JP2972235B2 - Silver halide photographic material - Google Patents

Description

Description: FIELD OF THE INVENTION The present invention relates to a photographic film capable of ultra-rapid processing by an automatic processor, and more particularly to a black-and-white electronic image-forming film capable of rapid processing or to room light. Related to various graphic art films.

2. Description of the Related Art A consistent objective in photography has been to reduce the time required to process photographic film to obtain high quality images. A number of improvements had to be made to both photographic film and processing chemistry before medical imaging moved from manual processing to automated processors that produced high quality images in 90 seconds. Four important functions, development, fixing, washing and drying, had to be improved. These functions themselves had to be improved because one or more of them would not be completed if the processing cycle was shortened. This can result in low image densities, smeared pigments, wet films, and other defects. While the goal of faster processing is desirable, shortening the time of the development, fixing, washing and drying cycles makes the conditions for photographic films more stringent.

Significant progress has been made with the advent of automated processors with a dry-to-dry cycle time of 90 seconds. One example of an automatic processor is described in Russel et al., U.S. Pat. No. 3,025,779, and films are disclosed in Barnes et al., U.S. Pat. No. 3,545,971.
In the specification. Studies have also been conducted on additives to reduce swelling and improve drying, as described in Allen et al., U.S. Pat. No. 3,232,761 and British Patent 1,336,113. Improvements in the development described in US Pat. No. 4,145,218 to Habu et al., US Pat. No. 3,832,178 to Jacobson and US Pat. No. 4,132,551 to Pollet et al. Machid
a) et al., EP 89,231 and Sakam
(oto) et al. in European Patent No. 237,256 for fog stability also attracted attention. Finally, an ultra-rapid processing apparatus is disclosed in Suzuki et al., EP 239,363, Suzuki et al., EP 238,271, Suzuki et al., EP 248,390. And U.S. Pat. No. 3,694,209 to Schwienbacher.

The object of the present invention is a laser scanner, in particular a laser scanner using a helium / neon laser or a laser diode. Of course, any other laser source may be used. Diodes have the advantage that the power increase is very large compared to other laser sources. Commercially available 3M laser imagers use a 15 mW diode. However, literature on 100 mW diodes has already appeared.

Ultra-rapid processing is defined in the context of the present invention as a dry-to-dry time of 10 to 60 seconds in an automatic processor.

The present invention is specifically directed to electronic image formation with a more powerful exposure device potential. The introduction of more powerful image-forming equipment results in finer grain silver halide films which are thinner or require less gelatin. Emulsions with reduced amounts of gelatin and finer grains are extremely advantageous for rapid processing equipment.
Increasing the hardness is also important to reduce swelling and water retention and reduce the need for drying.

A good example of an increased output from a recording device is a laser diode. Current laser diode scanners (3M laser imagers) use near infrared, usually 77
A 15 milliwatt diode that emits 0-830 nm. Literature on experimental laser diodes capable of producing 100 milliwatts of power has also emerged. This represents a 6 to 7 fold increase in power over current 15 milliwatt diodes. As the output increases,
Because much smaller silver halide grains can be used, the transition to ultra-rapid processing equipment is very easy.

The impetus for ultra-rapid processing is very basic. The first is to improve productivity. More film can be processed within a given time. Second, each film is produced more quickly, reducing latency from 90 seconds to 30 seconds. This can be useful in determining whether more images are needed to complete a diagnosis of a medical facility or patient, such as an emergency room.

It is also very advantageous to make the layers thinner and to produce them quickly in various fields using prepress, graphic arts films. If the layer is made thinner and the amount of gelatin per unit area is reduced, preconditioning,
The advantage is that the change in film dimensions due to the effects of processing and drying is reduced. Further, if the cycle time is further shortened, a specific exposure can be evaluated immediately, which helps to increase the productivity. This is particularly advantageous for stripping operations that make many contact and deep replicating films as part of the preparation of the composite for the production of printing plates.
Rapid production is also advantageous when making masks or causing color changes such as dry etching.

Means and Action for Solving the Problems The present invention describes an ultra-rapid processing apparatus for silver halide photographic films. An object of the present invention is a graphic arts film that can be processed with electronic light in the medical field, such as CRT or laser imaging, and with room light.
However, this is not meant to limit the invention to the medical field or electronic imaging. The present invention will be described using a fine grain silver halide film exposed by a laser scanning device.

