JPH01309047A - Heat development type dry silver salt composition - Google Patents

Abstract

PURPOSE:To obtain the title compsn. having high sensitivity for a short exposure by incorporating a specified amt. of Au atom into a silver salt compsn. CONSTITUTION:>=10<-3> and <=10<-7> atoms of Au atom per 1atom of Ag atom are incorporated into a silver salt compsn. contg. an oxidizing agent comprising an org. silver salt, a high molecular compd., a reducing agent, and a silver halide, as essential components. By the presence of a trace amt. of Au atom, the characteristic of a silver salt compsn. is improved remarkably. The sensitivity of said heat development type dry silver salt compsn. is improved remarkably when it is used for recording, so a writing speed is elevated, consumption of recording energy is saved, and a recording device is miniaturized.

Description

DETAILED DESCRIPTION OF THE INVENTION (Field of Industrial Application) The present invention relates to the improvement of the photosensitive characteristics of a heat-developable dry silver salt material, and in particular, the sensitivity when recording with high illuminance and short exposure is improved. This invention relates to a heat-developable dry silver salt material. Furthermore, it relates to a recording method using this material.

(Prior art) Unlike conventional wet-type silver salt materials, heat-developable dry-type silver salt materials are useful for image recording in medical imaging equipment, news photos, and meteorological satellites because the development method is simple, just adding heat. It is used in many fields such as photographic transmission, aerial photography and microfilm fields. Particularly recently, lasers that can achieve high illumination have become widespread, and there is a demand for improved recording speed and digitization of information, and there is a need for recording materials that can perform sufficient recording even with short exposures. Under these circumstances, this heat-developable dry-type silver salt material uses a silver halide photosensitive mechanism, so like wet-type silver salt materials, it is expensive compared to other non-silver salt recording materials. It has high sensitivity and is suitable for short exposure recording.

Furthermore, compared to wet silver salt, this heat-developable dry silver salt does not use any liquid, so it does not require complicated liquid processing and has the advantage of being maintenance-free. Although they have advantages over wet silver salt materials, heat-developable dry silver salt materials have the disadvantage of poor raw film stability because many organic compounds, especially reducing agents, are packed into one sheet. . Therefore, research was carried out with the aim of improving the raw film stability of heat-developable dry silver salt materials, and practical use was achieved. The misfortune has gotten worse.

Representative examples of heat-developable dry silver salt compositions include those disclosed in Japanese Patent Publication No. 13-4924, Japanese Patent Application Laid-Open No. 48-97523, and Japanese Patent Application Laid-open No. 114419-1983.

In response to these materials, recent information recording methods are typified by so-called scanner-based image forming methods and optical discs in which the recording material is exposed to light based on information signals to form negative or positive images. The default recording method has been developed.

There are various kinds of recording devices, and the exposure light source includes a glow lamp, a gysenon lamp, a mercury lamp, a light emitting diode,
He-Ne laser, argon laser, 1ie-cd
Examples include lasers and semiconductor lasers.

1/c, typical recording materials used in this field include wet silver salt materials, heat developable dry silver salt materials, and selenium.
Many materials can be mentioned, such as photoconductor materials such as cadmium sulfide and OPO, and photopolymers. However, for recording materials such as lasers, silver halide materials are most useful as materials that record in optical mode and have a large amplification coefficient, and there are many literatures and books related to these recording methods and recording materials. An example of this is the Japan Society for the Promotion of Science's ``Recording Materials and Photosensitive Resins'' (Society Publishing Center).

As described above, recent information recording methods have undergone remarkable technological innovations, including improved recording speed and miniaturization of devices, regardless of whether they are analog recording or digital recording. Under these circumstances, commercialization of devices that record with high illuminance and short exposure using a laser or the like as an exposure light source is progressing. Examples include laser printers, laser color cokies, computer discs, laser discs, laser phototypesetting machines, computer output microfilmers, optical filing systems,
It is being used in systems in a very wide range of fields, such as laser OAD systems. Under these circumstances, there is a strong demand for materials with high sensitivity and high illuminance and short exposure, and if highly sensitive layer materials can be supplied, it will have great industrial effects such as increasing recording speed, miniaturizing devices, and saving energy. .

