JPS63113534A - Image forming method - Google Patents

Abstract

PURPOSE:To permit formation of an image on a silver halide photographic sensitive material which has high sensitivity, is stable and has a good preservable property by using a light source combined with a semiconductor laser and wavelength conversion element consisting of a nonlinear optical element as a light source for exposing. CONSTITUTION:The silver halide photographic sensitive material subjected to spectral sensitization in a visible region is exposed by using the light source combined with the semiconductor laser and the wavelength conversion element consisting of the nonlinear optical material. The nonlinear optical material is a material which can develop the nonlinearity-nonlinear optical effect between polarization and electric field appearing when a strong optoelectric field such as laser light is applied thereto. The example of such material includes inorg. compds. as represented by lithium niobate, potassium dihydrogenphosphate, potassium iodate, and BaB2O4. The constitution of the light source for exposing which is smaller in size and shorter in wavelength is permitted by combining the semiconductor laser and the wavelength conversion element consisting of the nonlinear optical material in the above-mentioned manner. The silver halide photographic sensitive material to be used is formable as a material having the high stability sensible to the visible region.

Description

[Detailed description of the invention]

"Industrial Application Field" The present invention relates to an image forming method using a silver halide photographic light-sensitive material, and relates to a miniaturized and short-wavelength light source in an image forming method using a so-called scanner method. . ``Prior art'' One of the exposure methods for photographic light-sensitive materials is to scan an original image, and perform two exposures on the silver halide photographic light-sensitive material based on the image signal to create a negative or positive image corresponding to the image on the original image. An image forming method using a so-called scanner is known. There are various recording apparatuses that utilize a scanner-based image forming method, and glow lamps, xenon lamps, mercury lamps, tungsten lamps, light-emitting diodes, and the like have conventionally been used as recording light sources for these scanner-type recording apparatuses. However, all of these light sources had the practical drawback of low output (short lifespan).To compensate for these drawbacks, Ne-NeL/-zer, Argo 7L/-zer, [-1e- There are scanners that use a coherent laser light source, such as a Cd laser, as a one-side light source.These can provide high output, but they have drawbacks such as large size, low profile, and the need for a modulator. On the other hand, semiconductor lasers are small, inexpensive, easy to modulate, and have a longer lifespan than the lasers mentioned above.However, semiconductor lasers have high sensitivity in the infrared region and excellent storage stability. It is not easy to produce photosensitive materials (commercially available infrared sensitized films include Eastman Kodak's [-]
, ] E/3j-20, and its catalog 9'C instructs to store photosensitive materials refrigerated or frozen. As can be seen from this, the sensitivity of infrared-sensitized photosensitive materials is unstable, and special consideration is required for storage. Therefore, it has not been possible to take full advantage of the characteristics of the semiconductor laser, which has excellent performance as described above. Therefore, it is desired to develop a method of forming images by exposing a silver halogenide photographic material which is spectrally sensitized in the visible region and has good storage stability while retaining the advantages of a semiconductor laser. ``Problems to be Solved by the Invention'' That is, the object of the present invention is to provide a silver halide photographic material that is spectrally sensitized in the visible region, which is highly sensitive, stable, and has a good shelf life. An object of the present invention is to provide a method of forming an image by applying exposure from a light source using a light source. "Means for Solving the Problems" The present inventors have achieved the above object by spectrally sensitizing the visible region using a light source that combines a semiconductor laser and a wavelength conversion element made of a nonlinear optical material. - We have discovered that this can be achieved by an image forming method that exposes a silver halide photographic material, and have completed the present invention. A wavelength conversion element made of a nonlinear optical material used in the present invention will be explained. Nonlinear optical materials are materials that can exhibit nonlinearity between polarization and electric field (nonlinear optical effect) that appears when a strong optical electric field such as that of a laser beam is applied. Potassium hydrogen (
KDP) Lithium iodate, inorganic compounds such as BaB2O4, urea derivatives and nitroaniline derivatives (fflJ, tJ-methyl-≠-nitroani!Jy(
MNA), J-N, N-dimethylamino-y-nitroacetanilide (DAN), metanitroaniline, L-N
-(e-nitrophenyl)--2-(hydroxymethyl)pyrrolidine and %*m Showj/-j! ≠ 6λ, Japanese Patent Application No. 4/-JJIr-Hiroshi, Japanese Patent Application No. 1999-2 Tata Tata], nitropyridine-N-oxide derivatives (e.g., 3-methyl-Hiroshi-nitropyridine-7
