JPS6152642A - Image forming method - Google Patents

Abstract

PURPOSE:To reduce variations of image density and color balance by reducing variation of an effective exposure amt. to be given to a photosensitive material. CONSTITUTION:When the photosensitive material is exposed by using a light source varied in light emission intensity and spectral wavelengths by variation of the temp. of the light source, the max. of the spectral sensitivity distribution of the photosensitive material is set to the side longer in wavelength than the variation region of the max. wavelength of the light emission spectra, and the material is exposed to form an image, thus permitting the effects of the light intensity and wavelength variation to be exerted on the photosensitive material to be canceled with the spectral sensitivity of the photosensitive material and variation of the effective exposure amt. to be given to the photosensitive material to be reduced, and variation of image density and deformation of color balance, etc., to be prevented.

Description

[Detailed Description of the Invention] [Technical Field of the Invention] The present invention [! l11 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 technology]

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-Sho! Coo/! /ri No. 33, Proc, of 5P
IE+jde0. /4tter/j4t (/rirt) etc.

Among these, a light emitting diode converts electrical energy into light by passing forward current through the pn junction of a semiconductor.
Depending on its composition, its emission wavelength spans a wide range from the infrared region to the visible region. Also, its composition is GaA
s (infrared), GaAsP (red), GaAsP:N(
red, yellow), GaH (blue), 5iC(f), GaAlAs
Various types are known, such as (infrared, red) and GaP (red, green). Methods of forming images by exposing photosensitive materials using these light sources include, for example, using electrical signals of images taken by a video camera, images sent from a television station, or original images using a phototube or COD.
The electrical signals obtained by reading the light-receiving element (these may be stored in a memory and subjected to image processing if necessary) are used to control the light emission of a light-emitting diode or semiconductor laser, etc. Synchronize with
There is a method of scanning exposure by moving the photosensitive material, these light sources, or both.

In general, the above-mentioned light-emitting diodes are susceptible to environmental temperature fluctuations (fluctuations in the temperature of the light-emitting diode due to a heat source external to the light-emitting diode, or seasonal fluctuations in the external temperature). ? The light emitting characteristics fluctuate due to self-heating caused by energization. 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 shift in the maximum emission wavelength and a change in the half-width.
To give seven examples, every time the temperature of a light emitting diode (self-heating or external factors) increases by 10 c, the GaAl
Approximately 0°@nm for As infrared light emitting diodes, GaAlA
In the case of a red light emitting diode, the emission maximum wavelength may be shifted to the longer wavelength side by approximately 0./7 nm in the case of a green light emitting diode.

The first characteristic change due to temperature of a light emitting diode is a decrease in light emitting output.As an example, for a temperature increase of 10C,
The light emission output may decrease by about Δ1ogI=o,oo~0,003 (I is the light emission output).

Thus, for example, if the temperature of the light-emitting diode increases by 7°C, the change in the effective exposure given to the photosensitive material will be Δl OK I=0, both due to the shift in wavelength and due to the reduction in output.

/~0.2. The temperature increase due to the 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. .

[Purpose of the invention]

The present invention can be achieved by reducing the variation in the effective exposure amount given to the photosensitive material when the photosensitive material is exposed using a light source whose emission characteristics vary due to variations in the temperature of the light source. The purpose is to reduce variations in image density and color balance.

[Structure of the invention]

The object of the present invention is to provide a method for forming an image by exposing a photosensitive material to light using a light source whose emission intensity and emission spectrum wavelength vary depending on temperature. This is achieved by an image forming method characterized in that the photosensitive material is exposed to light at a wavelength longer than the maximum variation range of the emission spectrum wavelength of the light source.

Generally, the effective exposure amount given to a photosensitive material is given by the product of the energy distribution Pλ of the light source and the spectral sensitivity distribution Sλ of the photosensitive material, but in the present invention, even when Pλ fluctuates, the effective exposure amount is 70X)
Fluctuations in image density are eliminated by configuring Sλ so that pλSλdλ=constant relationship is established. As mentioned above, in light-emitting diodes, as the temperature rises, the emission wavelength shifts to the longer wavelength side and the emission intensity decreases. By configuring it to increase, it is possible to correct variations in the effective exposure amount given to the photosensitive material.

The photosensitive material used in the present invention may be either a silver salt photosensitive material or a 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 can be spectrally sensitized. The silver salt photosensitive material may be one that uses an inorganic silver salt such as silver chloride, or one that uses an organic silver salt in addition to an inorganic silver salt, but there is a risk of spectroscopic sensitization. desirable. The silver salt photosensitive material may undergo an image forming process either wet or dry.