(Problems to be Solved by the Invention) As mentioned above, when recording with crystal illuminance such as a laser and short exposure, the sensitivity of heat-developable dry silver salt is higher than that of other recording materials. It is insufficient. Higher sensitivity naturally leads to improved recording speed and energy savings, which also leads to smaller devices.

In view of this, the present inventors attempted to increase the sensitivity by changing the quantitative ratio of the components in this heat-developable dry silver salt composition and by changing the manufacturing method of this composition. However, it was thought that these changes alone would reach a limit in improving the performance of the heat-developable dry silver salt composition. For example, if the sensitivity is increased, the storage stability of the photosensitive material deteriorates, and if the storage stability is maintained, the sensitivity cannot be increased.

(Means to Solve the Problems) Under these circumstances, the present inventors have conducted studies from a wide range of perspectives, including the search for new additives and the introduction of new processes, and have evaluated the properties. As a result of conducting a huge number of experiments, we completed a heat-developable dry silver salt material whose sensitivity was significantly increased by introducing certain new additives and which was sufficiently usable for practical use.

It was discovered that even short exposures can provide sufficient sensitivity. Further, the present invention uses this recording material,
erg! By writing in optical mode under conditions of high illuminance of i/'an2 or higher and short exposure of 10-3 seconds or less, and then thermal development, it is possible to practically record with digital recording methods. .

Also, unlike wet silver salt compositions that use water as a solvent and only silver halide as the image-forming iron, an organic solvent is used as the solvent and silver halide and an organic silver salt oxidizing agent are used as the image-forming silver. It has been discovered that a trace amount of gold atoms significantly improves the properties of a dry silver salt composition.

That is, the present invention provides a heat-developable dry silver salt containing (7) an organic silver salt oxidizing agent, (a) a polymer compound, (ii) a reducing agent, and (gradient silver halide or a silver halide forming component) as essential components. The present invention provides a dry silver salt material characterized in that the composition contains 10 -3 or more and 10 -7 or less gold atoms per silver atom.

In addition, using the dry silver salt material containing this gold atom, this material was exposed to 10 -
Writing with short exposure of 3 seconds or less, developing temperature 110℃ or higher1
The present invention provides a recording method characterized by heating at a temperature of 40° C. or lower.

The heat-developable dry silver salt composition used in the present invention contains an organic silver salt oxidizing agent, a polymer compound, a reducing agent, a silver halide or a silver halide-forming component, and a gold atom as essential components, and contains a toning agent, a thermal Optional ingredients include antifoggants, sensitizers, and spectral sensitizing dyes. The heat-developable dry silver salt composition referred to herein may be either normally photosensitive or normally non-photosensitive, and a normally non-photosensitive heat-developable dry silver salt composition is particularly preferred. The reason for this is that normally non-photosensitive heat-developable dry silver salt compositions have excellent raw film stability, but high illuminance failure is greater than that of normal photo-sensitive heat-developable dry silver salt compositions. This is thought to be due to the remarkable effect of introducing atoms.

Examples of optional ingredients include phthalazinone derivatives, cyclic imides, uracils, oxadiones, etc. as color toning agents, and mercury ions such as mercury acetate and mercury halides as heat fog preventive agents. Zinc acetate, calcium acetate, rosin, phthalic acid, etc. are used as sensitizers, organic amides such as formamide, N,N-dimethylformamide, tetramethylurea, N-methyl-2-pyrrolidone, nicotinamide, butyrolactone, 1 -vinyl-2
- Pyrrolidone, etc., and spectral sensitizing dyes include cyanine, merocyanine, styrylquinoline, rhodacyanine dyes, etc.

As the organic silver salt oxidizing agent which is an essential composition component, silver salts of long chain fatty acids, such as silver salts of stearic acid and silver salts of behenic acid, are particularly useful. However, other non-photosensitive silver salts can also be used, such as silver saccharate, silver lyazole, etc.

Examples of the polymer compound in the present invention include polyvinyl butyral, polymethyl methacrylate, vinyl formal, cellulose acetate, cellulose butyrate,
Examples include polystyrene and vinyl chloride/vinyl acetate copolymer.