-oxide (POM), etc.), diacetylene derivatives (such as the compounds described in JP-A-56-μ32-0),
Furthermore, JP-A-4/-40631, JP-A-J/-7171
AI No. 1) [No. 1526μ7, JP Shoj/-
Compounds described in JP-A/37/36, JP-A/-/μ 7231, JP-A-A/-/μ KO 33, JP-A 61-/67, 3Q, and “Nonliner Optical
Properties of Organica
nd Polymeric Materials″AC
8SYMPO8IUM 5ERTES 233,
D3vidJ - Will i ams (Ame
rican Chemical Society, IT
3rd edition), ``Organic Nonlinear Optical Materials'', supervised by Masao Kato and He Nakanishi Department (CM7-sha, /Yrj, 2013). Organic compounds such as the compounds described in are known. Regarding the present invention, among these materials, those with high blue light transmittance, such as KDP, lithium iodate, lithium niobate, BaB2O4, urea, POM, and
Compounds described in No./-43μ6.2 and Japanese Patent Application No. Shoj/-j31117 are preferred, and organic compounds of POM or less are more preferred. The nonlinear optical effect 1c includes second-order effects such as co-harmonic generation, pre-mixing 1. There are R-lamometric oscillations, pre-rectification, Pockels effect, etc., and third-order effects include third harmonic generation,
These include the Kerr effect, optical bistability, and prior mixing, as well as higher-order effects. In the present invention, the purpose of using a nonlinear optical material is to convert the light of a semiconductor laser with a wavelength in the infrared region to a wavelength in the visible region. , pre-mixing 1. Two e-rametrifus oscillations and third harmonic generation are important. The wavelength conversion element using a semiconductor laser and a nonlinear optical material used in the present invention can be a single crystal optical waveguide type,
Fiber type etc. are known. As for the optical waveguide type, JP-A-61-/≠2,2gμ, JP-A-Sho! 2-10r, No. 779, % Kaisho 52-l Ko! ,
Planographic waveguide-like thing described in No. 214, JP-A-70-/
≠Iko λλ No., JP-A-60-17゜121, JP-A-Sho 1
．． 0-//2,023; There is a chip-shaped waveguide described in JJIA. As a fiber type, there is one that satisfies the phase matching condition of an incident laser wave and a converted laser wave as described in Japanese Patent Application Laid-open No. Sho J7-2/i, i2s. Silver halide photographic materials that can be used in the present invention include various color and black and white photographic materials. can be mentioned. For example, color negative film for photography (general use, movie use, etc.)
, color reversal film (for slides, movies, etc., and may or may not contain couplers), color photographic paper, color positive film (for movies, etc.), color reversal photographic paper, M developing power 2-photosensitive material, Color photosensitive materials using the silver dye bleaching method, photosensitive materials for plate making (lith film,
scanner film, etc.), X-ray photosensitive material #+ (direct/indirect medical use, industrial use, etc.), black and white negative film for photography,
Examples include black and white photographic paper, microphotosensitive materials (for COM, microfilm, etc.), color diffusion transfer photosensitive materials (DTRJ, daughter salt diffusion transfer photosensitive materials, printout photosensitive materials, etc.) Silver halide used in the present invention Photographic processing of light-sensitive materialsvcV
Any known method can be used for 'i' and any known method can be used for treatment liquid vc. Further, the processing temperature is usually selected between /♂0C and jOoC, but it may be lower than l♂0C or higher than 500C. Depending on the purpose, development processing (
Either a black and white photographic process or a color photographic process consisting of a development process to form a dye image can be applied. For details regarding the development processing method, see Research Disclosure 7f No. 6, pages 2f to %JO (1'(l)
-/7A 4LJ) (Dec, /7f). These silver halide photographic materials may have a single photosensitive layer or a plurality of photosensitive layers, and in the case of a plurality of photosensitive layers, the spectral sensitivity distributions of these layers may be the same or different. In the case of the silver halide photographic material used in the present invention,
Spectral sensitization is possible from the blue region to the infrared region, but for example, u! Around OQm, j! Examples of spectral sensitizing dyes capable of spectrally sensitizing wavelengths around Onm and around tronm are listed below. A, ≠so, spectral sensitization around mA-ko02out-j-A

[(CH2J4S03(CH2J4SO3H small(C2Hs
)3A-4 SO3H-N(C2H5) 3 A-tar-l0 8O3H-N(CzHs) a B,! ! C2H5 (CH
2-3SO3- n-C7Hxs B' c,,E(,. ,'-7 C-t C-10 CF(2CF2CF2F((CH2)4803C-/
The dyes used for these spectral sensitizations are F, M
, Hamer, "Heterocyclic Compounds - Cyanine Dyes and Related Compounds", John Wiley & Punns (New York, 77172, 1994, A4A Annual). Also, these spectral sensitizing dyes are - silver halide. Per 1 mole, usually /x10 mole to jx0-3 mole, preferably /x/Q mole to λ, jX10-" mole, preferably dax10 mole to /X10 mole... In the present invention, the dye compounds used can be directly dispersed in the silver halide emulsion.Also, they are first dispersed in a suitable solvent such as methyl alcohol, ethyl alcohol, methyl cellosol, water, etc. It can also be added in the form of #j liquid by being dissolved in , pyridine, or a mixed solvent of these. It can also be added using the following method. That is, using ultrasonic waves for dissolution. Also, the method of adding this dye compound is described in US Pat. No. 3. Hiroshi 62.