The silver salt light-sensitive material may be a black-and-white light-sensitive material using silver as an image-forming substance, or a color light-sensitive material using a coupler, a mobile dye-donating substance, or the like as an image-forming substance.

Examples of silver halide emulsions used in silver halide photosensitive materials include Basics of Photographic Engineering (Silver Salt Photography Edition) 2/0
Page~, 2 Otsu! It is possible to use the one described in page (/979 Coronasha).

Photosensitive materials that undergo dry processing used in the present invention include, for example, Basics of Photographic Engineering (Silver Halide Photography Edition)! Evening page 3~! ! ! Page (Coronasha, /?7?), Video information / 2nd year Gu month issue, page 4t0, NebleLLsHandbook of
Photography and Reprogr
aphy 7Lh Ed, (Van Nortr
snd Re1nhold Company) 32~
Page 33, US Patent No.! ,/! 2.90Z No. 3゜3
No. 07.372, No. 3.3 Octopus, No. 020, No. j,
4tj7, 0';#, British Patent No. 1, /, 3/
.

/θ issue, No. 1,7g7.777 and Research Disclosure magazine /97♂G issue 2~/! page(
RD-/7 (7, 27).

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 !-pyrazolone couplers, pyrazolopenzimidazole couplers, cyanoacetylcoumaron couplers, and open-chain acylacetonitrile). Yellow couplers such as acylacetamide couplers (for example, benzoylacetanilides, pivaloylacetanilides), etc., and cyanogen couplers such as naphthol couplers, phenol couplers, etc. can be used.

These couplers are desirably non-diffusible and have a hydrophilic group called a ballast group in their molecules, or are polymerized. The coupler may be either 4- 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 cufffree).

In addition, by photosensitive silver dye bleaching method, dyes that form color images,
For example, Research Disclosure magazine/Deaf Otsu Year Monthly Issue 3θ~32 pages (RD-/tag 33), the same magazine/Wa7≦2017 issue/Da~/Tapage (RD-/j227)
, U.S. Patent Gu, 23! , U.S. Patent No. J, 91''!, JTJ No. 4T, etc.
, 022,477, may also be used as imaging materials.

Also, Research Disclosure Magazine/WA7R! Monthly issue J
'G~J'! Dyes into which a nitrogen-containing heterocyclic group is introduced, as described on page RD-/4, can also be used as image-forming substances.

Furthermore, European Patent No. 79. Q! No. 6, West German Patent No. 3゜co/7
．． ♂! 3, European Patent No. 7. Get it! A dye-donating substance 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 the European Patent No. 74, 4g92, West German Patent No. 3, 2. /! ,
'1rJ-, European Patent No. 66.2♂ko, special request!
A redox reaction is carried out with silver halide or organic silver salt at high temperatures as described in ♂-, 2F9.2r, and r-, y, toor, and as a result, all mobile dyes are released. Dye-providing materials can be used as all-imaging materials.

The above dye-donating substance preferably has the following general formula (1):
It is expressed as

(Dye-X) -Y (1) DYe is a dye that becomes mobile when released from the molecule, and preferably has a hydrophilic base. Available dyes include azo dyes, azomethine dyes, anthraquinone dyes, naphthoquinone dyes, styryl dyes, nitro dyes, quinoline dyes, carbonyl dyes, and 7-talocyanine dyes. It is also possible to temporarily shorten the wavelength and use it as a T-type.

Specifically, the dyes described in European Patent Publication No. 76, μ Octopus can be used.

X is Rinnaru combination or consolidated fund, for example -NF
-(R is a hydrogen atom, an alkyl group or a substituted alkyl group) group, -802- group, (2) -CQ
- group, alkylene group, substituted alkylene group, phenylene group, a-substituted phenylene group, naphthylene group, substituted naphthylene group, -0- group, -5O- group, and groups formed by combining two or more of these groups.

Y corresponds to the photosensitive silver salt that forms a latent image in the form of an image, and inversely releases Dye, and the released dye and Dye-X-
Y is a base aragonite that contains properties that cause a difference in diffusivity between the compound and the abrasive compound. General formula (1
) is a specific example of the dye-donating substance represented by (3)? Examples of kimono friends described in No. 2 include the following.