The reducing agent in the present invention is an inhibiting phenol in which a sterically bulky group is bonded to the carbon adjacent to the carbon to which the hydroxyl group is bonded, sterically inhibiting the hydroxyl group, such as 2.6- Di-t-butyl-4-methylphenol, 2.2'-methylenebis-(4-methyl-6-1-butylphenol), 2.2'-methylenebis-(4-ethyl-6-t-butylphenol), 2, 4.4-Trimethylpentylbis-(2-hydroxy-3,5-,)
methylphenyl)-methane, 2,5-di-t-butyl-
Examples include 4-methoxyphenol. In addition, reducing agents for silver salts such as hydroquinone, 2.5-dimethylhyproquinone, chlorohydroquinone, p-aminephenol, methylhydronaphthalene, phenidone, eroded, methyl fertate, p-phenylphenol, bisphenol A, 2.4 -) Hydroxybenzoic a2) p-methoxyphenol can also be used.

...silver rosinide or...silver rosinide forming components include silver chloride, silver bromide, silver iodide, iodine, calcium iodide, dilium iodide, rubidium iodide, cesium iodide, aluminum iodide. , magnesium iodide,
Sodium iodide, etc., and corresponding bromides, chlorides, ionizable organic rosin compounds, non-fluorescent rosin compounds, rosin-containing organic metals, etc. can be mentioned. Representative examples of heat-developable dry silver salt compositions include Japanese Patent Publication No. 43-4924 and Japanese Unexamined Patent Application Publication No. 48-1989.
- -97523 Publication, Japanese Patent Publication No. 52-17415, Japanese Patent Publication No. 53-2687, Japanese Patent Publication No. 59-289
Examples include those described in Publication No. 5.

The amount of the essential component of the heat-transferable dry silver salt composition is such that the polymer compound is in a weight ratio of about 10:1 to about 1:10, preferably about 4:1 to about 1:10, relative to the organic silver salt oxidizing agent. The ratio of the reducing agent varies depending on the type of reducing agent, etc., but generally it is about 0.01 mol to 1 mol of the organic silver salt oxidizing agent.
The amount is about 10 mol, preferably about 0.1 mol to about 3 mol, and the silver halide or silver halide forming component is preferably 0.01 mol to 0.5 mol per mol of the organic silver salt oxidizing agent.

In the present invention, the term "silver atom" refers to silver and silver halide in an organic silver salt oxidizing agent or silver contained in a silver halide forming component. Furthermore, gold atoms may be in any form such as gold atoms, gold ions, total complexes, total complex ions, and gold compounds. Representative examples include gold atoms, gold ions, gold chloride ions, and gold thionoanate ions. , thiosulfate gold ion, etc., and it is particularly preferable to select it within the range of 10-4 to 10-6. If gold atoms are contained in a ratio exceeding 10-3, strong fog will occur after heat development, which is undesirable;
Less than 0-7 is 1. Since the sensitivity is the same as that of a heat-developable dry silver salt material that does not contain gold atoms, no increase in sensitivity, which is an effect of the present invention, is observed.

Generally, in the case of a non-photosensitive heat-developable dry silver salt composition, a photoreactive organic halogen oxidizing agent is an essential component in addition to the above-mentioned essential components. Suitable for the present invention are halogen compounds capable of generating halogen free radicals upon irradiation with light. Preferred examples of such rosin compounds are halogen compounds in which a carbon atom and a bromine atom or an iodine atom are bonded.

Preferred examples include 1,1,1',1'-tetrabromo-〇-xylene, 1,1,1',1'-
Tetrabromo-m-xylene, 1,1.1-1-dibromo-p-bromotoluene, 1,1.1-)dibromo-2
, 2-diphenylethane, 2 + 2 + 2- t+
) Furomonitanol, meso-1,2,3,4-tetrabromobutane, etc. can be mentioned. Typical examples of normally non-photosensitive dry silver salt compositions include JP-A No. 48-975
Publication No. 23, Special Publication No. 53-2687, Special Publication No. 53
-41967 publication, JP-A-48-51626 publication,
JP-A-53-114419, JP-A-53-114
Examples include those described in Publication No. 420 and the like.

