JPH05241271A - Silver halide photographic sensitive material - Google Patents

Abstract

PURPOSE:To enable a transparent and opaque pattern to be selectively formed in a heat sensitive layer by forming on a support the heat-sensitive layer comprising a resin base and an organic low-molecular substance dispersed into the resin base and reversibly changing transparency in accordance with temperature. CONSTITUTION:At least one heat-sensitive layer composed essentially of the resin base and the organic low-molecular substance dispersed into the resin base and changing its transparency in accordance with temperature is formed on the support, and at least one photosensitive silver halide emulsion layer is also formed. This heat-sensitive layer may be formed on either side of the support so long as it is to be heated, but it is preferred to form it on the side reverse to the emulsion layer. It is also preferred to form an overcoat layer in order to prevent deformation and scratching due to heat or pressure when the surface of the heat-sensitive layer is heated with a thermal head or a heat roller.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a silver halide photographic light-sensitive material having both a silver halide photographic light-sensitive layer and a reversible heat-sensitive recording layer, and the light-sensitive material exposed by a laser beam, a CRT image or an LED scan. The present invention relates to an image forming method for obtaining an image.

[0002]

2. Description of the Related Art A photographic light-sensitive material (hereinafter referred to as a light-sensitive material) which obtains a transmission image is a silver halide on a transparent support having a silver halide light-sensitive layer and a reflection image which is an opaque support such as paper It is widely known to have a photosensitive layer. Therefore, in the case of recording the transmitted image and the reflected image with one device, conventionally, it was necessary to replace two kinds of photosensitive materials. Further, the same problem occurs when the color of the support is changed by the reflected image.

[0003]

SUMMARY OF THE INVENTION Therefore, an object of the present invention is to enable the use of transparent or opaque support as a single photosensitive material. It is also possible to change the color of the support with an opaque support.

[0004]

The above objects of the present invention are as follows.
At least one heat-sensitive layer comprising a resin base material and an organic low-molecular substance dispersed in the resin base material as a main component on a support, and the transparency reversibly changes depending on temperature, and at least one layer It is achieved by a silver halide photographic light-sensitive material characterized by having a light-sensitive silver halide emulsion layer of

The reversible thermosensitive layer used in the present invention may be provided in any layer as long as a heating means is used.
When the silver halide emulsion is provided on one side of the support, it is preferable to provide a reversible thermosensitive layer on the opposite side of the support. An overcoat layer is preferably provided in order to prevent the surface from being deformed or scratched by heat or pressure when the reversible heat-sensitive layer on the surface is heated by a thermal head or a heat roller. When a reversible thermosensitive layer is provided on the same surface of the silver halide emulsion and the support,
Depending on the developability of the silver halide emulsion layer, it is preferable to set it on the upper side or the lower side of the silver halide layer. It may be appropriately determined in consideration of the developability of the silver halide emulsion. For example, when the silver halide emulsion layer has sufficient developability, the reversible heat-sensitive layer is preferably provided on the surface so that heat can be effectively applied, while the reversible heat-sensitive layer of the silver halide emulsion layer is When there is no room in the developability, the reversible thermosensitive layer is preferably placed on the lower side. Usually, it is preferable that the reversible heat-sensitive layer is provided below the silver halide emulsion layer.

The reversible thermosensitive recording layer of the present invention comprises a resin base material and an organic low molecular weight substance dispersed in the resin base material as a main component, and the transparency reversibly changes depending on temperature. Is. Various solvents can be used as the solvent for forming the heat-sensitive layer depending on the types of the organic low molecular weight substance and the resin base material. For example, tetrahydrofuran, methyl ethyl ketone, methyl isobutyl ketone, chloroform,
Organic solvents such as carbon tetrachloride, ethanol, toluene and benzene can be mentioned. In the heat-sensitive layer formed as described above, the organic low molecular weight substance is present in the resin base material as fine particles in a dispersed state.

