Toning in a modified Sabin 870 copier, as described in Examples 18-24, gave a 4-98 dot 760 line screen with a maximum density of 2.5 and a minimum density α01.

Examples 30-31 These examples compare the properties of diffusion transfer films containing either gelatin or styrene-acrylic terpolymer as the image-receiving layer.

(1) Diffusion transfer film with gelatin binder in image-receiving layer (Example 30) Lucero-ILLS Gelatin 60r Total deionized water 136
01! J and stirred at room temperature for 20 minutes with rapid stirring. Heat to 52℃ for 30 minutes and then heat to 35℃.
℃, 0.15 M instant lead sulfate solution 106111Il and a
6 added at 1 minute intervals to 15M ferrous sulfate solution 6111
Q. 336 mj of 05M sodium sulfide solution was added through the orifice so that the addition time was about 2 minutes. The following solutions were then added.

Section 15 PolyStep B-27 (Ste 7 60d manufactured by Ankagaku Co., Ltd.) Solution 1, 33 M formaldehyde 40 ml (
L264M chromium) 40μ This solution is immediately applied onto the conductive side of the indium tin oxide coated mylar, with a coating volume of 11 v0.7 to 1 m2.
．． Of gelatin.

Ortho-sensitized camera speed high contrast chlorobromide steel emulsion (30 molar silver bromide, average grain volume 0.025 μm3)
) is applied on top of this gelatin layer, and the silver application ffi is 51 per 1 Sakai 2? This emulsion does not contain a hardening agent.

This multilayer film was imagewise exposed with a tungsten source, and approximately 20%
It was developed for 60 seconds at 0.degree. C. with little stirring. Emulsion W1 was then removed with pressure water at 30°C. The samples were washed with 38°C water for 2 minutes and dried at room temperature.

(11) Diffusion transfer film with improved polymer/inner gold (5ii! Example 31) For a solution of 265 t of triethanolamine and 4. Of polymer E in 80 ml of water, a 4 t aqueous solution of zinc sulfate. 6□t-1 minute, and then 1q, 2m of sodium sulfide aqueous solution was added for 25 seconds.After stirring for 5 minutes, the precipitate was filtered out, and the solution containing salivary lead sulfide cores was mixed with innowous tin oxide [F] coated mylar. The conductive side (surface resistance value = 500 ohms) was coated with Vc to obtain a transparent ?limmer image-receiving layer having 71q of zinc sulfide nuclei per 100c!IL2.

1 at 125°C to improve adhesion to the conductive substrate.
Heated for 0 minutes.

Blue-sensitive camera speed high contrast silver chloride iodide (AgCt8α0/AgBr) dispersed 2:1 in gelatin.
19.5/AgI CL5 moht4, average particle volume 0.
01 μm3) The emulsion is coated without hardener onto a polymeric image-receiving layer, the coverage being 69 capes/100 cm2.

This multilayer coating was imagewise exposed in a commercially available Kodak PM film.
12.5 TD developer (manufactured by Eastman Kodak)
Among those modified with potassium carbonate (No. 4) and potassium carbonate (No. 54), most were developed without stirring. The developed image was stirred for 30 seconds at 28°C in a 10% vinegar stop solution.
Most of the top gelatin layer was removed. The diffusion transfer image of the black bonotibs in the image-receiving layer remained on the conductive base layer and was rinsed with water at 40°C to remove gelatin and loose silver debris, dried, and dried to remove volatile deposits. It was heated at 125°C for 5 minutes. The image shows the highest daytime density of 50-55 and the lowest density of almost 0? I had it.

The area of the image receiving layer corresponding to the unexposed image is 1001J1
Fine black metallic silver dispersed in a polymer matrix of 6.6 WIg per 2 '1zlQQc+12 Roar a
I had sisy. This silver to polymer ratio of 1.34
: 1 is above the threshold of about 1.2, and the surface resistance value of the area containing @ is very low, 5-14 ohms.
The area corresponding to the exposed image is fairly clean, mostly colorless, and has a surface resistance t of over 107 ohms. This master was toned on a modified Servin 87011 copying machine as in Examples 18-24. At a developing electrode potential of 50 V, the background part of the toner image transferred to the paper (corresponding to the silver area of the master) was completely free of toner, and the halftone dot was 2 to 95 dots/60 line screen.

(iii) Electrostatic Data Data for the diffusion transfer films of Examples 30-31 at each relative humidity were obtained according to the method described in Examples 18-24. In all cases the temperature was 22°C. The results at 77 μm are summarized in Table 11.

Table 11 Example R) I = = 114 3Q 0 13 RH = 3096 15 , 0 17 RH = = 49% The diffusion transfer film of Example 30 with gelatin as the binder was heated at 100° C. for 10 minutes and then subjected to relative humidity. 48
1 minute or 10 minutes. The 7 μm data measured immediately after this adjustment is shown in Table 12 below.

Table 12 Conditioning Time (IV) Toning Results l The films of Examples 30-31 were toned as in Examples 18-24 at 21° C. relative humidity 43 parts. 5j! The reflected optical densities measured as in Examples 18 to 24 are shown in Table 13 below.

Table 13 30 Q, OOQ, 73 31 1.83 , a Heated at 100° C. for 10 minutes and conditioned for 1 minute at ambient temperature prior to toning.

2m''・↑′,... Zn8 development nucleus 1 as described in Example 3
A solution of Poly□Ma□-E containing: 28119/100 cWL2 was applied onto a gelatin-subbed polyester film to give a clear colorless film. A sheet of Kodak PMT negative photographic paper is imagewise exposed 1
1:1-.

