JPH0559416B2 - - Google Patents

Description

[Detailed description of the invention]

(Technical Field of the Invention) The present invention relates to an image forming method, and more specifically,
The present invention relates to a method of forming an image by exposing a photosensitive material using a light source such as a light emitting diode. (Background Art) A method of image exposure by scanning a photosensitive material using a light source such as a light emitting diode (LED) or a semiconductor laser is described, for example, in JP-A-57-151933, Proc.
It is known from SPIE, 390 , 149-154 (1983). Among these, light-emitting diodes convert electrical energy into light by passing a forward current through a pn junction of a semiconductor, and depending on their composition, their emission wavelengths span a wide range from the infrared region to the visible region. Also, its composition is GaAs (infrared), GaAsP
(red), GaAsP:N (red, yellow), GaAlAs (infrared,
red), GaN (blue), SiC (blue), GaP (red, green), etc.
Various types are known. Methods of forming images by exposing photosensitive materials using these light sources include, for example, using electrical signals of images taken with a video camera, images sent from a television station, or original images using a phototube or phototube. Electrical signals obtained by reading with a light receiving element such as a CCD (these may be stored in memory and subjected to image processing if necessary) are used to control the light emission of a light emitting diode or semiconductor laser, etc. ,
There is a method of scanning exposure by moving the photosensitive material, these light sources, or both in synchronization with this. In general, the above-mentioned light-emitting diodes emit light due to fluctuations in environmental temperature (fluctuations in the temperature of the light-emitting diode due to a heat source external to the light-emitting diode, or seasonal fluctuations in external temperature) or self-heating due to the energization of the light-emitting diode itself. Characteristics vary. The first of these characteristic variations is a variation in the emission wavelength, which generally shifts to longer wavelengths due to self-heating or an increase in external temperature. This shift in the emission wavelength may be accompanied by a change in the half-width along with a shift in the maximum emission wavelength, but to give one example, each time the temperature of the light emitting diode (whether self-heating or external factors) rises by 1°C, , about 0.4 nm for GaAlAs infrared light emitting diodes,
Approximately 0.17 nm for GaAlAs red light emitting diodes;
In GaP green light emitting diodes, the maximum emission wavelength may be shifted to the longer wavelength side by about 0.1 nm. The second characteristic variation due to temperature of light emitting diode
is a decrease in luminous output; as an example, for every 1°C of temperature rise, the luminous output (I) is △log=0.002 ~
It may decrease by about 0.003. Therefore, for example, if the temperature of the light emitting diode increases by 7°C, the change in the effective exposure amount (E) given to the photosensitive material will be due to a shift in wavelength.
△logE=0.1~0.2, both due to output reduction
reach a certain degree. The temperature increase due to self-heating of the light emitting diode itself is about this amount, and since the temperature increase due to external factors is added to this, this value actually becomes even larger. As a result of such variations in the characteristics of the light source, proper exposure is no longer given to the photosensitive material, resulting in problems such as a decrease in image density, uneven image density, and fluctuations in the color balance of images in the case of color photosensitive materials. . (Object of the Invention) The present invention aims to reduce variations in density and color balance of the final image even when there are variations in the light emitting characteristics of the light emitting diode as described above. be. (Structure of the Invention) The above object of the present invention is to provide a method for forming an image by exposing a photosensitive material using a light source whose emission intensity and emission spectrum maximum wavelength vary depending on temperature. An image forming method characterized in that the photosensitive material is exposed so that the center wavelength of the fluctuation substantially matches the maximum wavelength of spectral sensitivity of the photosensitive material, and the fluctuation in emission intensity due to the temperature of the light source is compensated for. This is achieved by Generally, the light emitting output of a light emitting diode increases approximately in proportion to the current. Therefore, the brightness of the light emitting element can be easily controlled by changing the diode current. Among the above-mentioned variations in the characteristics of light emitting diodes, the decrease in light emitting output due to temperature rise can be achieved by, for example, measuring the temperature of the light emitting diode with a temperature detection element and increasing the diode current in inverse response to the measured value. can be compensated by. Alternatively, the amount of light emitted may be directly measured by a light receiving element and compensated. Generally, when exposing a photosensitive material using a certain light source, the effective exposure amount is given by the product of the energy distribution Pλ of the light source and the spectral sensitivity distribution Sλ of the photosensitive material, ∫ ^∞ ₀ PλSλdλ. By compensating for the output drop, the value of ∫ ^∞ ₀ Pλdλ can be kept constant. Therefore, even if the maximum emission wavelength shifts to longer wavelengths as the temperature of the light emitting diode increases, the effective exposure amount given to the photosensitive material ∫ ^∞ ₀
In order to prevent PλSλdλ from changing, the spectral sensitivity of the photosensitive material should be kept approximately constant within the range in which the maximum emission wavelength varies. In other words, the maximum wavelength of the emission spectrum of the light source and the maximum wavelength of spectral sensitivity of the light-sensitive material may be approximately matched. The photosensitive materials used in the present invention are silver salt photosensitive materials,
It may be any non-silver salt photosensitive material. Examples of non-silver salt photosensitive materials include those made by electrophotography using zinc oxide or selenium as a photosensitive material, and those using photopolymers, but it is desirable that they be spectrally sensitizable. The silver salt photosensitive material may be one that uses an inorganic silver salt such as silver halide, or one that uses an organic silver salt in addition to an inorganic silver salt, but it is desirable that it can be spectrally sensitized. The silver salt photosensitive material may be one in which the image forming process is performed wet or dry. The silver salt photosensitive material may be a black and white photosensitive material using silver as an image forming substance, or a color photosensitive material using a coupler, a mobile dye-donating substance, etc. as a color image forming substance. As the silver halide emulsion used in the silver halide light-sensitive material, for example, those described in Basics of the Photographic Industry (Silver Salt Photography Edition), pages 240 to 268 (Corona Publishing, 1979) can be used. Photosensitive materials that undergo dry processing used in the present invention include, for example, Basics of Photographic Engineering (Silver Halide Photography Edition) 553
Pages ~ 555 (Corona Publishing, 1979), Eizo Information April 1978 issue, page 40, Nebletts Handbook of
Photography and Reprography 7th Ed.