A method of dissolving a dye compound in a volatile organic solvent, dispersing the solution in a hydrophilic colloid, and adding this dispersion to an emulsion, as described in Japanese Patent Publication No. 7, etc., published by Tokko Sho! 4
A method of dispersing a water-insoluble dye compound in a water-bathable solvent without dissolving it and adding this dispersion to an emulsion, as described in U.S. Pat.
．． /31@Details@VCDescriptionOfuna, a method of dissolving a dye compound in a surfactant and adding the I@liquid to an emulsion, in which a dye compound as described in JP-A No. 5 O-rotλ is substantially dissolved. For example, a method is used in which the compound is bath-dissolved in a water-free acid and the solution is added to the emulsion. Other additions to emulsions include U.S. Patent No. λ. 12.3da No. 3, 3.3μλ, 406. 2.51A, Jr. 7, 1129
, f3, etc. may also be used. Further, in the present invention, two or more dye compounds may be added in a mixed state, or each may be added individually. They are for example U.S. Pat. No. 703.377, U.S. Pat. try, r≠j, U.S. Patent No. 3,377
．． No. 040, U.S. Patent No. J, A/j. No. tJj, U.S. Patent No. 3. t, 2r, ritμ, British Patent No./, 2μ2. sty No., British Patent No./. Kota 3. Irt No. 2, Special Publication Sho μ3-4L 3 No., Special Publication Akihirohiro-/μ030, Special Publication Sho μJ-10773, US Patent No.! , It/l, No. 7.27, Special Publication Show 1tJ-u
FJO No., US Patent $3. A/s, A73, US Patent No. 3. t/j, t3co, U.S. Patent No. J, 4/7. ．． 2
The sensitizing dyes described in Pj No. 3,633.72/U.S. The silver rogenide emulsion used in the present invention is usually prepared by combining a water-bathable silver salt (e.g. silver nitrate) solution and a water-bathable rogen salt (e.g. potassium bromide) solution in the presence of a water-soluble polymer solution such as gelatin. It is made by mixing. As the silver halide, in addition to silver chloride and silver bromide, mixed silver halides such as silver chlorobromide, silver iodobromide, silver chloroiodobromide, etc. can be used.・・・Average particle size of rogens particles (particle diameter for spherical or approximately spherical particles, particle diameter for cubic particles,
It is preferable that the particle size is long and the projected area (average surface area) is 4 μm or less. The particle size distribution may be narrow (so-called "monodisperse") or broad. The shape of these silver halide grains may be cubic, l≠hedron, rhombohedron, octahedron, mixed crystal forms thereof, or spherical, plate-like, etc. It is also possible to use an emulsion in which supertabular silver halide grains having a grain diameter of five times or more the grain diameter occupy 30% or more of the total projected area. For more details, please visit Tokukai Akira! r-/279
It is described in publications such as No. 2/No. Furthermore, four or more separately formed silver halide photographic emulsions may be mixed. Furthermore, even if the crystal structure of silver halogenide grains is similar to the inside, there are also those with a layered structure in which the inside and outside halogen compositions are different,
UK%I&Fi, 3! It may be of a so-called conversion type, as described in U.S. Pat. Further, either a type in which a latent image is mainly formed on the surface or an internal latent image type in which a latent image is formed inside the particle may be used. These photographic emulsions are from "The Theory of Photographic Process" by James, 1st edition published by Matsukubaransha (1976); by P. Grafkide, "The Theory of Photographic Process" ( Paul Montel & Co., 1767), G. F. Daaffin, 1 Photographic Emulsion Chemistry (Focal Press, 1766), V', L. Zelikmann et al., 1 Making and Coating Chemistry. "Photographic Emulsion" (published by Focal Press, /6μ) (Jamesl'-The Theoryo
f the Photographic Pro
cessJThe4'th edition, Mac
Millan (/ri76). P. Glafkides, “Chimie et.