It was done. s second exposure, 7j,, T7: The T photographic paper and the polymer/nucleus image Qa are printed, the emulsion side of the paper is the nuclear coating film, ,,,' is facing both sheets? I-Feed spread apart into the nip of the laminator. Kodasoku's PMT-D developer was applied to the nip between both sheets, and both sheets were wet laminated together at 1 m/min under light nip pressure for 30 min at room temperature.
The sheets are left for a few seconds, then the two sheets are separated and the gj! A □ black positive image with a maximum density of α7 and a minimum density of α02 was obtained on the coating film, and a strong positive image on the PMT photographic paper was obtained. This is a well-known photographic process and shows that Polymer E can be used to create silver images.

[Brief explanation of the drawing]

FIG. 1 shows an electrostatic stamp cape IJ of the present invention having a photosensitive material 11 in which photographic silver halide is dispersed in an insulating substrate.
z
The figure ``The Master of Figure 1, who has been pardoned and revealed,''
Figures 3 and 4 show the same master after it has been fused, Figures 4 and 4 show it after it has been charged, and Figure 5 shows the master with toner particles attracted to the charged surface. . 3 to 9 illustrate a diffusion transfer film according to a second embodiment of the present invention, in which FIG. 3 is a schematic cross-sectional view of a diffusion transfer film having a photosensitive layer 8, and FIG. 7 is an exposure Figure 8 shows the same film after development has been completed, and Figure 9 shows the same film after the photosensitive layer 8 has been removed and it is ready for use as a printing master. There is. In the figure, 1 and 8 are photosensitive layers, 3 is a conductive base layer, and 4 is a supporting substrate. 2 people outside

Claims (1)

Claims: 1) A composition consisting essentially of a photographic silver halide salt dispersed in an insulating synthetic polymer binder that is swellable in an aqueous solution having a pH value greater than about 8.5. In this case, the composition maintains an apparent macroscopic electric field of at least about 5 V/μm when measured 2 seconds after fully charging a surface that has been allowed to equilibrate for 1 hour at 50% relative humidity. A photographic light-sensitive composition having such an insulating value. 2) The binder is swellable in an aqueous solution having a pH value in the range of about 9 to 14 and has an insulating value of at least about 30 V/μm. Compositions as described in Section. 3) The composition of claim 2, wherein the binder has an acid value of about 70-160. 4) The composition according to claim 3, wherein the binder is a copolymer of an aromatic monomer and acrylic acid or methacrylic acid. 5) The composition of claim 4, wherein the binder is a copolymer comprising 10-50% by weight styrene monomer, 5-50% by weight carboxylic acid monomer, and 0-85% by weight acrylate monomer. thing. 6) The composition of claim 5, wherein the binder is a copolymer comprising 25-35% by weight styrene monomer, 10-25% by weight carboxylic acid monomer, and 40-65% by weight acrylate monomer. thing. 7) The composition of claim 4, wherein the weight ratio of silver ions to binder ranges from about 0.5 to 3 parts silver per part binder. 8) An electrostatic printing master comprising an electrically conductive substrate carrying a photosensitive coating of silver halide crystals dispersed in an insulating binder, wherein the binder has a p of greater than about 8.5.
An electrostatic printing master which is a synthetic polymer swellable in an aqueous solution having a H value and an insulating value such that it maintains an apparent macroscopic electric field of at least about 5 V/μm. 9) The binder is swellable in an aqueous solution with a pH value in the range of about 9 to 14 and a relative humidity of 5.
When fully charged and measured 2 seconds after the surface was allowed to equilibrate for 1 hour at 0%, at least about 30
9. The master according to claim 8, which has an insulation value of V/μm. 10) The master according to claim 9, wherein the binder has an acid value of about 70 to 160. 11) The master according to claim 10, wherein the binder is a copolymer of an aromatic monomer and acrylic acid or methacrylic acid. 12) The master according to claim 10, wherein the binder is a copolymer comprising 10-50% by weight of styrene monomer, 5-50% by weight of carboxylic acid monomer and 0-85% by weight of acrylate monomer. . 13) The master according to claim 12, wherein the binder is a copolymer comprising 25-65% by weight styrene monomer, 10-25% by weight carboxylic acid monomer and 40-65% by weight acrylate monomer. . 14) The weight range of the silver halide, expressed as silver to binder, is approximately 0.5 parts silver per part binder.
13. The master according to claim 12, in .about.3 parts. 15) A diffusion transfer film comprising development nuclei dispersed in a binder, said binder being a synthetic insulating polymeric binder swellable in an aqueous solution having a pH value greater than about 8.5, and said film having a relative humidity of 50
% at least about 5 V/μm when measured 2 seconds after fully charging a surface that has been allowed to equilibrate for 1 hour.
A diffusion transfer film that has an insulating value that maintains the apparent macroscopic electric field. 16) The binder is swellable in an aqueous solution having a pH value in the range of about 9 to 14 and has a pH value of at least about 30
The film according to claim 15, which has an insulation value of V/μm. 17) The film of claim 16, wherein the binder has an acid value of about 70-160. 18) The film according to claim 17, wherein the binder is a copolymer of an aromatic monomer and acrylic acid or methacrylic acid. 19) The film of claim 18, wherein the binder is a copolymer comprising 10-50% by weight styrene monomer, 5-50% by weight carboxylic acid monomer, and 0-85% by weight acrylate monomer. . 20) The film of claim 19, wherein the binder is a copolymer comprising 25-35% by weight styrene monomer, 10-25% by weight carboxylic acid monomer, and 40-65% by weight acrylate monomer. . 21) The film of claim 18, wherein the weight ratio of silver ions to binder ranges from about 0.5 to 3 parts silver per part binder.