Northnd Reinhold Company), pages 32-33, U.S. Patent No. 3152904, No. 3301678, No. 3392020,
No. 3457075, British Patent No. 1131108, No. 1167777
issue and Research Disclosure Magazine, June 1978 issue, pages 9-15 (RD-17028). In the present invention, as described above, silver can be used as an image forming substance, and in the case of an electrophotographic photosensitive material, a toner mainly composed of carbon can also be used as an image forming substance. Other image-forming substances include couplers that form a color image by combining with the oxidized form of a developer (for example, magenta couplers include 5-pyrazolone couplers, pyrazolobenzimidazole couplers, cyanoacetylcoumaron couplers, and open-chain acylacetate couplers). Nyltolyl couplers, etc.; as yellow couplers, acylacetamide couplers (eg, benzoylacetanilides, pivaloylacetanilides), etc.; as cyan couplers, naphthol couplers, phenol couplers, etc. can be used. These couplers are preferably non-diffusible and have a hydrophobic group called a ballast group in their molecules, or are polymerized. The coupler may be either 4-equivalent or 2-equivalent to silver ions. It may also be a colored coupler that has a color correction effect or a coupler that releases a development inhibitor during development (so-called DIR coupler). In addition, dyes that form color images can be produced using the photosensitive silver dye bleaching method. 15227), US Pat. No. 4,235,957, and leuco dyes described in US Pat. Nos. 3,985,565 and 4,022,617 can also be used as image-forming substances. Further, dyes into which a nitrogen-containing heterocyclic group is introduced, as described in Research Disclosure Magazine, May 1978 issue, pages 54-58, RD-16966, can also be used as image-forming substances. Furthermore, European Patent No. 79056, West German Patent No. 3217853
A dye that releases a mobile dye by utilizing a coupling reaction with a reducing agent that is oxidized by a redox reaction with silver halide or an organic silver salt at high temperatures, as described in European Patent No. 67455. donor substance,
European Patent No. 76492, West German Patent No. 3215485, European Patent No. 66282, Japanese Patent Application No. 58-28928, 58-
26008, which undergoes a redox reaction with silver halides or organic silver salts at high temperatures, resulting in the release of mobile dyes, can be used as image-forming substances. The above dye-donating substance is preferably one represented by the following general formula (). (Dye-X) _e -Y...() Dye represents a dye that becomes mobile when released from the molecule, and preferably has a hydrophilic group. Available dyes include azo dyes, azomethine dyes, anthraquinone dyes, naphthoquinone dyes, styryl dyes, nitro dyes, quinoline dyes, carbonyl dyes, and phthalocyanine dyes. It can also be used in short wave form. Specifically, the dyes described in European Patent Publication No. 76492 can be used. X represents a simple bond or linking group, such as -NP- (R represents a hydrogen atom, an alkyl group or a substituted alkyl group) group, -SO ₂ - group, -CO
- group, alkylene group, substituted alkylene group, phenylene group, substituted phenylene group, naphthylene group, substituted naphthylene group, -O- group, -SO- group, and a group formed by combining two or more of these. Y releases Dye in response to or inversely with the photosensitive silver salt that has a latent image, and the released dye and
Represents a group having properties that cause a difference in diffusivity from the compound represented by Dye-X-Y. Specific examples of the dye-donating substance represented by the general formula () are those described in Japanese Patent Application No. 58-42092, and include the following. The light-sensitive material of the present invention, preferably silver halide, is desirably spectrally sensitized with methine dyes or the like. The dyes used include cyanine dyes, merocyanine dyes, complex cyanine dyes, complex merocyanine dyes, holopolar cyanine dyes, hemicyanine dyes, styryl dyes and hemioxonol dyes. Particularly useful dyes are those belonging to the cyanine dyes, merocyanine dyes, and complex merocyanine dyes. These pigments include
Any of the nuclei commonly used for cyanine dyes can be used as the basic heterocyclic nucleus. That is, pyrroline nucleus, oxazoline nucleus, thiazoline nucleus, pyrrole nucleus, oxazole nucleus, thiazole nucleus, selenazole nucleus, imidazole nucleus, tetrazole nucleus, pyridine nucleus, etc.; a nucleus in which an alicyclic hydrocarbon ring is fused to these nuclei; and these A nucleus in which an aromatic hydrocarbon ring is fused to the nucleus of Imidazole nuclei, quinoline nuclei, etc. can be applied. These nuclei may be substituted on carbon atoms. The merocyanine dye or composite merocyanine dye includes a nucleus having a ketomethylene structure such as a pyrazolin-5-one nucleus, a thiohydantoin nucleus, a 2-thioxazolidine-2,4-dione nucleus, a thiazolidine-2,4-dione nucleus, a rhodanine nucleus, A 5- to 6-membered heteroartic ring nucleus such as a thiobarbituric acid nucleus can be applied. These sensitizing dyes may be used alone or in combination, and combinations of sensitizing dyes are often used particularly for the purpose of supersensitization.