The fat base material used for the heat-sensitive layer is a material that forms a film or sheet in which an organic low molecular weight substance is uniformly dispersed and held, and has an effect on the transparency at maximum transparency.
Therefore, the resin base material is preferably a resin having good transparency, mechanical stability, and good film forming property. Such resins include polyvinyl chloride; vinyl chloride-vinyl acetate copolymers, vinyl chloride-vinyl acetate-vinyl alcohol copolymers, vinyl chloride-vinyl acetate-maleic acid copolymers, vinyl chloride-acrylate copolymers. Vinylidene chloride such as coalescing ~
Vinylidene chloride copolymers such as vinyl chloride copolymers and vinylidene chloride-acrylonitrile copolymers; polyesters; polyamides; polyacrylates or polymethacrylates or acrylate-methacrylate copolymers, silicone resins and the like. These may be used alone or in admixture of two or more. On the other hand, the organic low molecular weight substance preferably has a melting point of 30 to 200 ° C, particularly about 50 to 150 ° C. Alkanols; alkane diols; halogen alkanols or halogen alkane diols; alkylamines; alkanes;
Alkenes; alkynes; halogen alkanes; halogen alkenes; halogen alkynes; cycloalkanes; cycloalkenes; cycloalkynes; saturated or unsaturated mono- or carboxylic acids or their esters, amides, or ammonium salts; saturated or unsaturated halogen fatty acids or their Ester, amide, or ammonium salt; Allylcarboxylic acid or ester, amide or ammonium salt thereof; Halogenallylcarboxylic acid or ester, amide, or ammonium salt thereof; Thioalcohol; Thiocarboxylic acid or ester, amine, or ammonium thereof Salts: carboxylic acid esters of thioalcohol and the like can be mentioned. These may be used alone or in admixture of two or more. The carbon number of these compounds is 10
-60, preferably 10-38, and especially 10-30 are preferred. The alcohol group portion in the ester may be saturated or unsaturated, and may be halogen-substituted.

More specifically, these compounds include laurin.
Acid, dodecanoic acid, myristic acid, pentadecanoic acid, pal
Mitic acid, stearic acid, behenic acid, nonadecanoic acid, a
Higher fatty acids such as laquinic acid and oleic acid; stearic acid
Chill, tetradecyl stearate, octastearate
Decyl, octadecyl laurate, tetra palmitate
Esters of higher fatty acids such as decyl and docosyl behenate;
C₁₆H₃₃-O-C₁₃H₃₃, C₁₆H₃₃-S-C₁₆H₃₃, C₁₂H_{twenty five}-S-C
₁₂H₂₅, C₁₈H₃₇-O-C₁₈H₃₇, C₁₂H_{twenty five}-S-S-C
₁₂H₂₅, C₁₇H₃₅OCOCH₂CH₂OCH₂CH₂OCOC₁₇H₃₅, C₁₂H
_{twenty five}OCOCH₂CH₂SCH₂CH₂OCOC ₁₂H₂₅, Etc. ether or chi
There is Oether. In addition, the organic low molecular weight substance in the heat sensitive layer
The weight ratio with the resin base material is about 1: 0.5 to 1:16.
Is preferred. In the present invention, the organic low molecular weight substance is
A substance that controls crystal growth can be used in combination. For example
It is generally used as a surfactant and
Alcohol higher fatty acid ester; polyhydric alcohol higher alcohol
Rutile ether; polyhydric alcohol higher fatty acid ester,
Higher alcohol, higher alkylphenol, higher fatty acid
Higher alkyl amines, higher fatty acid amides, and the like. Existence
To control crystal growth of organic low molecular weight materials and organic low molecular weight materials
It is preferable that the weight ratio of the substance is about 1: 0.01 to 1: 0.8.
Good

In the present invention, an overcoat layer may be provided for the purpose of protecting the heat sensitive layer. As the ultraviolet curable resin used for forming the overcoat layer, any monomer or oligomer (or prepolymer) which undergoes a polymerization reaction upon irradiation with ultraviolet rays and is cured into a resin can be used. Examples of such monomers or oligomers include (poly) ester acrylate, (poly) urethane acrylate, epoxy acrylate, polybutadiene acrylate, silicone acrylate, and melamine acrylate. (Poly) ester acrylate is 1,6
-A polyhydric alcohol such as hexanediol, propylene glycol (as propylene oxide), and diethylene glycol, and a polybasic acid such as adipic acid, phthalic anhydride, and trimellitic acid are reacted with acrylic acid. Details of the reversible thermosensitive recording layer and overcoat layer of the present invention are described in JP-A-2-566, pages 2 to 8.
The description on the page can be referred to.