Any of a variety of photographic silver halide emulsions may be used in the practice of the present invention. For example, silver chloride, silver bromide,
Silver iodobromide, silver chlorobromide, silver chlorobromoiodide and mixtures thereof may be used. Particles of any shape, such as equiaxed orthorhombic, hexagonal, epitaxial, and lamellar platelets, or mixtures thereof may be used. These emulsions are described, for example, in U.S. Pat. No. 2,222,264 to Nietz 5, and U.S. Pat.
No. 3,320,069; McBride U.S. Pat. No. 3,271,157; and U.S. Pat. No. 4,425,425.
And any of the well-known methods, such as the single or double jet emulsions described in U.S. Pat. No. 4,425,426.

The silver halide emulsion of the present invention can be washed without washing or by washing to remove soluble salts. In the latter case, the soluble salts can be removed by chill hardening and leaching, or the emulsion can be removed, for example, by Hewitsson.
on) et al., U.S. Pat. No. 2,618,556;
zy) et al., U.S. Patent No. 2,614,928, to Yackel
kel), U.S. Pat. No. 2,565,418, Hart
No. 3,241,969 to Waller et al. And US Pat. No. 2,489,341 to Waller et al.

The photographic emulsions of the present invention can be sensitized with chemical sensitizers such as reducing agents; sulfur, selenium or tellurium compounds; gold, platinum or palladium compounds, or combinations thereof. A suitable chemical sensitization method is Shepard (Shep
ard) U.S. Pat. No. 1,623,499 to Wahler.
U.S. Pat. No. 2,399,083 to McBay (M.
cVeigh) US Patent 3,297,447 and Dan (D
unn) in US Pat. No. 3,297,446.

The silver halide emulsions of the present invention are described in US Pat. No. 2,886,437 to Piper, Checha.
k) U.S. Pat. No. 3,046,134 to Carol
l) et al., US Pat. No. 2,944,900 and Gofe
ffe) of US Pat. No. 3,294,540, cationic surfactants and rate increasing compounds such as thioethers or combinations thereof.

The silver halide emulsion of the present invention can be protected from fogging and can be stabilized to prevent loss of sensitivity during storage. Suitable antifoggants and stabilizers which can be used alone or in combination include the thiazolium salts described in Staud US Pat. No. 2,131,038 and Allen US Pat. No. 2,694,716; U.S. Pat. No. 2,886,437 to Piper and Heimbac
h) U.S. Pat. No. 2,444,605 to Azaindene; U.S. Pat. No. 2,728,663 to Allen; mercury salts described in U.S. Pat. No. 2,728,663; Anderson U.S. Pat.
Urazole described in 3,287,135; Kennard (K
ennard) US Pat. No. 3,235,652; sulfocatechol; Carroll et al. US Pat.
No. 448, oxime; nitrone; nitroindazole; Jones, U.S. Pat.
Metal salts described in US Pat. No. 3,220,839 to Herz; and U.S. Pat. No. 2,566,263 to Trivelli and US Pat. No. 2,566,263 to Damschroder. Palladium, platinum and gold salts described in Japanese Patent No. 2,597,915.

The silver halide grains according to the present invention are dispersed in a colloid, and are dispersed in aldehydes and blocked aldehydes, ketones, carboxylic acids and carboxylic acid derivatives, sulfonic acid esters, sulfonyl halides and vinyl sulfones, active halogen compounds, epoxy compounds aziridines,
Various organic or inorganic curing agents such as active olefins, isocyanates, carbodiimides, alone or in combination, mixed function curing agents and polymeric curing agents, such as oxidized polysaccharides, such as dialdehyde starch, oxyguar gum, etc. Can be.

The photographic emulsions of the present invention can contain various colloids alone or in combination as vehicles or binders. Suitable hydrophilic materials include naturally occurring substances such as gelatin, gelatin derivatives (eg, phthalated gelatin)
Such as proteins, cellulose derivatives, dextran,
Polysaccharides such as arabic gum and the like; and synthetic polymeric substances, such as water-soluble polyvinyl compounds, such as poly (vinylpyrrolidone) acrylamide polymers or other synthetic polymeric compounds, such as latex-like dispersed vinyl compounds, especially dimensional stability of photographic materials. There are compounds that increase sex. Suitable synthetic polymers include, for example, Nottorf U.S. Pat. No. 3,142,568, White U.S. Pat. No. 3,193,386, Houck, Smith, and Yutelson.
elson), U.S. Pat. No. 3,287,289 to Ream and Fowler, and U.S. Pat. No. 3,411,911 to Dystra, and are particularly useful. Those are water-insoluble polymers of alkyl acrylates and methacrylates, acrylic acid, sulfoalkyl acrylates or methacrylates, those having crosslinking sites which promote curing or crosslinking and those having repeating sulfobetaine units as described in Canadian Patent No. 774,054 It is.