Typical examples are U.S. Patent No. 2688545, U.S. Patent No. 2977229,
3397060, 3522052, 3527641, 3527641, 3522052, 3527641,
No. 3617293, No. 3628964, No. 36666480, No.
No. 3672898, No. 3679428, No. 3703377, No. 3672898, No. 3679428, No. 3703377, No.
No. 3769301, No. 3814609, No. 3837862, No. 3837862, No. 3814609, No. 3837862, No.
4026707, British Patent No. 1344281, British Patent No. 1507803,
Special Publication No. 43-4936, No. 53-12375, Japanese Patent Publication No. 52-
No. 110618 and No. 52-109925. Along with the sensitizing dye, the emulsion may contain a dye that itself does not have a spectral sensitizing effect or a substance that does not substantially absorb visible light and exhibits supersensitization. For example, aminostyryl compounds substituted with nitrogen-containing heterocyclic groups (e.g.,
2933390 and 3635721), aromatic organic acid formaldehyde condensates (for example, those described in US Pat. No. 3743510), cadmium salts, azaindene compounds, and the like. US patent
No. 3615613, No. 3615641, No. 3617295, No. 3615613, No. 3615641, No. 3617295, No.
The combination described in No. 3635721 is particularly useful. The maximum spectral sensitization obtained by spectral sensitization as described above needs to be on the longer wavelength side than the temperature-dependent variation range of the maximum emission wavelength of the light source used for exposure. When the light-sensitive material of the present invention is a multilayer color light-sensitive material and has a plurality of spectral sensitization regions,
As described above, as the wavelength of the spectral sensitization region increases, the spectral sensitization regions of each layer may overlap. In such a case, overlapping of the spectral sensitized regions can be prevented by dyeing the photosensitive layer, intermediate layer, filter layer, protective layer, etc. with a dye. A particularly preferred embodiment of the present invention is one in which silver halide and organic silver salt coexist.
Temperature above 80℃ in the presence of photosensitive silver halide,
Preferably, when heated to 100° C. or higher, it reacts with the image-forming substance or a reducing agent coexisting with the image-forming substance if necessary to form a silver image. By coexisting with an organic silver salt oxidizing agent, it is possible to obtain a photosensitive material that develops color with higher density. The silver halide that can be used in this case does not necessarily have to have the characteristic of containing pure silver iodide crystals when silver halide is used alone; All silver halides such as silver chloride, silver chloroiodide, silver bromide, silver iodobromide, silver chloroiodobromide, and silver iodide can be used. Two or more of the above silver halides having different sizes and/or silver halide compositions may be used in combination. The average grain size of the silver halide grains used in the present invention is preferably from 0.001 .mu.m to 10 .mu.m, more preferably from 0.001 .mu.m to 5 .mu.m. The silver halide used in the present invention may be used as it is, but it may also be compounded with compounds such as sulfur, selenium, tellurium, etc., chemical imaging agents such as compounds such as gold, platinum, palladium, rhodium and iridium, tin halide, etc. The image may be chemically imaged by the use of reducing agents such as or combinations thereof. For details,
“The.theory of the Photo graphic Process”
4th edition, by TH James, chapter 5, pages 149-169. In the present invention, the coating amount of photosensitive silver halide is suitably 1 mg to 10 g/m ² in terms of silver. Examples of the above-mentioned organic silver salt oxidizing agents include JP-A-58-
There is one described in No. 58543, and one example is the following. Silver salts of organic compounds having a carboxyl group can be mentioned first, and typical examples include silver salts of aliphatic carboxylic acids and silver salts of aromatic carboxylic acids. In addition, there are compounds having a mercapto group or a thione group, and silver salts of derivatives thereof. In addition, there are silver salts of compounds having imino groups. For example, silver salts of benzotriazole and its derivatives described in Japanese Patent Publications No. 44-30270 and No. 45-18416, silver salts of alkyl-substituted benzotriazoles such as benzotriazole silver salts, methylbenzotriazole silver salts, 5- Silver salts of halogen-substituted benzotriazoles such as silver salts of chlorobenzotriazole, silver salts of carboimidobenzotriazoles such as silver salts of butylcarboimidobenzotriazole, 1, 2, 4 described in U.S. Pat. No. 4,220,709; Examples include silver salts of -triazole and 1-H-tetrazole, silver salts of carbazole, silver salts of saccharin, and silver salts of imidazole and imidazole derivatives. Also, Research Day Closure No. 170, 17029
Organometallic salts such as the silver salts and steel stearates described in the above are also organometallic salt oxidizing agents that can be used in the present invention. For information on how to make these silver halides and organic silver salts, and how to mix both, see Research Disclosure No. 170, No. 17029, JP-A No. 50-32928,
JP-A-51-42529, JP-A-49-13224, JP-A-50-
17216, US Pat. No. 3,700,458. In the present invention, the coating amount of photosensitive silver halide and organic silver salt is 50 mg to 10 g in total in terms of silver.