A material layer that absorbs laser light and converts it into heat energy is provided in the vicinity of the reversible heat-sensitive layer provided in accordance with the silver halide emulsion layer of the present invention, or laser light is included in the reversible heat-sensitive layer. A material capable of laser-induced thermal recording in the reversible thermosensitive layer by containing a material that absorbs light and converts light energy into heat energy, or a combination thereof, is not contacted with the reversible thermosensitive layer. It is particularly preferable because it can provide heat at high speed and high density. Here, an infrared absorbing dye is particularly preferable as the substance that absorbs laser light and converts light energy into heat energy. It is particularly preferable that the reversible thermosensitive layer contains an infrared absorbing dye. The infrared absorbing dye contained in the layer adjacent to the reversible heat-sensitive layer or in the reversible heat-sensitive layer may be used in any concentration. Further, two or more kinds of infrared absorbing dyes may be used in combination, and may also be used in combination with another substance that converts the light energy of laser light into heat energy. Generally, it is preferable to use the infrared absorbing dye in a layer adjacent to the reversible thermosensitive layer or in the reversible thermosensitive layer at a concentration of 0.02 to 0.5 g / m ² .

The laser used in the present invention is an ion gas laser, a metal vapor laser, a solid-state laser,
A laser such as a semiconductor laser can be used. Among these lasers, semiconductor lasers are small, low cost, stable,
It is particularly preferable because it is advantageous in terms of reliability, durability, ease of modulation, and the like.

The infrared absorbing dye used in the present invention is
It is preferable that the absorption of light in the visible region is small and the wavelength of light in the infrared region is particularly high. It is also preferable that the absorption peak of the infrared absorbing dye matches the wavelength of the laser used. Examples of the dye include cyanine dyes, phthalocyanine dyes, pyrylium / thiopyrylium dyes, azurenium dyes, squarylium dyes, N
Metal complex salt dyes such as i and Cr, naphthoquinone dyes / anthraquinone dyes, indophenol dyes, indoaniline dyes, triphenylmethane dyes, triallylmethane dyes, aminium dyes, diimmonium dyes, and nitroso compounds be able to. Among these, it is preferable to use one having a high absorption rate of light in the near-infrared region having a wavelength of 700 nm to 900 nm from the viewpoint of practical use of a semiconductor laser that oscillates near-infrared light. Specific examples thereof include dyes represented by the following formula.

(1) Cyanine dye: (CH ₃ ) ₂ N- (CH = CH) ₅ -CH = ⁺ N (CH ₃ ) ₂
ClO ₄ ^-,

[0014]

[Chemical 1]

(Where n is 2 or 3),

[0016]

[Chemical 2]

(However, R is a hydrogen atom or N (CH ₃ ) ₂
, A- (CH = CH) _n -CH = B, where A is a group represented by the following formula:

[0018]

[Chemical 3]

B is a group represented by the following formula:

[0020]

[Chemical 4]

[0021]

[Chemical 5]

R is an alkyl group, X is a counter ion, and a benzene ring or a naphthalene ring may optionally have a chlorine atom, an alkyl group, an alkoxy group or an aryl group. n is an integer of 0-3.

[0023]

[Chemical 6]

(Wherein R is an alkyl group and X is a halogen atom),

[0025]

[Chemical 7]

(Wherein R is a substituted or unsubstituted alkyl group, an alkoxy group or an alkenyl group, X is a hydrogen atom or a halogen atom, and Y is a halogen, perchlorate, a substituted or unsubstituted benzene sulfonate, or a para group. Toluene sulfonate, methyl sulfate, ethyl sulfate, benzenecarboxylate, methylcarboxylate or trifluoromethylcarboxylate, n is an integer of 0 to 3),

[0027]

[Chemical 8]

(However, R ¹ , R ² and R ³ are each a substituted or unsubstituted alkyl group and may be the same or different, and X ⁻ is a perhalogenate ion or toluenesulfonic acid. Is an ion or an alkylsulfate ion, and n is an integer of 0 to 3. 4 of the indolenine ring
A halogen atom is present in at least one of the 5-, 6-, and 7-positions, and in some cases, a halogen atom may be present in another position. The benzene ring may be optionally substituted with an alkyl group, an alkoxy group, a hydroxy group, an allyl group or an alkali carbonyl group),

[0029]

[Chemical 9]

(However, A¹And A²Is hydrogen source
Child or substituent, Z is necessary for forming a 5-membered heterocycle
Atomic group, R¹~ R^FourAre hydrogen atoms or substituents, respectively.
R ^FiveIs a 6-membered heterocycle with Z
May be done, X^-Is an anion, and n is an integer of 0 to 2
Is a number),

[0031]

[Chemical 10]

Chemical formula Φ-L = Ψ (X ⁻ ) _m (where Φ and Ψ are indole ring residue, thiazole ring residue, oxazole ring residue, selenazole ring residue, which may be condensed with aromatic rings, respectively) Group, an imidazole ring residue or a pyridine ring residue, L is a linking group for forming monocarbocyanine, dicarbocyanine, tricarbocyanine or tetracarbocyanine, and m is 0 or 1.). Particularly preferred are the compounds represented by the following general formula described in JP-A-2-2074.