Emulsions according to the present invention are described, for example, in antistatic or conductive layers, such as layers having soluble salts such as chlorides, nitrates, etc., evaporating metal layers, and in Minsk U.S. Pat. Nos. 2,861,056 and 3,206,312. Or an ionic polymer such as Trevoy US Pat. No. 3,428,45.
It can be used in a photographic element containing an insoluble inorganic salt as described in the specification.

The photographic emulsions of the present invention can be coated on a wide variety of supports. Typical supports include polyester films, primed polyester films, poly (ethylene terephthalate) films, cellulose nitrate films, cellulose ester films, poly (vinyl acetate) films, polycarbonate films and related or resinous materials, and Examples include glass, paper, and metal. Typically, a flexible support, specifically a paper support, is used, which is partially acetylated or barita and / or an α-olefin polymer, in particular a polyethylene, polypropylene, ethylene butene copolymer or the like. Polymers of α-olefins having 2 to 10 carbon atoms can be coated.

The emulsions of the present invention may be formulated with plasticizers and lubricants such as polyhydric alcohols, such as glycerin and diols of the type described in US Pat. No. 2,960.404 to Milton, US Pat. No. 2,588,765 to Robijns. Fatty acids or esters as described in the specification and U.S. Pat. No. 3,121,060 to Duane, and silicone resins as described in U.S. Pat. No. 955,061 to Dupont.

The photographic emulsions described herein are prepared from Aponin, an alkylaryl sulfonate described in Baldsiefen U.S. Pat. No. 2,600,831, a fluorinated surfactant, and Ben-Ezra. Surfactants such as the amphoteric compounds described in US Pat. No. 3,133,816 can be included.

Photographic elements comprising the emulsion layers described herein include starch,
Titanium dioxide, zinc oxide, silica, Jelley
U.S. Pat. No. 2,992,101 and Lynn.
Matting agents, such as polymeric beads, including beads of the type described in U.S. Patent No. 2,901,245.

The emulsions of this invention can be utilized in photographic elements containing stilbene, triazine, oxazole and coumarin brightener. As the water-soluble brightener, those described in German Patent No. 972,067 to Albers et al. And US Patent No. 2,933,390 to McFall et al. Can be used, or Janse (Janse) can be used.
The dispersants for brighteners described in n) German Patent 1,150,274 and Oetiker et al., US Pat. No. 3,406,070 can be used.

Photographic elements containing the emulsion layers of this invention were prepared using
ey) U.S. Pat. No. 3,253,921, Gaspe
r) U.S. Pat. No. 2,274,782, Carol
Photographic elements containing light absorbing materials and filter dyes as described in l) et al., U.S. Pat. No. 2,527,583 and Van Campen, U.S. Pat. No. 2,956,879, can be used. Milton (Milt
dyes can be mordant as described in U.S. Pat. No. 3,282,699 to J. On) and Jones.

Also useful are contrast enhancing additives such as hydrazine, rhodium, iridium and combinations thereof.

The photographic emulsions of the present invention may be coated by various coating methods, such as dip coating, air knife coating, curtin coating or extrusion coating using a hopper of the type described in Beguin, US Pat. No. 2,681,294. can do. If desired, Russell U.S. Pat.
Two or more layers may be coated simultaneously by the methods described in U.S. Patent No. 1 and Wynn GB 837,095.