^m2 is appropriate. Examples of the reducing agent to be coexisted with the above-mentioned image forming substance include hydroquinone compounds (e.g., hydroquinone, 2,5-dichlorohydroquinone, 2-chlorohydroquinone), aminophenol compounds (e.g., 4-aminophenol, N-methylaminophenol, 3-aminophenol, methyl-4-aminophenol, 3,5-dibromoaminophenol), catechol compounds (e.g. catechol, 4-cyclohexylcatechol, 3-methoxycatechol, 4-dibromoaminophenol),
-(N-octadecylamino)catechol), phenylenediamine compounds (e.g. N,N-diethyl-p-phenylenediamine, 3-methyl-N,N
-diethyl-p-phenylenediamine, 3-methoxy-N-ethyl-N-ethoxy-p-phenylenediamine, N,N,N',N'-tetramethyl-
p-phenylenediamine), 3-pyrazolidone compounds (e.g. 1-phenyl-3-hyrazolidone,
1-phenyl-4,4-dimethyl-3-pyrazolidone, 4-hydroxymethyl-4-methyl-1-
Phenyl-3-pyrazolidone, 1-m-tolyl-
3-pyrazolidone, 1-p-tolyl-3-pyrazolidone, 1-phenyl-4-methyl-3-pyrazolidone, 1-phenyl-5-methyl-3-pyrazolidone, 1-phenyl-4,4-bis-(hydroxy methyl)-3-pyrazolidone, 1,4-di-
Methyl-3-pyrazolidone, 4-methyl-3-pyrazolidone, 4,4-dimethyl-3-pyrazolidone, 1-(3-chlorophenyl)-4-methyl-3
-pyrazolidone, 1-(4-chlorophenyl)-4
-Methyl-3-pyrazolidone, 1-(4-tolyl)
-4-Methyl-3-pyrazolidone, 1-(2-tolyl)-4-methyl-3-pyrazolidone, 1-(4
-tolyl)-3-pyrazolidone, 1-(3-tolyl)-3-pyrazolidone, 1-(3-tolyl)-4,
Examples include 4-dimethyl-3-pyrazolidone, 1-(2-trifluoroethyl)-4,4-dimethyl-3-pyrazolidone, and 5-methyl-3-pyrazolidone). The amount of the above reducing agent added is 0.01 per mole of silver.
-20 mol, particularly preferably 0.1-10 mol. In the present invention, even when using a reducing dye-donating substance, a so-called auxiliary developer can be used as necessary. The auxiliary developer in this case is
Oxidized by silver halide, the oxidized product is
It has the ability to oxidize the reducing substrate in the dye-donating substance. Useful auxiliary developers include alkyl-substituted hydroquinones such as hydroquinone, t-butylhydroquinone, and 2,5-dimethylhydroquinone, catechols, pyrogallols, halogen-substituted hydroquinones such as chlorohydroquinone and dichlorohydroquinone, and alkyl-substituted hydroquinones such as methoxyhydroquinone. There are substituted hydroquinones and polyhydroxybenzene derivatives such as methylhydroxynaphthalene. Furthermore, methyl gallate, ascorbic acid, ascorbic acid derivatives, N,N'-
Hydroxylamines such as di-(2-ethoxyethyl)hydroxyamine, 1-phenyl-3-
Pyrazolidones such as pyrazolidone and 4-methyl-4-hydroxymethyl-1-phenyl-3-pyrazolidone, reductones, and hydroxytetronic acids are useful. In the present invention, the image-forming substance is U.S. Pat.
It can be introduced into the layer of the photosensitive material by a known method such as the method described in No. 2322027. In that case, the following high boiling point organic solvents and low boiling point organic solvents can be used. For example, phthalic acid alkyl esters (dibutyl phthalate, dioctyl phthalate, etc.), phosphoric acid esters (diphenyl phosphate, triphenyl phosphate, tricresyl phosphate, dioctyl butyl phosphate), citric acid esters (e.g. acetyl tributyl citrate) ,
High-boiling point organic solvents such as benzoic acid esters (octyl benzoate), alkylamides (e.g. diethyl laurylamide), fatty acid esters (e.g. dibutoxyethyl succinate, dioxyl azelate), trimesic acid esters (e.g. tributyl trimesate) , or boiling point approximately 30℃ to 160℃
After dissolving in an organic solvent such as lower alkyl acetate such as ethyl acetate or butyl acetate, ethyl propionate, secondary butyl alcohol, methyl isobutyl ketone, β-ethoxyethyl acetate, methyl cellosolve acetate, cyclohexanone, etc., it is converted into a hydrophilic colloid. distributed. The above-mentioned high boiling point organic solvent and low boiling point organic solvent may be mixed and used. Further, the dispersion method using a polymer described in Japanese Patent Publication No. 51-39853 and Japanese Patent Application Laid-open No. 51-59943 can also be used. Furthermore, various surfactants can be used when dispersing the image-forming substance in the hydrophilic colloid.
As such surfactants, those mentioned as surfactants elsewhere in this specification can be used. The amount of the high-boiling organic solvent used in the present invention is 10 g or less, preferably 5 g or less, per 1 g of the image-forming substance used. In the present invention, it is preferable to use a base or a base precursor as the dye release aid. In this case, the base or base precursor can be used in either the light-sensitive material or the dye-fixing material. When included in a light-sensitive material, it is particularly advantageous to use a base precursor. The base precursor referred to herein is one that releases a basic component upon heating, and the released basic component may be either an inorganic base or an organic base. Preferred inorganic bases include alkali metal or alkaline earth metal hydroxides, secondary or tertiary
Examples include phosphates, borates, carbonates, quinolates, metaborates, ammonium hydroxides, quaternary alkyl ammonium hydroxides, and other metal hydroxides. Preferred organic bases include aliphatic amines, aromatic amines, heterocyclic amines, amidines, cyclic amidines, guanidines, and cyclic guanidines, especially those with pKa8
The above are particularly useful in the present invention. Examples of base precursors include salts of organic acids and bases that are decarboxylated and decomposed by heating, and compounds that open and release amines through reactions such as intramolecular nucleophilic substitution reactions, Lothsen rearrangement, and Beckman rearrangement. Those that release a base by causing some kind of reaction are preferably used. Preferred base precursors include trichloroacetic acid salts described in British Patent No. 998949, α-sulfonylacetic acid salts described in U.S. Pat. Patent No.