C4Hg(t) H H H H 0C16H33-n OH (11) □H OH ]Cx5H [33 (IQ OH OCH2COOH) The light-sensitive material of the present invention, preferably silver chloride, is spectral sensitized by methine dyes or the like. It is desirable that the

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. Any of the nuclei commonly used for cyanine dyes can be used as the basic heterocyclic nucleus for these dyes. That is, pyrroline nucleus, oxazoline nucleus, thiazoline nucleus, virol 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 Nuclei, quinoline nuclei, etc. can be applied.

These nuclei may be substituted on carbon atoms.

Merocyanine dyes or composite merocyanine dyes contain pyrazoline-! as a core having a ketomethylene structure. -one nucleus, thiohydantoin nucleus, 2-thioxazolidine-2
, 4t-dione nucleus, thiazolidine-, 2, goudion nucleus, rhodanine nucleus, thiobarbic acid nucleus, etc.! ~g-membered heteroartic ring nuclei 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.

A typical example is U.S. Patent No. 2.47/, j@J-, 2
1ri 77.22ri No. 3.3ri 7.0gO No. 1ri J'
, j22. Ojλ issue, same? , J-27, Ig/issue, same 3. t/7. ．． 2ri No. 3, 3.1 < 21. Taigu, same 3. Gott, tro issue, same 3. The 2nd one.

♂ri No. 2, same 3. Otsu 72, 4t2♂ issue, 3.70!
, No. 377, No. 3, 76, No. 3θ/, No. 31r/4t
, No. 40, same j, 737, J' Otsuko, same t
it, okotsu, No. 707, British Patent/13 Google, 2//
No., same/, J-07,203, special public Shoda 3-Geta No. 34, same! 3-/ko, 37! No., Tokukai Akira! Two/10
．． Otsu // issue, same! Ko70ri, octopus! listed in the number.

Along with the sensitizing dye, it is a dye that itself does not have a spectral sensitizing effect or a substance that does not substantially absorb visible light,
A substance exhibiting supersensitization may also be included in the emulsion. for example,
Aminostyryl compounds substituted with nitrogen-containing heterocyclic groups (
For example, US Patent Co.

33,3de0, tJj-, 72/), aromatic organic acid formaldehyde condensates (for example, those described in U.S. Patent J, 7'13.610)
, cadmium salts, azaindene compounds, etc. U.S. Patent J, T/J, T/3, 3. Otsu/j, No. 77, 3. t/7゜kota! No., same J, tJj,
The combinations described in No. 72/ are particularly useful.

The maximum spectral sensitization resulting from the above-described spectral sensitization must 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 or a multilayer color light-sensitive material has a plurality of spectral sensitization regions, the spectral sensitization regions of each layer may overlap as the spectral sensitization region becomes longer wavelength as described above. arise. 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.

Particularly preferred Example 2II in the present invention! Embodiment i is one in which silver halide and an organic silver salt coexist; When heated to 0° C. or higher, preferably 10θ0° C. or higher, it reacts with the image forming substance or, if necessary, a reducing agent coexisting with the image forming substance 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 bromide, silver chloroiodide, silver bromide, silver iodobromide, silver chloroiodobromide, and silver iodide can be used.

Two or more types of the above-mentioned 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 0.007 μm to 70 μm, more preferably from 0.00/μm to J μm.

The silver halide used in the present invention may be used as it is, but it may also be treated with chemical sensitizers such as compounds such as sulfur, selenium, tellurium, etc., gold, platinum, palladium, rhodium, iridium, etc. Chemical sensitization may also be achieved by the use of reducing agents such as tin chloride and the like or combinations thereof. For more information, see l”The theo
ry of the Photographic
Process” Z edition, written by T, H1 James, chapter !, pages /data to /d9.

In the present invention, the coating amount of photosensitive silver halide is suitably from /mg to /Og/m2 in terms of silver.

An example of the above-mentioned organic silver salt oxidizing agent is JP-A-Sho. -jrj
There are seven examples listed in No. 'lj, and the following are seven examples.

Silver salts of organic compounds having a carboxy 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, the special public Shogu G-3022θ, the same! -/,! 76
Silver salts of benzotriazole and its derivatives described in the publication, such as benzo) Silver salts of alkyl-substituted benzotriazoles such as silver salts of IJ azole and silver salts of methylbenzotriazole,! - silver salts of halogen-substituted benzotriazoles, such as silver salts of chlorobenzotriazole, carbimidobenzos, such as silver salts of butylcarboimidobenzotriazole), silver salts of IJ azoles, US Pat.