In the heat-developable dry silver salt composition, the above-mentioned essential components and optional components are usually dispersed and dissolved in an organic solvent and then applied onto a support. The organic solvent used may be one having a boiling point of 150° C. or less, such as toluene, methyl ethyl ketone, acetate, methanol, ethanol, impronominol, hexane, dioxane, and tetrahydrofuran.

In addition, as described above, examples of short exposure light sources used in the present invention include glow lamps, xenon lamps, mercury lamps, light emitting diodes, )(e-Ne lasers, argon lasers, He-Cd lasers, semiconductor lasers, etc.). These light sources can easily generate 103 ergs.
It is possible to achieve high illuminance of /cM2 or more.

At an illuminance of less than 103ergs 7cm", the improvement in sensitivity is not significant. It is difficult to define an upper limit, and it is acceptable until the composition deteriorates. Examples of methods for short exposure include He-Ne laser, etc. With gas lasers, short exposures of 10-3 seconds or less are achieved by passing the laser light through an optical component that functions as a shutter, such as an AO modulator.Also, with semiconductor lasers, the laser beam itself has an on-off function. In the present invention, the sensitivity is significantly improved with a short exposure of 10-3 seconds or less, and preferably with a short exposure of 10-9 seconds or less.
Seconds or less are used.

It is difficult to realize short exposures of 10-10 seconds or less using the sage technology.

The developing method may be of any type as long as it is thermally developed, such as direct heating typified by Calo heat on a hot plate, heating in silicone oil, indirect heating typified by heating with hot air, etc. It will be done. At temperatures below 110°C, lI! J
If the temperature exceeds 140° C., image fogging occurs, making it impractical. Especially above 120℃140
It is preferable to select the temperature below ℃.

The optical density was measured using a density measuring device equipped with a halogen lamp as a light source, a Rattenna 106 as a filter, and a circular aperture. The measured value of this diffuse transmission concentration is based on the American ANSI standard PH2.1.
9-1959.

Book? ]+;Ft゛τThe terms "illuminance", "high illuminance", and "high illuminance failure" used are generally used as photographic technical terms, and "illuminance" in the present invention refers to The amount of energy ergs/crn.

Next, the present invention will be described in detail with reference to Examples, but these Examples are not intended to limit the scope of the present invention in any way.

Example 1 First, a dry silver salt composition solution 102 having the following component ratio was prepared.

Silver behenate 2t Polyvinyl butyral resin 1.5F Calcium iodide 1011q
Sodium bromide 50η Phthalazinone 122.2'-methylenebis-(4-ethyl-6-tert-butyl-phenol) 2.3 tQuinoline
0.7fN-Methylpyrrolidone 1tMethyl ether ketone
2 evenings 2 toluene
9f mercury acetate 0.5■
Methanol 3? Sensitizing dye 0.2 ■ Tetrachloro gold (
2) Sodium chloride listed in Table 1 All of the above components were mixed in a dark room, stirred for about 2 o'clock at 23°C, and then kept at a constant temperature of 23°C as a coating solution. Next, apply this coating solution for about 10 minutes using a Reno roll coater.
After drying at 65° C., the coating was applied onto a polyethylene terephthalate film having a thickness of 0 μm to a film thickness of 10 μm. Coating and drying were performed under safe light.

The recording method used a He-Ne laser of 2 mW, and the energy on the sensitive material surface was 3.7 x 10' ergs/cm.
2) Exposure time was 2.5 x 10-6 seconds. After exposure, heating was performed on a hot plate at 125° C. for 5 seconds.

From the results shown in Table 1, it can be seen that, according to the present invention, when gold atoms are included in the heat-developable dry silver salt composition, the sensitivity is dramatically improved.

Example 2 First, a dry silver salt composition solution having the following component ratio was prepared at about 10°C.