2-carboxycarboxamide derivatives described in No. 4088496, salts with thermally decomposable acids using alkali metals and alkaline earth metals in addition to organic bases as the base component (Patent Application No. 1982-69597), utilizing Lotusene rearrangement Hydroxam carbamates described in Japanese Patent Application No. 1986-43860, which produce nitriles by heating
Examples include aldoxyl carbamates described in No. 58-31641. Others, UK Patent No. 998945
No., U.S. Patent No. 3220846, Japanese Patent Application Publication No. 50-22625,
Base precursors described in British Patent No. 2079480 and the like are useful. Specific examples of base precursors particularly useful in the present invention are shown below. Guanidine trichloroacetate, methylguanidine trichloroacetate, lorium trichloroacetate, guanidine phenylsulfonylacetate, guanidine P-chlorophenylsulfonylacetate, guanidine P-methanesulfonylsulfenylsulfonylacetate,
Potassium phenylpropiolate, cesium phenylpropiolate, guanidine phenylpropiolate, guanidine P-chlorophenylpropiolate, guanidine 2,4-dichlorophenylpropiolate, P-phenylene-bis-propiolate Diguanidine, tetramethylammonium phenylsulfonylacetate, tetramethylammonium phenylpropiolate. The light-sensitive material used in the present invention is formed by coating a support with a light-sensitive layer, such as a silver halide photographic emulsion layer, but it can also have a multilayer structure. When the light-sensitive material used in the present invention is a color photographic light-sensitive material, one example is one in which a red-sensitive light-sensitive layer, a green-sensitive light-sensitive layer, and a blue-sensitive light-sensitive layer are coated on a support in this order, or an infrared-sensitive light-sensitive material. It is formed by coating a photosensitive layer, a red-sensitive photosensitive layer, and a green-sensitive photosensitive layer in this order, and each photosensitive layer preferably forms a cyan, magenta, and yellow image, respectively.
In this case, each photosensitive layer may have a multilayer structure of two or more layers, and an intermediate layer or filter layer may be provided between each photosensitive layer. A protective layer can also be provided as the layer furthest from the support. Furthermore, the spectral sensitivity characteristics and color image forming characteristics of each photosensitive layer of the photosensitive material are not limited to the above examples. It is also possible to use a combination in which the green-sensitive photosensitive layer forms a yellow image, or a combination in which the red-sensitive photosensitive layer forms a magenta image, the green-sensitive photosensitive layer forms a cyan image, and the blue-sensitive photosensitive layer forms a yellow image. The order of coating the photosensitive layers is not limited to the above example. For example, a red-sensitive photosensitive layer, a green-sensitive photosensitive layer, and an infrared-sensitive photosensitive layer are coated in this order from the support side, or a blue-sensitive photosensitive layer is coated in this order. Sensitive photosensitive layer, red sensitive photosensitive layer,
It may be formed by coating the green-sensitive photosensitive layer in this order. One of the preferable embodiments of the light-sensitive material used in the present invention uses silver halide spectrally sensitized with the above-mentioned spectral sensitizing dye as the photosensitive substance, and uses the above-mentioned developer as the image-forming substance. A coupler that reacts with an oxidized form of to form a dye, or a dye-donating substance that releases a mobile dye by performing a redox reaction with silver halide or organic silver salt at high temperature, preferably the general formula () A compound represented by the formula is used. When using a dye-providing substance that releases the above-mentioned mobile dye, the light-sensitive material is subjected to imagewise exposure, heated (thermal developer) to form an image, and then overlaid with a dye-fixing material to form an image. An image can be obtained by transferring it to a fixed material. In this case, the image forming step by heating and the transfer step can be performed in one step. The above-mentioned dye fixing material has a dye fixing layer on a support and, if necessary, a white reflective layer containing a white material such as titanium dioxide. The dye fixing layer contains a binder and a mordant for fixing the dye, and preferably contains a polymer containing a secondary or tertiary amino group, a polymer having a nitrogen-containing heterocyclic group, or a quaternary cation group thereof. Molecular weight of polymers etc. 5000~200000, especially 10000~
A mordant in the range of 50,000 is preferred. In addition to these mordants, the dye fixing layer can contain a base, a base precursor, a thermal solvent, and the like.
Furthermore, the photosensitive layer containing a photosensitive substance and the dye fixing layer can be provided on the same support. The binders used in the present invention can be contained alone or in combination. A hydrophilic binder can also be used. Typical hydrophilic binders are transparent or translucent hydrophilic binders, such as proteins such as gelatin, gelatin derivatives, and cellulose derivatives, natural substances such as starch, polysaccharides such as gum arabic, polyvinylpyrrolidone, Includes synthetic polymeric materials such as water-soluble polyvinyl compounds such as acrylamide polymers. Other synthetic polymeric materials include dispersed vinyl compounds, particularly in the form of latexes, which increase the dimensional stability of photographic materials. Further, in the present invention, it is possible to use a compound that activates the development and stabilizes the image at the same time.