Silver salts of monotriazole and /-H-tetrazole, silver salts of carbazole, silver salts of tetucarin, silver salts of imidazole and imidazole fat conductors, and the like include silver salts of 7,2.4 described in 20.702.

Further, organometallic salts such as silver salts and copper stearate described in Research Disclosure No. 770/702 are also organometallic salt oxidizing agents that can be used in the present invention.

For details on how to make these silver halides and organic silver salts, and how to mix both, please refer to Research Disclosure 7.
7θ No./7θ Kota and Tokukai Sho! 0-32927. Tokukai Showa J-7-4t! 2wa, JP-A-Sho Geter/322g, JP-A-10-77.2/≦, US Patent 3,700.4t6♂
listed in the number.

In the present invention, the total amount of photosensitive silver halide and organic silver salt coated in terms of silver is suitably from Omg to /θ/m2.

Examples of the reducing agent coexisting with the above-mentioned image forming substance include hydroquinone compounds (e.g., hydroquinone, co-, j-dichlorohydroquinone, co-chlorohydroquinone),
Aminophenol compounds (e.g. gu-aminophenol, N-methylaminephenol, 3-methyl-der-aminophenol, 3,z-c-y'romoaminophenol), catechol compounds (e.g. catechol, gu-cyclohexylcatechol, 3-methoxycatechol, g
(N-octadecylamino)catechol), phenylenediamine compounds (e.g. N,N-diethyl-p-72-2-diamine, 3-methyl-N,N-diethyl-
p-phenylenediamine, J-methoxy-N-ethyl-
N-ethoxy-p-)unilene diamine, N, N, N'
, N'-tetramethyl-p-phenylenediamine),
3-pyrazolidone compounds (e.g. /-phenyl-3-hyrazolidone, /-phenyl-<t, q-dimethyl-j-
Hyrazolidone, goohydroxymethyl-goomethyl-/
-phenyl-3-pyrazolidone, /-m-to1j-3
-pyrazolidone, /-p-)dyl-3-pyrazolidone, /-phenyl-gumethyl-3-pyrazolidone, /
-Phenyl-! -Methyl-3-pyrazolidone, /-Phenyluk, Coubis-(hydroxymethyl)-3-pyrazolidone, /, Coudi-methyl-3-pyrazolidone, Goomethyl-3-pyrazolidone, Ri, 4t-dimethyl-3
-pyrazolidore, /-(j-chlorophenyl)-4-y
'f-3-pyrazolidone, /-(4t-chlorophenyl)-gumethyl-3-pyrazolidone, /-(4t-)
t-(4t-
tolyl)-3-pyrazolidone, /-(3-tolyl)-3
-pyrazolidone, /-(j-tolyl)-y, a-dimethyl-3-pyrazolidone, /-(,2-trifluoroethyl)=X, 4t-dimethyl-3-pyrazolidone,! -methyl-3-pyrazolidone).

The amount of the above reducing agent added is 0°Q/~ per mole of silver.
20 mol, particularly preferably 0.1 to 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 one that is oxidized by silver halide, and its oxidized product has the ability to oxidize the reducing substrate in the dye-donating substance.

Useful auxiliary developers include hydroquinone, alkyl-substituted hydroquinones such as t-butylhydroquinone, λ,j-dimethylhydroquinone, catechol L? "Logarols, rhodane-substituted hydroquinones such as chlorohydroquinone and dichlorohydroquinone, alkoxy-substituted hydroquinones such as methoxyhydroquinone, and polyhydroxybenzene derivatives such as methylhydroxynaphthalene.Furthermore, methyl gallate, ascorbic acid, and ascorbic acid. Acid conductors, N,N'-di(2-ethoxyethyl)hydroxylamine natohydroxylamines, /-phenyl-3-pyrazolidone,
Goomethyl-goohydroxymethyl-/-phenyl-3
- Pyrazolidones such as pyrazolidone, reductones,
Hydroxytetronic acids are useful.

In the present invention, the imaging material is described in US Patent λ.

They can be introduced into the layers of the photosensitive material by known methods such as the method described in J22.027. 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), benzoic acid esters (octyl benzoate),
Alkylamides (e.g. diethyl laurylamide), fatty acid esters (e.g. dibutoxyethyl succinate, dioctyl azelate), trimesic acid esters (e.g. dibutoxyethyl succinate, dioctyl azelate),
High boiling point organic solvents such as tributyl trimesate), or organic solvents with a boiling point of about 30°C to 100°C, such as lower alkyl acetates such as ethyl acetate, butyl acetate, ethyl propionate, secondary butyl alcohol, methyl isobutyl ketone, After being dissolved in β-ethoxyethyl acetate, methylselonorp acetate, cyclohexanone, etc., it is dispersed in a hydrophilic colloid.