A dye image can be formed by selectively forming a dye using a silver halide photographic element. The above photographic element for forming a silver image is disclosed in British Patent No. 47
No. 8,984, U.S. Pat.
No. 113,864, U.S. Pat. Nos. 3,002,836, 2,271,238 and 2,362,598 to Vittum et al., U.S. Pat. No. 2,950,970 to Schwan et al.
No. 2,592,24 to Carroll et al.
No. 3,343,703 to Porter et al.
Nos. 2,376,380 and 2,369,489; Spath, UK Patent 886,723 and U.S. Pat. No. 2,899,306; Tuite, U.S. Pat. No. 3,152,896; and Mannes U.S. Patent Nos. 2,115,394, 2,252,718 and 2,108,60.
No. 2 and Pilato U.S. Pat. No. 3,547,6
It can be used to form a dye image by using a developer containing a dye image-forming material such as a color coupler as described in JP-A-50. In this form, the developer contains a color developing agent (eg, a primary aromatic amine, in its oxidized form capable of reacting with a coupler to form an image dye). The instant automatic development nucleic acid transfer film can be used in the same manner as a color film for photothermography or paper using a silver source and silver halide close to a leuco dye catalytically.

The coupler may be present directly attached to the hydrophilic colloid, or it may be carried in a high boiling organic solvent, which is then dispersed in the hydrophilic colloid. The colloid may be partially or fully cured by any of a variety of known photographic hardeners. Such curing agents include free aldehydes (U.S. Pat. No. 3,232,724), aldehyde releasing compounds (U.S. Pat. Nos. 2,870,013 and 3,819,608), s-toluazine and diazine (U.S. Pat.
5,287 and 3,992,366) aziridine (US Pat. No. 3,271,175), vinyl sulfone (US Pat. No. 3,490,911) carbodiimide and the like are used.

Dye-forming couplers are described in Schneider et al., Die Chemie, Vol. 57, 1944, page 113;
US Pat. No. 2,304,940 to Martinez et al., US Pat. No. 2,269,158 to Martinez, US Pat. No. 2,322,027 to Jelley et al., US Pat. No. 2,376,679 to Frohlich et al. U.S. Patent No. 2,801,171 to Fierke et al .; U.S. Patent No. 3,748,141 to Smith; U.S. Patent No. 2,772,163 to Tong;
U.S. Pat. No. 2,835,579 to Thirtle et al., U.S. Pat. No. 2,533,514 to Sawdey et al., U.S. Pat. No. 2,353,75 to Peterson.
No. 4, U.S. Pat. No. 3,409,435 to Seidel
Issue Specification, and Chen Research Disclosure , Volume 159,
As noted in the July issue, 1977, para. 15930,
Can be incorporated into photographic iodine. Dye-forming couplers can be incorporated in various amounts to achieve various photographic effects. For example, British Patent No. 923,045 and U.S. Pat. No. 3,843,369 to Kumai et al. Disclose that coupler density to silver coverage is the amount commonly used in faster and medium speed emulsion layers. It teaches to be less restrictive.

The dye-forming couplers are generally selected to form subtractive subtractive (i.e., yellow, magenta, and cyan) image dyes, and are non-diffusing, colorless couplers;
For example, two to four equivalent couplers of open chain ketomethylene, pyrazolone, pyrazolotriazole, pyrazorobenzimidazole, phenol and naphthol type hydrophobically parastid, high boiling organic (coupler) solvents.

Other usual photographic additives, such as coating aids,
Antistatic agents, acutance dyes, antihalation dyes and layers, antifoggants, latent image stabilizers, anti-kinking agents and the like may be present.

A particularly important group of additives which, while not essential to the practice of the present invention, have been found to be particularly advantageous for the practice of the present invention, are high strength reciprocity failure (HIRF) reducers. Among the many classes of stabilizers for this purpose, chloroparadite and chloroplatinate (U.S. Pat. No. 2,566,263), iridium and / or rhodium salts (U.S. Pat. Nos. 2,566,263 and 3,901,713). , Cyanolodate (Beck et al., J.Signalaufzeichnungsm
aterialen , 1976, 4 , 131) and cyanoiridate .

The film is a modified 3M XP-515, 90 second automatic processor which can be adjusted (in standard operating mode) to give a dry to dry processing time of about 120 to 70 seconds. Tested. The standard structural model was improved by switching the drive gear. As a result, the dry-to-dry processing time could be reduced from 90 seconds to 22 seconds. This XP-515 treatment device uses a water jet device and has infrared drying. The processing unit is Kodak RP X-Omat (Kodak RP X-
Omat) with developer and fixer. Fixer temperature was 91 ° F throughout the study, but developer temperature was 95 and 1 ° C.
It was 04 ゜ F.