PhysiquePhotography” (P
aul Montel, /ri A 7), G, F, D
uffin, “Photographic Emulsi
on Chemistry” (The Focal
Press, /riA 6), V, L, Zelikma
n etat, “Making and Coa
tingPhotographic Emulsio
n” (The FocalPress, /ri+4L)
), etc.). In other words, any of the acid method, neutral method, ammonia method, etc. may be used, and the method for reacting the soluble silver salt with the soluble halogen salt may be a one-sided mixing method, a simultaneous mixing method, or a combination thereof. You can. It is also possible to use a method in which particles are formed in an excess of silver ions (so-called back-mixing method). As one type of simultaneous mixing method, it is also possible to use a method in which the pAg in the liquid phase in which silver rognide is produced is kept constant, that is, the so-called Chondrord method or double jet method. According to this method, a silver halide emulsion with a regular crystal shape and a nearly uniform grain size can be obtained. Two or more separately formed silver halogenide emulsions may be mixed and used. As the silver halide emulsion, a so-called immature emulsion (P-IJ emulsion) which is not chemically sensitized can be used, but it is usually chemically sensitized. For chemical sensitization,
The above-mentioned works by Grafikde or Zerlikmann et al., or by H. Friesel, ed.
dlagender Photography
en Przessemit Silberha
logeniden"Akademische Ver.
The method described in lagsgesellschaft (/ritr) can be used. Ding, sulfur that can react with activated gelatin and silver? Sulfur sensitization method using compounds containing (e.g. thiosulfates, thioureas, mercapto compounds, rhodanines), reducing substances!
(e.g., stannous salts, amines, hydrazine derivatives, formamidine sulfinic acid, silane compounds), noble metal compounds (e.g., gold compounds, platinum,
A noble metal sensitization method using a complex salt of a metal of group 1 of the periodic table such as iridium or .xiradium can be carried out alone or in combination. Binders or protective colloids used in photosensitive materials include:
Although gelatin is advantageously used, other hydrophilic colloids can also be used. As the gelatin, lime-treated gelatin, acid-treated gelatin, gelatin derivatives, etc. can be used. Furthermore, various other additives can be used, such as color formers (e.g., yellow couplers, magenta couplers, cyan couplers, etc.), fluorescent brighteners (stilbene series, etc.), anti-capri agents, stabilizers (/ -Phenyl-yo-mercaptotetrazole, Hiro-hydroxya substitution (/, 3.
Ja, 7) tetraazaindene, etc.], desensitizers, hardeners (e.g. l,!,!-)lyacryloyl-hexahydro-S-)lyazine, 21 μm dichloro-6-hydroxy-3-triazine, etc.), Coating aids, antistatic agents, plasticizers, slip agents, matting agents, development accelerators, oils (e.g. phthalate alkyl esters, phosphate esters, etc.)
, mordants, ultraviolet absorbers, anti-fading agents (hydroquinone derivatives, etc.), color anti-fogging agents (hydroquinone conductor, etc.), anti-padding agents (lambda-thiazolylbenzidazoles, isothiazolones, etc.), etc. It will be done. Regarding these additives, specifically, Research Disclosure (RESEARCE(DTSCLO8tJRE)
) No. 774, pages 22-31 (RD-t7&4!s) (
])ec, /ri71), etc. can be used. The finished emulsion is coated onto a suitable support such as baryta paper, resin coated paper, synthetic paper, triacetate film, polyethylene terephthalate film, other plastic bases or glass plates. coatings, such as dip coats, air knife coats, curtain coats, or US Pat.