The above-mentioned high boiling point organic solvent and low boiling point organic solvent may be mixed and used.

Tokko Akira again! /-39♂! No. 3, Tokukai Akira! /-! The dispersion method using a polymer described in Tag No. 3 can also be used. Also, when dispersing an image forming substance in a hydrophilic colloid,
A variety of surfactants can be used, including those listed as surfactants elsewhere in this specification.

The amount of the high-boiling organic solvent used in the present invention is 10 g or less, preferably 1 g or less, based on the image forming substance used/g.

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 photosensitive material or the dye fixing material described below. 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, co- or tertiary phosphates, borates, carbonates, quinolates, metaborates, ammonium hydroxides, fluorinated alkyl ammonium hydroxide,
Examples include hydroxides of other metals. Preferred organic bases include aliphatic amines, aromatic amines, heterocyclic amines, amidines, cyclic amidines, guanidines, and cyclic guanidines, particularly pKa? The above are particularly useful in the present invention.

Base precursors include salts of organic acids and bases that decarboxylate and decompose when heated, compounds that decompose υ and release amines through reactions such as intramolecular nucleophilic substitution, Rossen rearrangement, and Peckman rearrangement. Preferably used are those that cause some kind of reaction and release a base. Preferred base precursors include British Patent No. Wata♂ and Wo4t.
9, etc., salt of tricloacetic acid, U.S. Patent No. 9, etc.
θOtsu0, the salt of α-sulfonylacetic acid described in '420, the salt of propiolic acids described in Japanese Patent Application Shota R-JJ, No. 700, and the salts of propiolic acids described in US Patent No. 9. OJ'r, the gocarboxycarboxamide derivative described in No. t9, a salt with a thermally decomposable acid using an alkali metal or alkaline earth metal in addition to an organic base as the base component (patent application Shozr-≦2.! No. 27), special request using Rossen rearrangement! ? -G3. Hydroxam carbamates described in No. ♂Bu No. 0, aldoxime carbamates described in Japanese Patent Application No. Sho J-r-3/4/4 which produce dinitrile upon heating, and the like. In addition, British patent No. 1 pig ♂, ri 4t! No., U.S. Patent No. 3.220゜296, JP-A-Sho! θ-22. t2J-, British Patent No. 2.029. The base precursors described in y:to, etc. are useful.

Specific examples of base precursors particularly useful in the present invention are shown below.

Guanidine trichloroacetate, methylguanidine trichloroacetate, potassium trichloroacetate, guanidine phenylsulfonylacetate, p-chlorophenylsulfonylacetate guanidine, p-methanesulfonylphenylsulfonylacetate quanidine, potassium phenylpropiolate, cesium phenylpropiolate, guanidine phenylpropiolate, p - Chlorophenylpropiol acid diguanidine 7, J + 'l V chloro, lophenylpropiol acid diguanidine, p-phenylene-pisugropiolate diguanidine, phenylsulfonylacetate tetramethylammonium, phenylpropiolate tetramethylammonium.

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, the seven examples include one in which a red-sensitive light-sensitive layer, a green-sensitive light-sensitive layer, and a 1V-sensitive light-sensitive layer are coated on a support in this order; 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 can have a multilayer structure of layer A or more, and
An intermediate layer or filter layer may be provided between each photosensitive layer. Further, a retention layer may be provided as the layer furthest from the support.

In addition, the spectral sensitivity characteristics and color image forming characteristics of each photosensitive layer of the photosensitive material are not limited to the above examples; for example, an infrared-sensitive photosensitive layer is a magenta image, a red-sensitive photosensitive layer is a cyan image, and a red-sensitive photosensitive layer is a cyan image. A combination in which a green-sensitive photosensitive layer forms a yellow image, or a combination in which a red-sensitive photosensitive layer forms a magenta image, a green-sensitive photosensitive layer forms a cyan image, and a blue-sensitive photosensitive layer forms a yellow image may be used. can. 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. It may be formed by coating a sensitive photosensitive layer, a red-sensitive photosensitive layer, and a green-sensitive photosensitive layer in this order.