Hardness tests were performed on many of the coatings. In this test, the melting time of the photosensitive material is determined as described in Suzuki EP-A-238,271.
It was previously described on page 10. A 1 cm x 2 cm film strip was cut and immersed in a 1.5% aqueous sodium hydroxide solution. Sodium hydroxide solution without stirring
C. was maintained. The melting time is the time required for the emulsion layer to dissolve in the sodium hydroxide solution.

The drying characteristics and water content of the film were determined by Suzuk
i) European Patent Application Publication No. 238,271, each of 11
Evaluation was carried out by the method described on pages 7 and 108. The drying properties of the films were evaluated by the degree of tack between the treated films. In each case, the treatment cycle time was 30 seconds dry to dry and the scale was from 1 (insufficient) to 5 (excellent). Grades 3-5
Was considered available, but grade 2 was insufficiently dry for practical applications. The water content of the photographic material was determined in a manner very similar to that described in EP-A-238,271. Films are 95 ゜ F and 9 respectively
Performed at 0 ° F on a Kodak M6 processor with Kodak RP X-Omat developer and fixer. A 20 × 20 cm test film was exposed and then partially processed. After the water washing step and before reaching the drying zone, they were removed from the M6 processor. The elapsed time from when the film entered the processor to when it came out of the water wash was 60 seconds. Next, the wet film was measured within 60 diseases to obtain a wet weight (Ww) (g). After drying the film, the dry weight Wd (g) was measured, and the equilibration time was at least 1 hour at 70 ° F and 55% relative humidity. Next, the water content of the film is
It was calculated from the following equation.

Water content (g / m ²⁾ = with (Ww-Wd) x (10,000cm 2 / 20cm x 20cm) 4 kinds of halide emulsions The present invention has been described. All were prepared by double jet precipitation. Emulsion A was a 64% chloride and 36% bromide emulsion with an average particle size of 0.24 μm. Emulsion B was an ammoniacal iodobromide emulsion with all potassium iodide and ammonia in the reaction vessel prior to precipitation. The resulting emulsion was 3% iodide and 97% bromide and had an average particle size of 0.24 µm. Emulsion C was a 64% chloride and 36% bromide emulsion with an average particle size of 0.17 μm. Emulsion D was a 90% chloride and 10% bromide emulsion with an average grain size of 0.09 µm. Emulsions A, C and D were chemically ripened with p-toluenesulfonic acid, sodium thiosulfate, and sodium gold tetrachloride. Sulfur and gold ripeners were used in Emulsion B.

For the final preparation of the emulsion, adjust the pH to 6.5-7.0 and adjust the pAg
Consisted of adjusting to 7.2. Sensitizing dyes (1 to 3 below), phenyl-5-mercaptotetrazole (PM
T), ammonium salt and phosphonium salt were added as methanol solvents. Poly (ethyl acrylate) (PE
A) was added as a 20% aqueous dispersion. Formaldehyde hardener and leuco dye BCF (LEUC, Sandoz)
Was added as an aqueous liquid.

After aging the coated and dried films for one week, they were exposed on a sensitometer for ^10-3 seconds through various narrow band filters simulating the light exits of various laser devices. As a result of sensitometry,
D _min , D _max , speed (optical density = 1.0), average contrast (CONT), and processing time from 90 seconds to 30 seconds (Δ
90 → 30) Changes in speed and contrast due to the decrease.

Examples Examples 1-5 Experiments were performed to test the importance of gelatin levels for ultra-rapid processing. Emulsion A (0.24 μm, Cl / Br) was coated with various levels of gelatin and overcoated with various topcoats (TC). Coating additive per mole of silver is 30mg infrared dye, dye 2, 115mg PMT, 20g
PEA and 11 mg of formaldehyde (per g of gelatin). The filter was coated with an infrared-absorbing antihalation backcoat at 2.4 g silver / m ² in a blue 7 mm polyester base. The formulation of AH was described in Example 2 of US Patent Application No. 59,931. The AH flow was reduced to 68% for this application producing an AH layer with 2.80 g gelatin / m ² and 3.65 mg formaldehyde / g gelatin. The materials were exposed through a 820 nm narrow band filter and developed at developer temperatures of 104 ° and 95 ° F. with processor cycle times of 90, 45 and 30 seconds. The results are shown in Table 1.