Among them, isothiuroniums represented by 2-hydroxyethylisothiuronium trichloroacetate described in U.S. Patent No. 3301678, 1,8-(3,6-dioxaoctane)bis(isothiuronium・Bis(isothiuroniums) such as trichloroacetate, thiol compounds described in West German Patent No. 2162714,
Thiazolium compounds such as 2-amino-2-thiazolium trichloroacetate and 2-amino-5-bromoethyl-2-thiazolium trichloroacetate described in U.S. Pat. No. 4,012,260, bis(2-amino -2
Compounds having α-sulfonylacetate as an acidic moiety, such as -thiazolium)methylenebis(sulfonylacetate) and 2-amino-2-thiazoliumphenylsulfonylacetate;
Compounds having 2-carboxycarboxamide as the acidic moiety described in US Pat. No. 4,088,496 are preferably used. Furthermore, azole thioether and blocked azolinthionic compounds described in Belgian Patent No. 768071, and 4-aryl-
1-bamyl-2-tetrazoline-5-thione compound, and other U.S. Patent Nos. 3839041 and 3844788,
The compounds described in No. 3877940 are also preferably used. The support used in the light-sensitive material and the dye-fixing material used in some cases in the present invention is one that can withstand processing temperatures. Common supports include glass, paper, metal and their analogs, as well as cellulose acetate film, cellulose ester film,
Included are polyvinyl acetal film, polystyrene film, polycarbonate film, polyethylene terephthalate film, and films or resin materials related thereto. Paper supports laminated with polymers such as polyethylene can also be used. US Patent 3634089
The polyester described in No. 3,725,070 is preferably used. The photographic material and dye fixing material of the present invention include:
The photographic emulsion layer and other binder layers may contain an inorganic or organic hardener. For example, chromium salts (chromium alum, chromium acetate, etc.), aldehydes (formaldehyde, cryoxal, glutaraldehyde, etc.), N-methylol compounds (dimethylol urea, methylol dimethylhydantoin, etc.), dioxanoic acid derivatives (2,3-dihydroxydioxane, etc.) etc.), activated vinyl compounds (1,
3,5-Triacryloyl-hexahydro-s-
triazine, 1,3-vinylsulfonyl-2-propanol, etc.), active halogen compounds (2,4
-dichloro-6-hydroxy-s-triazine, etc.), mucohalogen acids (mucochloric acid, mucophenoxychloroic acid, etc.), etc. can be used alone or in combination. A dye transfer aid can be used to transfer the dye from the photosensitive layer to the dye fixed layer. In the method of supplying the dye transfer aid externally, water, caustic soda, caustic potash,
A basic aqueous solution containing an inorganic alkali metal salt is used. Further, a low boiling point solvent such as methanol, N,N-dimethylformamide, acetone, diisobutyl ketone, or a mixed solution of these low boiling point solvents and water or a basic aqueous solution is used.
The dye transfer aid may be used by wetting the image receiving layer with the transfer aid. If the transfer aid is incorporated into the photosensitive material or dye fixing material, there is no need to supply the transfer aid from the outside.
The above transfer aid may be incorporated into the material in the form of crystal water or microcapsules, or may be incorporated as a precursor that releases the solvent at high temperatures. More preferably, a hydrophilic thermal solvent that is solid at room temperature and soluble at high temperature is incorporated into the light-sensitive material or dye-fixing material. The hydrophilic heat solvent may be incorporated into either the photosensitive material or the dye fixing material, or may be incorporated into both. Further, the layer to be incorporated may be any of an emulsion layer, an intermediate layer, a protective layer, and a dye fixing layer, but it is preferably incorporated in the dye fixing layer and/or a layer adjacent thereto. Examples of hydrophilic heat solvents include ureas, pyridines, amides, sulfonamides, imides, alcohols, oximes, and other heterocycles. Other compounds that can be used in the light-sensitive material in the present invention, such as sulfamide derivatives, cationic compounds having a pyridinium group, surfactants having a polyethylene oxide chain, filter dye halation and anti-irradiation dyes, hardeners, mordants, etc. European patent for
Those described in German Patent No. 76492, No. 66282, West German Patent No. 3315485, Japanese Patent Application No. 58-28928, and Japanese Patent Application No. 58-26008 can be used. The silver salt photosensitive material used in the present invention can form either a positive image or a negative image by selecting silver halide as the photosensitive material. For example, US Pat. No. 2,592,250, US Pat. No. 3,206,313, US Pat.
No. 3,447,927, as well as mixtures of surface-imaged silver halide emulsions and internal-imaged silver halide emulsions such as those described in U.S. Pat. No. 2,996,382. can. The heating temperature in the heat development process is approximately 80℃ to approximately 250℃
It can be developed at a temperature of about 110°C to about 160°C, but is particularly useful. The heating temperature in the transfer step can be in the range from the temperature in the heat development step to room temperature, but a temperature range of about 60° C. or more and about 10° C. or more lower than the temperature in the heat development step is particularly preferable. The heating means in the heat development process is heated by passing between hot plates or heating by contacting with the hot plates (for example,
-62635), heating by contacting a heated drum or roller while rotating (e.g. Japanese Patent Publication No. 10791/1979),
Heating by passing through hot air (for example, JP-A-53-
32737), heating by passing through an inert liquid kept at a constant temperature, heating by passing it along a heat source with a roller, belt, or guide member (for example, Japanese Patent Publication No. 44-2546), etc. I can do it. Alternatively, a heat-developable photosensitive material may be coated with layers of conductive material such as graphite, carbon black, or metal, and this conductive layer may be heated directly by passing an electric current through it (for example, (Sho 48-66442). The heating means in the transfer step can also be the same as in the heat development step described above. The light emitting diodes of the light source used in the present invention include GaAsP (red), GaP (red, green), and GaAsP:N.