One of the preferred embodiments of the light-sensitive material used in the present invention is to use silver halide spectrally sensitized with the above-mentioned spectral sensitizing dye as the light-sensitive substance, and to use the above-mentioned oxidation of the developer as the image-forming substance. A coupler that forms a dye by reacting with a silver halide or a dye-donating substance that releases a mobile dye by performing an oxidation-reduction reaction with silver halide or an organic silver salt at high temperature, preferably represented by the general formula (1). The compounds shown are used. When using a dye-donating substance that releases the above-mentioned mobile dye, the photosensitive dye is subjected to imagewise exposure, heated (thermally developed) to form an image, and then overlaid with a dye-fixing material to form the image. The image can be transferred to a dye-fixing 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 amine group, a polymer having a nitrogen-containing heterocyclic group, or a da-class cation group of these. Molecular weight of polymers etc! , θQ0~ko0θ, θθ0,
In particular, mordants in the range of /θ, ooo-to, ooo are 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 be used for this binder.

Typical examples of current aqueous binders include transparent or translucent hydrophilic binders, such as reeds, proteins such as gelatin, gelatin derivatives, and cellulose derivatives, natural substances such as starch, polysaccharides such as gum arabic, and polyvinylpyrrolidone. , synthetic polymeric materials such as water-soluble polyvinyl compounds such as acrylamide polymers. Other synthetic polymeric substances include dispersed vinyl compounds in the form of latexes, which increase the dimensional stability of photographic materials, among others.

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, U.S. Patent No. 3.30/47J'
- Isothiuroniums represented by hydroxyethylisothiuronium trichloroacetate, US Patent No. 3
．． 4≦, bis(intiuroniums such as /, ♂-(31g-dioxaoctane)bis(intiuronium trichloroacetate) described in No. 670, West German Patent No. 2
．． Thiol compounds disclosed in US Pat.

0/2. ．． 2-Amine-thiazolium trichloroacetate described in No. 2 No. 0, Coamino! - Thiazolium compounds such as bromoethyl-cortiazolium trichloroacetate, U.S. Patent No. G, 060.4t,
Compounds having α-sulfonylacetate as an acidic moiety, such as bis(2-amino-thiazolium)methylenebis(sulfonylacetate) and co-amino-cortiazolium phenylsulfonylacetate described in No. 20, U.S. Pat. θr? , ￥9 Compounds having a cocarboxylic/carboxyamide as the acidic moiety described in No. 2 are preferably used.

Further, azole thioethers and blocked azolinthione compounds described in Belgian Patent No. 7 O♂ and θ7/, US Patent No. 3. ♂93. Guaryl described in ♂J-9
/-Carbamyl-cochitrazoline-! -thione compounds, other U.S. patents 3゜♂3, No. 04t/3. ♂
Compounds described in Google, No. 7//, No. 3, No. 77.220 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, but also cellulose acetate film, cellulose ester film, polyvinyl acetal film, polystyrene film, polycarbonate film, polyethylene terephthalate film and related materials. containing film or resin materials. Paper supports laminated with polymers such as polyethylene can also be used. US Patent 3. ≦3g, θt, 3rd and 7th
Polyesters described in Koj, No. 070 are preferably used.

The photographic light-sensitive material and dye-fixing material of the present invention may contain an inorganic or organic hardening agent in the photographic emulsion layer or other binder layer. Examples include chromium salts (chromium alum, chromium acetate, etc.), aldehydes (formaldehyde, glyoxal, geltaraldehyde, etc.), N-methylol compounds (dimethylol urea, methylol dimethylhydantoin, etc.), dioxane derivatives (co,3-dihydroxydioxane, etc.) ), activated vinyl compound (/, J
, J--triacryloyl-hexahydro-3-triazine, /,3-vinylsulfonyl-coglobanol, etc.), active no-rogen compounds (,2,4t-dichloro-
6-hydroxy-5-)') azine), mucohalogen acids (such as mucochloric acid and mucophenoxychloric acid), and the like 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 a system in which the transfer aid is externally supplied, water or a basic aqueous solution containing caustic acid, caustic potash, or inorganic alkali gold F'h salt is used as the dye transfer aid. Also,
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 in such a way that the image-receiving layer is wetted with the transfer aid.

If the transfer aid is incorporated into the light-sensitive 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 dyes, antihalation and irradiation dyes, hardening materials, European patent 2g for mordants etc.

41.9λ No., same≦Goko/No. 2, West German patent,! , 3/!
.

Gu♂! No. Tokugan Shota? -2792♂, same type♂-2t0
Those described in No. 0r 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, U.S. Pat. ! Octopus, 2yo No. 0, same j, 20/.