It can be made into a photographic light-sensitive material by coating by the above-mentioned polishing method including an extrusion coat using a hopper as described in Kota Hiroshi. "Effects of the Invention" According to the present invention, by combining a semiconductor laser and a wavelength conversion element made of a nonlinear optical material, a light source for exposure can be made smaller and have a shorter wavelength. As a result, it has become possible to use a highly stable material that is sensitive to visible light in the silver oxide photographic material used at the same time. "Example" Next, the present invention will be explained in further detail based on an example. However, the present invention is not limited to these examples. Example 1 A silver iodobromide gelatin emulsion (average size of silver halide grains of 06 μm) containing silver iodide of /, j mole was ripened by adding sodium thiosulfate and potassium chloroaurate. 3,3'-disulfopropyl-j,
After adding j'-dichloro-terethyl-oxacarbocyanine sodium salt, the spectral sensitized color chart A--2y21
In addition, a coating aid (sodium dodenlebenzenesulfonate), hard Jl.
1J (2.≠-dichloro6-hydroxy-5-)riazine) was added, coated on a cellulose triacetate support, and dried to obtain sample 1. Further, samples λ to μ and comparative sample A were obtained in the same manner using the sensitizing dyes shown in Table 7. Note that the sensitizing dyes are indicated by the symbols listed in the specific examples above. Next, the exposure device will be described. As a semiconductor racer, the launch wavelength is 30 nm. A device with an output μOmW was used, and a single crystal of β-B a B 204, which is a nonlinear optical material, was used as a wavelength conversion element. The wavelength-converted blue laser beam was scanned and exposed by a rotating polyhedron onto a sample moving in a direction perpendicular to the scanning direction. The amount of exposure was electrically controlled by the amount of light from a semiconductor laser. In addition, exposure of comparative sample A was performed with infrared light except for the wavelength conversion element, and in the case of sample G, a semiconductor laser with an oscillation wavelength of 7.3μ and an output of 30mW and the above wavelength conversion element were used. Red light was used. Next, use a PQ developer with the following composition to create 330C13! After developing for a second, fixing by the pass method, washing with water, and drying, the photographic properties (g and capri) f! -Measurements were made and the results shown in Table 1 were obtained. In this case, the sensitivity of sample-7 is set as 100, and the others are set as relative I.
It's me, C9. Also, samples and comparison samples! Adjusted to 0°CVc. Inside the air temperature chamber! Sensitivity changes over time after being left for a day and then exposed and developed! It was measured. Results 2 are shown in Table 1. From the results in developer composition Table 1, the method of the present invention is superior to the method using Comparative Sample A, which is sensitive to the infrared region, because it allows the use of a sensitive material with higher sensitivity and better stability. It can be seen that it is. Example 2 Silver halide grains were precipitated by the double jet method, and after physical ripening and desalting treatment, they were chemically ripened with fire to produce silver chloroiodobromide (bromine content 70 mol%, iodine content 001 mol%).
An emulsion was obtained. The average diameter of the rogenated button particles contained in this emulsion is 0. It was μ micron. This emulsion/Ky
0 tmol of silver halide was contained in VCO. This emulsion was weighed/Ky and after heating to ≠o'C, a methanol solution of a sensitizing dye was added as shown in Table 1, and a predetermined amount of an aqueous solution of sodium bromide was added thereto. Furthermore, l-hydroxy-3゜j-dichlorotriazine sodium salt/, OMmti water bath solution was added,
Furthermore, dodecylbenzenesulfonic acid sodium salt/,0
10 ml of aqueous solution was added and stirred. This completed emulsion was coated and dried on a cellulose triacetate film base to a dry film thickness of 5 microns to obtain light-sensitive material samples j to 7 and comparative sample B. Next, the exposure device will be described. As a semiconductor laser, the oscillation wavelength is 10! Onm, output/
jmW'Y was used, and as a wavelength conversion element, a fiber type n which was made by crystallizing 2-methyl-≠-nitroaniline, which is a nonlinear optical material, in a glass fiber was used. The wavelength-converted green laser beam was scanned and exposed onto the samples j to 7 moving in a direction perpendicular to the scanning direction using a rotating polyhedron. The amount of exposure was electrically controlled by the amount of light from a semiconductor laser. Comparative sample-B was exposed using a semiconductor laser with an oscillation wavelength of 7.
The experiment was conducted using infrared light using a device with rOnm and output of 20 mW without a wavelength conversion element. After exposure, the strips were developed using a developer having the composition shown below at 70C for ≠ minutes, stopped, and subjected to a fixing bath, and then washed with water to obtain strips with a predetermined black and white image. Comparative sample B Kihiro j0C 3
It was left for a day, then exposed and developed. Second result
Shown in the table. Developer formulation Metho/, 0.31
g anhydrous sodium sulfite 3, B hydroquinone tIIog anhydrous sodium carbonate /r, 7g potassium bromide
0°rtg citric acid
o, t♂9 potassium metabisulfite i,
sg Add water /1 2nd
It is clear from the table that the method of the present invention is an excellent method because a sensitive material with high sensitivity and good stability can be used by using comparative sample B that is sensitive to the infrared region. . Example 3 A third layer was placed on a paper support coated on both sides with polyethylene.