[0033]

[Chemical 11]

In the formula, R ¹ , R ² , R ³ , R ⁴ and R ⁵ each independently represent a substituted or unsubstituted alkyl group,
You may form a ring through a methine chain. Z ¹ and Z ² each represent a hydrogen atom or an atomic group necessary for forming a substituted or unsubstituted aromatic ring. Y ¹ and Y ² represent a carbon atom substituted with an alkyl group, a vinylene group, an oxygen atom, a sulfur atom or a selenium atom. J represents a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, a halogen atom, or a nitrogen atom substituted with an atom necessary for forming a 5- or 6-membered ring, and n is 0 or 1 and X is a monovalent anion. Preferably, R ¹ and R ² are methyl groups, J is hydrogen, R ³ and R ⁴ form a 6-membered ring, and Z ¹ and Z ² are benzene substituted with a nitro group, a halogen atom or a cyano group. It represents atoms forming a ring, and is the case where Y ¹ and Y ² are dialkyl-substituted carbon atoms. Examples of preferred compounds included in the above general formula include compounds 1 to 12 described in JP-A-2-2074.

Further, squalium dye, azurenium dye, indophenol dye, metal complex dye,
Naphthoquinone-based and anthraquinone-based dyes can also be preferably used.

In the silver halide light-sensitive material of the present invention, when one side of the support is coated with a silver halide emulsion, it is preferable to provide a back layer on the opposite side of the light-sensitive emulsion layer. It is preferable to contain an antihalation dye therein. The antihalation dye may be provided between the emulsion layer and the support. When the silver halide emulsion is coated on both sides of the support, the antihalation dye is preferably provided between the emulsion layer and the support. The amount of the dye used as the antihalation dye of the present invention is such that the transmission density of the dye-containing layer at the wavelength of the exposure light source is 0.15 to 0.15.
It is preferable to set it to 1.5, preferably 0.3 to 1.2. As a method of incorporating a dye, there is a method of dissolving a soluble dye in a hydrophilic colloid layer, which is disclosed in British Patent Nos. 1,414,456, 1,477,638 and 1,477,639. Has been done. Further, a method in which a hydrophilic polymer having a charge opposite to that of the dissociated anionic dye is allowed to coexist in the layer as a mordant to localize the dye in a specific layer by the interaction between the dye molecule and the polymer is disclosed in US Pat. 548,564, 4,124,386
No. 3,625,694, JP-A-1-126645.
No., etc. Also, a method of allowing a dye dispersed in a microcrystalline state to exist is disclosed in US Pat. No. 4,803,150.
No. 1, WO88 / 04794, JP-A-1-87367 and the like.

To fix the dye, a method of adsorbing the dye on a mordant, a method of dispersing the dye as a solid, or a method of emulsifying and dispersing a dye dissolved in oil in the form of oil droplets (Japanese Patent Application No. 1) -142688), a method of adsorbing a dye on the surface of an inorganic material (Japanese Patent Application No. 1-139691), and a method of adsorbing a dye to a polymer (Japanese Patent Application No. 1-11985).
No. 1) etc. Among these, the method of dispersing the dye as a solid is a preferable method. Regarding the antihalation dye used in the present invention, Research Disclosure RD-17643, pp. 25-26, RD-
18716, pages 649-650, International Patent WO88 / 0
4794, JP-A-2-247927, and Japanese Patent Application No. 2-1.
The dyes described in Japanese Patent Application No. 18043 and Japanese Patent Application No. 2-303170 can be used. Examples of preferred compounds are shown below, but the invention is not limited thereto.

[0038]

[Chemical 12]

[0039]

[Chemical 13]

Specific examples of the antihalation dyes preferably used in the present invention are, in addition to the above, Japanese Patent Application No. 3-25.
AH-1 to AH-20 of No. 2748 can also be preferably used. The addition amount of the antihalation dye used in the back surface of the present invention cannot be unconditionally determined depending on the transmittance of the dye, the decolorization speed, and the influence on the film quality, but it is generally preferably 10 ^{-3 to 1} g / m ² , More preferably 5 × 10 ^-3
~ 800 mg / m ² . These dyes may be used alone or in combination of two or more.