3/3 No. J, J[7, No. 77J, No. 3. Guda 7
．． No. 9J7, the internal image silver halide emulsion described in U.S. Pat. ? Mixtures of surface image silver halide emulsions and internal image silver halide emulsions as described in No. 3/2 can be used.

The heating temperature in the heat development process is approximately 70°C or higher and 2!0°C.
It can be developed at a temperature of about //θ℃ to about /d00 (:
is useful. The heating temperature in the transfer process can be in the range from the temperature in the heat development process to room temperature, but in particular, it is about 0°C or higher and about 70°C higher than the temperature in the heat development process.
A temperature range lower than or equal to C is more preferable.

The heating means in the heat development process is a cylinder passed between hot plates,
Heating by contacting with a hot plate (for example, JP-A-Sho! 0-J, 243
J), heating by contacting a heated drum or heat roller while rotating (e.g., JP-A No. 3-/θ7-7), heating by passing through hot air (e.g., JP-A-3-3273)
7), heating by passing through an inert liquid kept at a constant temperature, heating by passing it along a heat source with a lawn, belt, or guide member (for example,
t4t-23-'It) etc. can be used.

Alternatively, a layer of conductive material such as graphite, carbon black, or metal may be applied to the heat-developable photosensitive material, and an electric current may be passed through the conductive layer to heat it directly (for example, as described in JP-A Akihiro). ?-ot4t<ta).

The heating means in the transfer step can also be the same as in the heat development step described above.

As the light emitting diode of the light source used in the present invention, G
aAsP (red), GaP (red, green), GaAsP:N
(red, yellow), GaAs (infrared), GaAlAs (infrared, red), GaP:N (red, green, yellow), GaAa
Various materials can be used, such as iS i (infrared), GaN (blue), and 5iC (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 phosphor, a phosphor activated with a rare earth element is preferably used, and the rare earth element is E r
3+, Tma+, Yba+, etc. can be used.

Image exposure of the photosensitive material of the present invention is performed by scanning exposure using a light emitting diode. In this case, as a scanning method, for example, the method disclosed in Japanese Unexamined Patent Application Publication No. 7-7-7 filed by the present applicant is
! As described in No. 733 or Japanese Patent Application No. 7-22TJJJ, 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. In this method, as is known in the so-called scanner, a photosensitive material is wound around a drum and the drum is rotated, and a light source is provided or the light from the light source is guided through an optical fiber or the like. A method of scanning by moving a head in the direction of the rotation axis of the drum can be used.

Example/Silver chlorobromide emulsion/Q02 (containing gelatin!t1 silver 10P) prepared by a conventional method was prepared with the following structural formula/~6
A metalul solution of a spectral sensitizing dye (0.00 J%
) (in the case of /~Hiro) or methylseronlupe solution (0,0
0J-%) (for t and a) was added, and after adding an anti-capri agent, a hardening agent, a coating aid, etc. by a conventional method, the mixture was coated on a polyethylene terephthalate support.
The amount of υ silver applied per 2 hits! ? Apply the photosensitive material A so that
-I made F. This light-sensitive material was subjected to image exposure using a scanning type exposure apparatus similar to that described in JP-A No. 1987-11-133, and then 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 Fig. 1, the light emitting diode PG is made of GaP, and the input current value ♂
The luminescence characteristic at 0 mA, PR is made of GaAlAs, and the luminescence characteristic at input current value ♂OmA, P
IR is made of GaAlAs, and the input current value J'Om
The luminescence characteristics in A are shown.

FIG. 1 is a diagram showing the spectral sensitization characteristics of light-sensitive materials A to F that were spectrally sensitized using spectral sensitizing dyes A to O.

Structural formula of the spectral sensitizing dye %Formula %Sensitive material B (using spectral sensitizing dye), in which the maximum spectral sensitivity of the photosensitive layer is set on the longer wavelength side than the fluctuation range of the emission spectrum of the light source; (using spectral sensitizing dye 6), and photosensitive material F (using spectral sensitizing dye 6).
Light-sensitive material A (using spectral sensitizing dye),
Compared to Photosensitive Material C (using spectral sensitizing dye 3) and Photosensitive Material E (using spectral sensitizing dye!), the image had less unevenness.