Silver behenate 27, I? Rivinyl Butyral Jugetsuji 1.67 No9ium Iodide 90mI! Phthalazinone 0.422.2'-/' Terene bis(4-ethyl-6-tet t-butyl-phenol) t,sy Quinoline 0.82α, α, α
', α'-tetrabromo〇-xylene 0.7? N-
Methylpyrrolidone 1? Methyl ethyl ketone 252 toluene
9-mercury acetate
4 ■ Methanol 3
2 Sensitizing dye solution 0.2 mq Sodium tetrachloroaurate (2) Listed in Table 2 The above components were all mixed in a dark room.
After stirring for about 2 hours at ℃, add 2 hours as a coating solution.
The temperature was kept constant at 2°C. Next, this coating solution was applied as a first layer onto a polyethylene terephthalate film having a thickness of about 100 .mu.m using a reno-throttle coater so that the film thickness after drying was about 9 .mu.m.

Next, a second layer constituent liquid having the following component ratio was uniformly applied so that the film thickness after drying was approximately 7 μm, and a roll film was used which was dried and wound up.

2nd layer constituent liquid acid phthalazinone 1.322.2'
-Methylenebis-(4-methine-6-tert-butyl-phenol) 42 Polymethyl methacrylate 5.8y Methyl ethyl ketone 70 Gold atoms were included in the tetrachlorite base (TID sodium was included in the first layer).

The recording method uses a IIe-Ne laser 2 tnW to increase the energy on the surface of the sensitive material to 8. IXlX108er/1Yn
2) Experiments were conducted with an exposure time of 1×10″″7 seconds. However, since the heat-developable dry silver salt composition of this example is normally a non-photosensitive film, it was preheated at about 100° C. for 3 seconds prior to exposure. The development conditions were 130° C., 4 seconds, and heating on a hot plate.

From the results shown in Table 2 below, it can be seen that when gold atoms are included in the heat-developable dry silver salt composition according to the present invention, the sensitivity is dramatically improved.

Example 3 A heat-developable dry silver salt film is prepared in exactly the same manner as in Example 2. However, in this example, 37? Since an IW semiconductor laser was used as the exposure source, di-ethylthiatetracal dicyanine bromide having a sensitivity at 780 nm was used as the sensitizing dye for the first layer. In addition, the introduction of gold atoms was carried out using sodium gold thiocyanate. Experiments were conducted at a ratio of 2.3×10 −5 gold atoms to silver atoms. The developing method is the same as in Example 2. The benefits of heat-developable dry silver salt compositions containing atoms are now clear. As mentioned above, at this stage 1×10-9
Short exposures of less than a second are extremely difficult with current technology.

Example 4 A heat-developable dry silver salt film is prepared in the same manner as in Example 2. The amount of gold atoms is 2.3 x 10-5 relative to silver atoms. The light source used was also the same as in Example 2.

From the results of Example 4 shown in Table 4 below, it can be seen that the development temperature is preferably from 110°C to 140°C. Furthermore, if the current maintenance time exceeds 1 minute, it is difficult to put it into practical use, and if it becomes shorter than 1 second, the unevenness of the image becomes so severe that it is not practical.

(Effects of the Invention) If the recording method of the present invention is used to record on the heat-developable dry silver salt material of the present invention, the sensitivity will be dramatically improved, so that the writing speed can be increased and the recording speed can be increased. Energy saving and downsizing of equipment are realized. Laser printers, write-once optical discs, optical tapes, optical cards,
C! Possible applications include OM (Computer Output Microfilmer), electrophotography, and laser photography, and the industrial effect will be great.

Patent applicant: Asahi Kasei Industries, Ltd.

Claims (2)

[Claims] (1) (a) Organic silver salt oxidizing agent, (b) polymer compound, (
C) In a heat-developable dry silver salt composition containing a reducing agent and (e) silver halide or a silver halide forming component as essential components, 10^-^3 to 10^- of gold atoms per 1 silver atom are added. ^
7. Dry silver salt material characterized by containing (2) In the heat-developable dry silver salt material described in claim 1,
High illuminance of 0^3ergs/cm^2 or more and 10^
- A recording method characterized by writing with short exposure of 3 seconds or less and heating at a developing temperature of 110°C or higher and 140°C or lower.