A multilayer color photographic paper having the layer structure shown in the table was produced. The coating solution was prepared as follows. First layer coating solution preparation Yellow coupler (a)/li, 7g and color image stabilizer (
b) Pi, ≠g, ethyl acetate, 270.2Ce working solvent (c)7. ';' Add and dissolve cc, and add this bath solution to IQ%
1 containing sodium totenlebenzenesulfonate ♂CC
It was emulsified and dispersed in 1 rscc of 0% gelatin water bath solution. -A silver chloride bromide emulsion (containing silver bromide ro, mole, Ag70.!il/?) contains the following blue-sensitive sensitizing dye per mole of silver! , 0x10 moles were prepared. The above emulsified dispersion and this emulsion were dissolved in a mixed bath to prepare a first layer coating solution having the composition shown in Table 3. Coating liquids for layers #2 to #7 were also prepared in the same manner as the coating liquid for the first layer. The gelatin hardening agent for each layer is l-oxy-3°! −
DichloroS-) riazine sodium salt was used. The following spectral sensitizing dyes were used in each layer. Blue-sensitive emulsion layer (6.0 x 10 mol per mol of halogen) 5
O3H-N(C2Hs)3 (0x10 mol per mol of silver halide)
and SO3 (C2H5) 3 (7.0×/θ mol per 1 mol of silver halide) Red-sensitive emulsion layer 1-13 CCH3 For the red-sensitive emulsion layer, the following compounds were added per 1 mol of silver halide. λ, A×10 mol was added. In addition, for the blue-sensitive emulsion layer, the green-sensitive emulsion layer, and the red-sensitive emulsion layer, /-(j-methylureidophenyl)-y-mercaptotetrazole was added to r, zxio mol, 7°7 per mol of silver chloride, respectively. ×10-'mol, λ,
jt x 10' mol was added. Furthermore, for the blue-sensitive emulsion layer and the green-sensitive emulsion layer, g-hydroxy-t-methyl-/+'+'a*7-
Citrazaindene, 1.0% per mole of silver halide, respectively. λ×10 moles, /, /×/θ moles were added. The following dyes were added to the emulsion layer to prevent irradiation. S Oa K S 03 K and +a) Yellow coupler (b) Color image stabilizer (C) Solvent (dJ Color mixture inhibitor (e) Magenta coupler (f) Color image stabilizer (g) Color image stabilizer H H ( l cyan coupler α (mJ color image stabilizer CH2cH2coocs H17 j:l:ta mixture (weight ratio) (n) polymer C0NE (C4H9(t) (0) solvent Next, we will discuss the exposure equipment. As a semiconductor laser, the excavation wavelength r3onm, /Qyoθ
TRI (below), which is a nonlinear optical material, is used as a wavelength conversion element. A fiber type element crystallized in glass fiber was used. The wavelength-converted, green, and red laser beams were used to expose a color photographic paper moving in a direction perpendicular to the scanning direction using a rotating polyhedron in an axillary scan direction. The exposure amount is
The light m of the semiconductor laser was electrically controlled. (Chemical structure of TRI) O2 Next, development processing was carried out according to the following development process. Color development 33°C 3 minutes 30 seconds Bleach constant i JJ°C/minute 30 seconds Color separation 0 seconds The color development fixing solution is shown below. <Color developer> BC water roornl 100
m1 r00rnl nitrilotriacetic acid・J Na 2. Oji 2.09
2. Ojp benzyl alcohol 1 ml
--Diethylene glycol / 0rrrl --
-Sodium sulfite 2. Q2. Og 2.0
ji hydroxylamino sulfate 3. Oh! , 09 3. O
Potassium 9 bromide /, 011 /, 09
/, 0g sodium carbonate 30/i 3
09 - Potassium picolinate -- 309N
-ethyl-N- (β-memensulfonamide ether)-3-methyl-hiro-aminoaniline sulfate j, og s, og