(red, yellow), GaAs (infrared), GaAlAs (infrared, red),
GaP: N (red, green, yellow), GaAsiSi (infrared), GaN
Various types can be used, such as (blue) and Sic (blue). It is also possible to use an infrared-visible conversion element that converts infrared light from an infrared light emitting diode as described above into visible light using a phosphor. As such a fluorophore, a fluorophore activated with a rare earth element is preferably used, and as the rare earth element, Er ³⁺ , Tm ³⁺ , Yb ³⁺ , etc. can be used. In the present invention, various thermistors, CTR (Critical
Various types such as biristors (temperature resistors) are used. By arranging these temperature sensing elements as close to the light source as possible and increasing the input current as the detected temperature increases, the light emitting output can be kept constant. In addition, when using a P-n junction type light emitting device such as an LED, the forward voltage drop Vif of the P-n junction under constant current is measured, and this Vif has a characteristic that decreases in proportion to the junction temperature Tj. There is a method of controlling the input current of the light source using feedback. In this case, the light emitting element itself becomes a temperature detection element, allowing more precise control. In addition, as described in the specification filed by the applicant on June 18, 1982, under the name "Light Amount Correction Device for Image Output Device," the amount of light emitted by a light source is measured and converted into a voltage signal. It is also possible to provide a correction circuit that compares the voltage signal from the monitor circuit with a reference voltage and gives the image signal a deviation, thereby keeping the light emission output constant. FIG. 3 is a diagram showing a temperature output compensation circuit using a temperature sensing element. Input resistance R ₁ of the operational amplifier that amplifies the image signal
An example using a thermistor with negative characteristics is shown below. The amplification factor K of the inverting amplifier is expressed as K=R ₂ /R ₁ . The value of the thermistor _R1 decreases when the temperature rises, so K increases, and the current flowing to the LED through the voltage-current conversion circuit increases,
The amount of light emitted increases. If the temperature coefficient of R ₁ is selected to be equal to the rate of decrease in the amount of light emitted, the amount of light can be controlled to be constant. FIG. 4 is a diagram showing a temperature output compensation circuit using the forward voltage inorganic voltage drop of the LED. Immediately before recording an image, for example when recording using raster scanning, turn S ₁ during the blanking period.
Constant current I ₀ is applied to the LED by turning OFF and turning S ₂ ON.
is applied, and the forward voltage drop Vif at this time is amplified to a value of K=Ko−KaVif by an inverting amplifier. By storing the value of K at this time in the sample and hold circuit, and then turning off S ₂ and connecting S ₁ ,
The current flowing through the LED is controlled by the value obtained by multiplying the image signal by K. Since Vif becomes smaller as the temperature rises, K becomes larger, the current flowing through the LED increases, and the amount of light emitted increases. By setting the value of Ka appropriately, the amount of light emitted can be controlled to be constant even when the temperature changes. Image exposure of the photosensitive material of the present invention is performed by scanning exposure using a light emitting diode. In this case, the scanning method may be, for example, Japanese Patent Application Laid-open No. 57-151933 or Japanese Patent Application No. 57-151, filed by the present applicant.
As described in No. 226555, there is a scanning method in which light sources such as LEDs and semiconductor lasers are arranged in the circumferential direction of a disk-shaped rotor, and the rotor is rotated and moved in the direction of the rotation axis, or the so-called scanner. As is known in the art, a photosensitive material is wound around a drum, the drum is rotated, and a head, which is provided with a light source or the light from the light source is guided by an optical fiber, is moved in the direction of the drum's rotational axis. A method of scanning by moving or the like can be used. Example 1 A methanol solution (0.005%) of a spectral sensitizing dye having the following structural formulas 1 to 6 was added to 100 g of a silver iodobromide agent (containing 5 g of gelatin and 10 g of silver) prepared by a conventional method (0.005%) (1 ~4) or methyl cellosolve solution (0.005%) (for cases 5 and 6) at 10% each
cc and an antifoggant, a hardening agent, a coating aid, etc. in a conventional manner, and then coated on a polyethylene terephthalate support at a coating weight of 5 g of silver per 1 m ² of light-sensitive materials A to F. I made it. This light-sensitive material was subjected to image exposure using a scanning type exposure device similar to that described in JP-A-57-151933, and developed and fixed in a conventional manner to obtain a black and white image. The light emitting characteristics of the light emitting diode used for exposure and the spectral sensitizing characteristics of the spectral sensitizing dye are as shown in FIGS. 1 and 2, respectively. In Figure 1, the light emitting diode PG is made of GaP, and the light emitting characteristics, PR, at an input current value of 80 mA are
Made of GaAlAs, input current value 80mA
PIR is made of GaAlAs and shows the light emission characteristics at an input current value of 80 mA. FIG. 2 is a diagram showing the spectral sensitization characteristics of light-sensitive materials A to F spectrally sensitized using spectral sensitizing dyes 1 to 6. Structural formula of spectral sensitizing dye Photosensitive material A (using spectral sensitizing dye 1) and photosensitive material C (using spectral sensitizing dye 3), in which the spectral sensitivity wavelength of the photosensitive layer is made to almost match the center wavelength of the fluctuation of the wavelength maximum of the emission spectrum of the light source. ), photosensitive material E
(Using spectral sensitizing dye 5) is Photosensitive material B (Using spectral sensitizing dye 2), Photosensitive material D (Using spectral sensitizing dye 4), Photosensitive material F
(Using spectral sensitizing dye 6), the image had less unevenness. Example 2 20 g of a spectrally sensitized light-sensitive silver halide emulsion prepared by the same method as in Example 1 was added to
10 g of a silver benzotriazole emulsion prepared by the method described in No. 83154 and 33 g of an image-forming material dispersion prepared by the method described below were added as shown in the table below, and 10 c.c. of a 5% aqueous solution of guanidine trichloroacetic acid. and dimethylsulfonamide in 5% aqueous solution
After adding 10 c.c., the mixture was coated on a polyethylene terephthalate support to prepare photosensitive materials G to L. Preparation of image-forming substance dispersion (1) 5 g of image-forming substance (7), 0.5 g of sodium succinate-2-ethyl-hexyl ester sulfonate, 5 g of tricresyl fuphate, 30 ml of ethyl acetate
Dissolve by heating, add to 100 ml of 10% by weight aqueous gelatin solution, and stir to disperse. Preparation of image-forming substance dispersion (8) A dispersion of image-forming substance (8) was prepared in the same manner as image-forming substance (1), except that 5 g of image-forming substance (5) was used. Preparation of image-forming substance dispersion (3) Image-forming substance dispersion (3) was prepared in the same manner as image-forming substance dispersion (1), except that 7.5 g of image-forming substance (9) was used. Light-sensitive material Spectral sensitizing dye Image forming material (maximum sensitization)
Quality dispersion G 1 (570nm) (1) H 2 (585nm) (1) I 3 (670nm) (2) J 4 (695nm) (2) L 5 (785nm) (3) L 6 (810nm) (3 ) For the above photosensitive materials G to L, JP-A-57-
A scanning exposure apparatus similar to that described in No. 151,938 was used to provide imagewise exposure. The light emitting characteristics of the light emitting diode used for exposure are the same as those shown in FIG. Next, add approximately 150 G to L of the exposed photosensitive material above.