EXAMPLE A spectrally sensitized light-sensitive silver halide emulsion λ02 prepared by the same method as in Example 1 was used in JP-A-Sho! TarrJ/J
Benzotriazole silver emulsion 20 made by the method described in No. 4? and an image-forming substance dispersion made by the method below! 31 as shown in the table below, and 10 cc of an aqueous solution of guanidine trichloroacetic acid and dimethylsulfonamide! After adding 10 cc of aqueous solution,
The photosensitive material GL was prepared by coating it on a polyethylene terephthalate-1 support.

Preparation of image-forming substance dispersion (1) Image-forming substance (7) was mixed with succinic acid-λ-ethylhexyl ester sulfone Wi17 1"0,' gs
tricresyl phosphini) ' g % vinegar e 30 mt of ether was heated and dissolved / θ wt % gelatin aqueous solution io
omt and stir to disperse.

Preparation of image-forming substance dispersion (2) Image-forming substance dispersion (2) was prepared in the same manner as image-forming substance (1), except that 1 g of image-forming substance (8) 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 2.1 g of image-forming substance (9) was used.

G/(t70nm) (1)H,2(
r, rtnm) (1) I j<≦70
nm) (2) J da (core 9tnm)
(2) Kt(7, rJ-nm)
(3) L 6 (r/θn m ) (3
) For the above photosensitive material GL, JP-A-Sho! 7-/J-/
A scanning exposure apparatus similar to that described in No. 933 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, the above-exposed photosensitive material GL is heated to about /lθ0C and developed, and the image is transferred to the dye-fixing material by superimposing it on the image-receiving material prepared by the method described below.The photosensitive material and the dye-fixing material are then separated. It was peeled off to obtain an image on the dye-fixing material.

Preparation of dye fixing material Poly(methyl acrylate-NXN, N-trimethyl-N-vinylbenzylammonium chloride) (ratio of methyl acrylate and vinylbenzylammonium chloride is /:/) Dissolve 70 g in θOmL of water,
Mixed with 100 g of 0% 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 H (using a spectral sensitizing dye) in which the spectral sensitivity of the photosensitive layer is set to the longer wavelength side than the fluctuation range of the emission spectrum of the light source, Photosensitive material J (using a spectral sensitizing dye), Images obtained using Photosensitive Material L (using ultra-thick spectral sensitivity) are obtained using Photosensitive Material G (using spectral sensitizing dye/) and Photosensitive Material Processing (using spectral sensitizing dye 3), respectively. ), Photosensitive material K (using spectral sensitizing dye J)
The images were clearer and less uneven than those obtained using the .

Example 3 Photosensitive materials M and N were prepared by coating the same photosensitive layers as those used in Example C in multiple layers as described below.

1 3 2 (trtnm) / The above-mentioned photosensitive materials M and N were exposed to light in the same manner as in Example C, and after heat development, they were transferred to a dye-fixing material to obtain an image.

The images obtained using photosensitive material N were more uniform and showed less change in color balance than the images obtained using photosensitive material M.

〔Effect of the invention〕

By using the method of the present invention, changes in the amount of light and wavelength given to a photosensitive material when exposing the photosensitive material using a light source whose emission intensity and emission spectrum maximum wavelength change depending on temperature, and the spectral sensitivity of the photosensitive material can be realized. Since they cancel each other out, it is possible to prevent fluctuations in image density and disruption of color balance.

[Brief explanation of drawings]

FIG. 7 is a diagram showing an example of the light emitting characteristics of the 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. PER...Emission characteristics of GaAlAs light emitting diode PR...Emission characteristics of GaAlAs light emitting diode PG...Emission characteristics of GaP light emitting diode/...Green-sensitive photosensitive layer Spectral sensitivity characteristics (comparison)
λ... Spectral sensitivity characteristics of green-sensitive photosensitive layer (present invention) 3... Spectral sensitivity characteristics of red-sensitive photosensitive layer (comparison) ta... Spectral sensitivity of red-sensitive photosensitive layer Sensitivity characteristics (present invention)! ...... Spectral sensitivity characteristics of infrared-sensitive photosensitive layer (comparison) 6 ...... Spectral sensitivity characteristics of infrared-sensitive photosensitive layer (present invention)

Claims (2)

[Claims] (1) In a method of exposing a photosensitive material to form an image using a light source whose emission intensity and emission spectrum maximum wavelength vary depending on temperature, the maximum of the spectral sensitivity distribution of the photosensitive material is set to the emission spectrum maximum wavelength of the light source. A method for forming an image, characterized in that the photosensitive material is exposed to light at a wavelength longer than the variable region. (2) The image forming method as described in item 1 above, wherein the light source is a light emitting diode.