r, add og water (drink the amount on the right) 10100O10100O10
00rnlp H10,/r 10. /s The, Q
Bleach-fix solution〉 Water tA
oomt ammonium thiosulfate (70% solution) ijo sodium sulfite irg ethylenediaminetetraacetic acid iron acetate) ammonium yojg ethylenediaminetetraacetic acid disodium acetate Add 39 water (make it to the right) 1000mlpHt, 70 Below are the photographic results. Shown in the table. Table μ The results show that sufficient image density can be obtained even in the image forming method of the present invention. Example 4 A sample was prepared as follows. Don't stir/! Dispersion 70 containing 2 parts of behenic acid, 6 parts of methyl isobutyl ketone, 27 parts of toluene, and 60 parts of butane-λ-one kept at 0C
09, the materials were added in the following order at lj minute intervals: Butopal 3-F J (polyvinyl butyral resin, Monsando) at 7!9. /-methyl-/-pyrrolidone' to 7 L ethanol 9005 moles mercuric bromide wti-L ethanol 92 moles 20 g hydrobromic acid, 70 g Butopal B-76, 1 μ9 antioxidant, and 7 phthalazinone
Following the final addition of 6g0, the sensitizing dyes shown in Table 5 were added after stirring and forming for 1 minute. Coatings were applied to the polyester webs using a knife coater with an orifice set of 10 Oμ, and each was dried in a forced draft oven for μ minutes at o'C. A protective overcoat was then applied with a Kaif coater with orifice set 7jμ, and the coating was dried as described above. The overcoat bath liquid is polyvinyl acetate-polyvinyl chloride copolymer (Union Carbide VYN
S) 1 part and butane - coonta! It contained parts. In this way, samples g to 10 and comparative sample MC were obtained. Next, the exposure device will be described. As a semiconductor laser, oscillation wavelength ♂30nm, output 30
A waveguide type element in which a part of LiNbO3, which is a nonlinear optical material, was formed by proton diffusion was used as a wavelength conversion element. The wavelength-converted blue laser beam was scanned and exposed onto samples 1 to 10 moving in a direction perpendicular to the scanning direction using a rotating polyhedron. The amount of exposure is electrically controlled by the amount of light from the semiconductor laser.゛Comparative sample C was exposed to infrared light using the above-mentioned apparatus with the wavelength conversion element removed. Next, the exposed sample i/was placed between hot plates kept at -27°CK and processed for 20 seconds to obtain a sample with black and white images. A sample was also obtained by leaving it for 3 days under the condition of 3r0cro% RH and then exposing and developing it. The results of photographic properties are shown in Table 5. As shown in Table 5, the sample! It is clear that the method using ~io is superior to the conventional method using comparative sample C. Example 5 A method for preparing a benzotriazole silver emulsion will be described. 219g of gelatin and 13.2g of benzotriazole in water!
Dissolved in oOrrtl. This solution was stirred while maintaining the temperature at θ0C. A solution of silver nitrate/79 dissolved in 10 ml of water was added to this solution over 2 minutes. This benzotriazole silver emulsion QpH&X adjustment. Sedimentation was performed to remove excess salt. Then the pH was adjusted to t,
30 to obtain a benzotriazole silver emulsion with a yield of Ba o o g. Next, we will discuss how to make acetylene emulsion. Gelatin 219 and potassium acetylaminophenylpropiolate 26.79f7% were dissolved in 500ml. 4 times this solution! oOCvC was maintained and stirred. Add 2 m of silver nitrate/79 to 100 m of water to this solution.