The image was developed by heating to .degree. C., and the image was transferred to the image-receiving layer by superimposing it on an image-receiving material prepared by the method described below.The light-sensitive material and the dye-fixing material were then peeled off to obtain an image on the dye-fixing material. Preparation of dye fixing material 10g of poly(methyl acrylate-co-N,N,N-trimethyl-N-vinylbenzylammonium chloride) (ratio of methyl acrylate and vinylbenzylammonium chloride is 1:1)
It was dissolved in 200 ml of water and mixed with 100 g of 10% by weight lime processed gelatin. This mixture was applied onto a paper support laminated with polyethylene in which titanium dioxide was dispersed, and dried to produce a dye-fixing material. Photosensitive material G (using spectral sensitizing dye 1) in which the maximum spectral sensitivity wavelength of the photosensitive layer is made to almost match the center wavelength of fluctuation in the maximum wavelength of the emission spectrum of the light source, and photosensitive material I (using spectral sensitizing dye 3). Images obtained using Photosensitive Material H (using spectral sensitizing dye 2) and Photosensitive Material K (using spectral sensitizing dye 5) and Photosensitive Material J (using spectral sensitizing dye 2) Sensitive dye 4
The images were clearer and less uneven than the images obtained using Photosensitive Material L (using spectral sensitizing dye 6) and Photosensitive Material L (using spectral sensitizing dye 6). Example 3 Photosensitive materials M and N were prepared by coating multiple photosensitive layers similar to those used in Example 2 as described below.

[Table] The above photosensitive materials M and N were exposed to light in the same manner as in Example 2, and after heat development, images were obtained by transferring to a dye-fixing material. The image obtained using the photosensitive material M is more uniform than the image obtained using the photosensitive material N.
There was little change in color balance. (Effects of the Invention) By using the method of the present invention, when exposing a photosensitive material using a light source whose emission intensity and emission spectrum maximum wavelength change depending on temperature, the effective amount of exposure given to the photosensitive material is Since it is not dependent on temperature, it is possible to prevent fluctuations in image density and disruption of color balance.

[Brief explanation of the drawing]

FIG. 1 is a diagram showing an example of the light emitting characteristics of a light emitting diode used in the present invention. FIG. 2 is a diagram showing an example of the spectral sensitivity distribution characteristics of the photosensitive material used in the present invention and a photosensitive material for comparison. Figure 3 is an output compensation circuit using a temperature sensing element, Figure 4 is
FIG. 3 is a diagram showing an output compensation circuit using a forward voltage drop of an LED. PIR...Emission characteristics of GaAlAs light emitting diode,
PR...Emission characteristics of GaAlAs light emitting diode, PG
...Emission characteristics of GaP light emitting diode, 1... Spectral sensitivity characteristics of green-sensitive photosensitive layer (present invention), 2... Spectral sensitivity characteristics of green-sensitive photosensitive layer (comparison), 3... Spectral sensitivity of red-sensitive photosensitive layer Characteristics (present invention), 4... Spectral sensitivity characteristics of red-sensitive photosensitive layer (comparison), 5... Spectral sensitivity properties of infrared-sensitive photosensitive layer (present invention), 6... Spectral sensitivity of infrared-sensitive photosensitive layer Sensitivity characteristics (comparison), A... Image signal, 10... Thermistor, 11... Resistor,
12... operational amplifier, 13, 16... voltage-current converter, 14... LED, 15... analog multiplier,
17...Amplifier, 18...Sample hold, B
...Temperature measurement timing signal.

Claims (1)

[Scope of Claims] 1. A method of exposing a photosensitive material to form an image using a light source whose emission intensity and maximum wavelength of the emission spectrum vary depending on temperature, wherein the center wavelength of the variation of the maximum wavelength of the emission spectrum of the light source; An image forming method characterized in that the photosensitive material is exposed in such a manner that the wavelength of the maximum spectral sensitivity of the photosensitive material is almost the same, and fluctuations in emission intensity due to the temperature of the light source are compensated for. 2. The image forming method as described in item 1 above, characterized in that compensation for fluctuations in emission intensity of the light source is performed by a compensation circuit using a temperature detection element. 3. The image forming method as described in item 1 above, wherein compensation for fluctuations in emission intensity of the light source is performed by a compensation circuit using a light receiving element.