Table 1 shows that the gelatin level is low. It can be concluded that the loss of ultra-rapid processing speed and contrast is reduced. In addition, improvements are seen at higher developer temperatures of 104 ° F., increasing the initial speed and contrast of the film and reducing the speed and contrast loss when processing 30 seconds dry to dry.

Examples 6-16 The effects of hardener levels (formaldehyde), ammonium salts and phosphonium salts were evaluated using the same emulsions and methods described in Examples 1-5. Table of changes
2 and the amounts of formaldehyde and addition of ammonium and phosphonium salts described below.

PPh ₄ Cl: tetraphenylphosphonium chloride, PPh ₄ Br: tetraphenylphosphonium bromide, TPMP: triphenylmethylenetriphenylphosphonium bromide, THAI: tetraheptyl ammonium iodide.

The results are shown in Table 2, where all samples were coated with 2.4 g Ag / m ² . Ammonium and phosphonium salts show little improvement in speed and contrast loss when processed for 30 seconds at a developer temperature of 95 ° F. However, a developer temperature of 104 ° F. greatly reduces the speed of 30 second development and loss of contrast. A preferred salt is the ammonium salt THAI, which is
A 30 second treatment with 104 ° F developer (see Example 14) increased the initial speed and increased the sensitometric value to 9% with 95 ° F developer.
Equal to the system without additive treated with 0 seconds (Example 6).

Hardness level is also important for rapid processing. Low hardener quality (Examples C and D) reduces speed and contrast loss in rapid processing, but reduces drying characteristics and melting time. Therefore, the level of hardener is critical for ultra-rapid processing and must be sufficient to achieve fast drying.

Embodiment 17 The possibility of ultra-rapid processing in the exposure apparatus of the present invention has been described for Embodiment 14. Emit Example 14 at 820 nm 15
Exposure was with a 3M laser imager equipped with a milliequivalent watt laser diode. Example of staircase optical wedge
Printed on 14 films. The step optical wedge was printed on a typical 90 second processable film (Example B) with the same contrast and density settings (equal output) with a 3M laser imager. Example B was processed dry-to-dry in 90 seconds, and Example 14 was XP-51 in 30 seconds.
Processed in 5 processing units. Both of these films are 95
゜ Processed with F developer. Table of Density Steps
Plotted at 3, processing the film 14 for 30 seconds reveals that the standard film, dry to dry processed in 90 seconds, has the same density as Example B. In addition, film 14
After drying for 30 seconds, it passed the ANSI test for hypo retention, which accounts for 30 years old document stability.

Table 4 Summarizes the data described above for Example 14 and Example B. The sensitometric data in Table 4 was obtained from a ^10-3 Table Flash Sensitometer described at the beginning of the experiment in combination with a 820 nm narrow band filter. Using the 3M laser imager, the first two entries in Table 4 were processed in 90 seconds, Example B was roughly equivalent to Example 14 processed in 30 seconds. I support it. Entry 3 in Table 4 shows that the density of Example 14 processed in 30 seconds can be further increased by increasing the developer temperature from 95 ° F to 104 ° F. Therefore, the super-dust treatment (30 seconds dry-to-dry) was illustrated with experimental film 14 and a laser scanning device (3M laser imager).

Examples 18-24 Fine grain emulsions C and D were tested for ultra-rapid processing. The coating uses dyes D-2 and D-3,
Low silver coating weight of 1.7 and 1.4 g Ag / m ² respectively
Except as described above, it was prepared by the method described in Examples 1 to 16. Formaldehyde was the curing agent. Details of the coating additives are shown in Table-5. Set this set to 7 mils (0.
018 cm) of a clear polyester base and the sensitometric results were evaluated with a 820 nm narrow band filter.

The data in Table 5 is based on the current laser exposure equipmentNote.
This shows that a 0.16 μm emulsion can be used for the second dry-to-dry processing. After optimizing this 0.16 μm emulsion (Example 20) for speed with Dye D-3,
Treated with 4 ° F developer for 30 seconds cycle time. Sensitometric data for Example 20 is the same as Example B, which was processed in 90 seconds using a 95 ° developer. Therefore, 3M
The 15 milliequivalent watt laser diode of the laser imager was a 0.16 μm emulsion (Example 2) with a developer temperature of 104 ° F. and a processor cycle time of 30 seconds.
0) produces enough energy to image (see also Example 17).