and stirred for an additional 10 minutes. The pH of this emulsion was adjusted to 1.30 VC and centrifuged to obtain an acetylene silver emulsion with a yield of ≠OOg. I will tell you how to make the silver halide emulsion for the 5th and 7th layers. Water bath liquid AOO1rll containing sodium chloride and potassium bromide in a stirred aqueous gelatin solution (containing gelatin glass op and sodium chloride 3.!9 in water/000g and kept warm at 70C) and silver nitrate bath solution (
At the same time, 0.52 mol of silver nitrate dissolved in 100 ml of water was added at an equal flow rate over a period of 1 minute. In this way, a monodisperse cubic silver chlorobromide emulsion (50 mol % of bromine) with an average grain size of O, UO μm was prepared. After washing with water and desalting, jmg of sodium thiosulfate and 20 mgf of Hiro-Hydroxy-Ot-methyl-/,3.3a,7-titrazaindene were added, and chemical sensitization was performed using TOOC. Emulsion yield was toog. Next, I will explain how to make a silver halide emulsion for the third layer. Good (stirring aqueous gelatin solution (contains 20!9 gelatin and 3 g of sodium chloride in 1000 g of water, 7z0c)
AOOml of an aqueous solution containing sodium chloride and potassium bromide (vc kept warm) and a silver nitrate water bath solution (60ml of water)
At the same time, silver nitrate O,S tamole dissolved in 0 ml was added at an equal flow rate over ≠0 minutes. In this way, the average particle size is 0.3! A monodisperse cubic silver chlorobromide emulsion (bromine tθ mol %) of μm was prepared. After washing with water and desalting, sodium thiosulfate! ml and Hiro-hydroxy-6-methyl-/,3.3a,7-chitrazaindene λ0ml were added to perform chemical sensitization at to 0c. The yield of emulsion is too! It was 9. Next, how to make a gelatin dispersion of a dye-donating substance will be described. Yellow dye-donating substance (,A)! ji, as a surfactant, weigh 10 g of succinic acid-coether-hexyl ester sulfonic acid soda, 10 g of triisononyl phosphate, add 30 g of ethyl acetate, and make about to0
The mixture was heated and dissolved in c to form a homogeneous solution. After stirring and mixing this solution and 100 fl of a 70% solution of lime-treated gelatin, the mixture was heated to 10,000 fprr1 for 70 minutes using a homogenizer.
It was dispersed. This dispersion is called a yellow dye-providing substance dispersion. Using magenta dye-donating substance (B) and using tricresyl phosphate as a high boiling point bath medium at 7°sI! A magenta dye-providing substance dispersion v;5 was prepared in the same manner as described above except for v. In the same manner as the yellow dye dispersion, a cyan dye dispersion was prepared using the cyan dye-providing substance (C). Next, a method for preparing a dispersion of zinc hydroxide will be described. Zinc hydroxide/2. ! 9. As a dispersant, carboxymethyl cellulose/9 was added to 100 ml of tA% gelatin water bath solution and ground for 30 minutes using glass beads with an average particle size of 0.7 mrn. The glass beads were separated to obtain a dispersion of zinc hydroxide. With these, color photosensitive teeth (sample //) having a multilayer structure as shown in Table 6 were prepared. Similarly, samples /co~/≠ were prepared by changing the sensitizing dyes in Table 6 to the combinations shown in Table 7. Dye Donor Substance Dye Donor Substance OCl s H33 (n) Dye Donor Substance 0C1e H33G) Reducing Agent (E) Next, how to make the dye fixing element will be described. Gelatin & 39, mordant with the following structure /309 /300
The solution was dissolved in rnl water, coated with VC on a paper support laminated with polyethylene to a wet film thickness of μm, and then dried. (Mordant) 36 g of gelatin as a protective layer on top of this. λ-bis(vinylsulfonylacedoabado)ethane lA
, Og, guanidine picolinate/J! fi! 00m1
A dye-fixing element was prepared by applying a solution dissolved in water to a wet film thickness of 17 μm and drying. The following exposure apparatus will be described. As a semiconductor laser, the oscillation wavelength r30nm, 10! O
nm, and /300 nm, and a single crystal of β-BaB204, which is a nonlinear optical material, was used as a wavelength conversion element to serve as a light source for red, green, and blue light. Further, as the infrared light, the above-mentioned 130 nm semiconductor laser was used as a light source without using a wavelength conversion element. These light sources were placed on a rotating polyhedron and scanning exposure was carried out onto a photosensitive element (sample // to /4) moving in a direction perpendicular to the scanning direction.The exposure amount was controlled based on the light tvt of the semiconductor laser. 16 m 17 m 2 of water was supplied to the emulsion surface of the exposed light-sensitive element using a wire bar, and then the dye-fixing element and the film surface were superimposed so that they were in contact with each other.The temperature of the film that absorbed water was rt °
1. Using a heat roller adjusted to C.
2! After heating for a second, the dye-fixing element was peeled off from the photosensitive element, and clear yellow, magenta, and cyan images were obtained on the dye-fixing element. Maximum temperature of each color (Dmax)
Macbeth reflection of the minimum temperature (Dmin)! It was measured using an I-degree meter (RD-4/RI). The results obtained are shown in Table 7. From the results in Table 7, the method of the present invention and the conventional method procedure amendment

Claims (1)

[Claims] In a method of scanning an original image and exposing a silver halide photographic light-sensitive material based on the image signal to form an image corresponding to the original image, a wavelength conversion element consisting of a semiconductor laser and a nonlinear optical material is used as an exposure light source. An image forming method using a light source in combination with