Examples 21 to 24 do not have enough sensitivity to produce images from current production laser devices when processed in 30 seconds. These films are roughly 1.0l
Og E, which is slow and requires a 10-fold increase in power with laser scanners. This results in a significant increase in power, but will be available in the near future as paper and products have emerged with 100 milliequivalent watt laser diodes.

Examples 25-33 Fine grain emulsion D (0.09 µm, Cl / Br) was further tested for ultra-rapid processing. The emulsion layers were coated with various levels of gelatin and overcoated with various topcoat thicknesses (TC). The coating adhesive was the same as Example 21 in Table-5. The set was coated on a 7 mil (0.018 cm) clear polyester base and the sensitometric results were evaluated with a 820 nm narrow band filter. The AH formulation applied to the back side of the base was described in US Patent Application No. 59931, Example 2. The AH flow was reduced to 30% in those examples producing an AH layer with 1.24 g gelatin / m ² and 7.3 mg formaldehyde / g gelatin. The results are shown in Table-6.

The results of Examples 25 to 33 were basically the same as the results of Examples 21 to 24. Examples 25-33 are not sensitive enough to generate images from current production laser devices processed in 30 seconds. These films are roughly
1.0 log E, slow
Requires a double power increase. This results in a significant increase in power, but will be available in the near future as paper and products have emerged with 100 milliequivalent watt laser diodes.

Examples 34-38 Ultrafast processed helium-neon laser films were constructed to demonstrate the scope of the present invention.

Emulsion B (0.24 μm, Br / I) was prepared by adding 100 mg / mol Ag of Dye D-
Sensitized by 1. 20 g / mol Ag PEA and formaldehyde were also added. Sample on 7 mil clear polyester base
Coated with 2.2 g Ag / m ² . The polyester base had an antihalation backside coating with an AH dye absorbing at 633 nm, 2.80 g gelatin / m ² and 7.38 mg formaldehyde / g gelatin. Film
After exposure with a 633 nm narrow band filter, the results are shown in Table-7.

The data in Table 7 also demonstrates the importance of reducing gelatin for ultra-rapid processing, and shows that the invention can be used with other exposure devices as well as laser diodes.

──────────────────────────────────────────────────続 き Continued on front page (58) Field surveyed (Int.Cl. ⁶ , DB name) G03C 1/035

Claims (7)

(57) [Claims] 1. A silver halide photographic material comprising a support and at least one hardened hydrophilic colloidal silver halide emulsion layer, wherein the halide emulsion layer has an average diameter of 0.05 to 0.35. Contains micron silver halide grains, at least 80% of the grains
Wherein the melting time of a 1 cm × 2 cm film strip of the silver halide emulsion layer in a 1.5% by weight NaOH solution at 50 ° C. exceeds 45 minutes, wherein the photographic material comprises: the silver halide photographic material comprising a water content of the photographic material at the time the cleaning process is completed is 3.5~9.5g / m ² when processing with a roller transport type automatic processor. 2. A silver halide photographic material comprising a support and at least one hardened hydrophilic colloidal silver halide emulsion layer, wherein the silver halide emulsion layer has an average diameter of 0.05 to 0.05. Containing 0.35 micron silver halide grains, of which at least 80
% Are silver halide grains having a diameter of less than 0.80 micron and greater than 0.02 micron, wherein said silver halide emulsion layer has less than 3.50 g / m ² of gelatin, in a 1.5% by weight NaOH solution at 50 ° C. The melting time of the 1 cm × 2 cm film strip of the silver halide emulsion layer exceeded 45 minutes, and the photographic material was processed at a roller-conveying type automatic processing apparatus, and when the washing step was completed, the photographic material was A silver halide photographic material characterized by having a water content of 3.5 to 9.5 g / m ² . 3. A silver halide emulsion layer having a protective coating layer containing no photographic silver halide on the silver halide emulsion layer.
Or the material according to 2. 4. The material according to claim 3, wherein the total weight of gelatin in said emulsion layer and said protective coating layer is 0.8 to 3.50 g / m ² . 5. The silver halide grains having an average diameter of 0.05
A material according to any of the preceding claims, which is ~ 0.25 microns. 6. The material according to claim 5, wherein the weight of silver in said silver halide emulsion layer is less than 3.0 g / m ² . 7. The material according to claim 5, wherein the weight of silver in said silver halide emulsion layer is 1.0 to 2.5 g / m ² .