The antihalation dye and / or the antiirradiation dye used in the present invention when the exposure light source of the light-sensitive silver halide photographic material in the present invention is in the infrared region is substantially at a long wavelength of 750 nm or more. A dye having absorption is used. Here, the antihalation dye is an intermediate layer, an undercoat layer, an antihalation layer, a back layer,
The anti-irradiation dye used for emulsion layers is
It is used as an intermediate layer in addition to the emulsion layer. Further, these dyes are preferably 10 ^{−3 to 1} g / m ² , more preferably 10
^{-3 to 1} g / m ² , more preferably 10 ^{-3 to} 0.5 g / m ² is used. For example, US Pat. No. 2,895,
No. 955, No. 3,177,078, No. 4,581,3
No. 25, JP-A-50-100, 116, JP-A-62-
123454, dyes described in JP-A-62-181381, JP-A-63-23148, and JP-A-63-89.
Dyes such as those described in No. 838 are preferably used. These dyes may be used alone or in combination of two or more. Further, instead of the above-mentioned dyes, these dyes may be used in combination with other dyes. Examples of dyes used instead or in combination include pyrazolone oxonol dyes described in US Pat. No. 2,274,782, diarylazo dyes described in US Pat. No. 2,956,879, and US Pat. 3,423,207
No. 3,384,487, styryl dyes and butanedienyl dyes, US Pat. No. 2,527,583, merocyanine dyes, US Pat. No. 3,486,8.
No. 97, No. 3,652,284, No. 3,718,
Examples thereof include merocyanine dyes and oxonol dyes described in US Pat. No. 472, and enaminohemioxonol dyes described in US Pat. No. 3,976,661. Further, the dyes described in JP-A-61-174540 can be mentioned.

The silver amount of the light-sensitive material used in the present invention can be set to any value depending on the purpose. Write generally less is set preferably per one side 0.3g / m ² ~4g / m ² since the development processing speed can be faster.

Next, the emulsion grains contained in the light-sensitive material used in the present invention will be described. The diameter of a sphere having the same volume as the emulsion grains (hereinafter referred to as sphere-equivalent average grain size) is preferably 0.2 μm or more and less than 2.0 μm, and particularly 0.25.
It is preferably not less than 1.5 μm. The particle size distribution should be narrow. The silver halide grains in the emulsion may have a regular crystal form such as a cube, an octahedron or a tetrahedron, or may have an irregular crystal form such as a sphere, a plate or a potato. Good. It may consist of a mixture of particles of various crystal forms. When a monodisperse emulsion is used as an emulsion in the practice of the present invention, the rate of addition of the aqueous solution of silver nitrate and the water-soluble halide can be increased with the growth of silver halide grains in the preparation of the monodisperse emulsion. By increasing the addition rate, the particle size distribution can be made more monodisperse, and the addition time can be shortened, which is advantageous for industrial production. Further, it is also preferable in that the chance of structural defects being formed inside the silver halide grain is reduced.

As a method for accelerating the addition rate, as described in JP-B-48-36890, JP-A-52-16364 and JP-A-55-142329, the addition rate of an aqueous silver salt solution and an aqueous halide solution can be used. May be increased continuously or stepwise. The upper limit of the addition rate may be a flow rate just before the generation of new grains, and the values are temperature, pH, pAg, degree of stirring, composition of silver halide grains, solubility, grain size, inter-grain distance, or protection. It changes depending on the type and concentration of colloid. A method for producing a monodisperse emulsion is known, and for example, J. Phot. Sci. 12, 242-251.
(1963), JP-B-48-36890, 52-1.
6364 and JP-A-55-142329, and the technology described in JP-A-57-179835 can be employed. The silver halide emulsion used in the present invention may be a core-gel type monodisperse emulsion, and these core-shell emulsions are disclosed in JP-A-54-4.
It is known from No. 8521 and the like. When a polydisperse emulsion is used as an emulsion in carrying out the present invention, a known method can be used for producing the polydisperse emulsion. For example THJ
ames "The Theory of the Photographic Process" 4th
Edition, published by Macmillan (1977), pages 38-104, etc., neutral method, acidic method, ammonia method, forward mixing, back mixing, double jet method, controlled double jet method, conversion method. , Core / shell method, etc. can be applied to manufacture.

Further, tabular grains having a grain size 5 times or more the grain thickness are preferably used in the present invention (for details, RE
SEARCH DISCLOSURE 225 Volume Item 22534P. 20
~ P. 58, January issue, 1983, and JP-A-58-1.
No. 27921, 58-113926). The tabular silver halide grains can be produced by appropriately combining the methods known in the art. Tabular silver halide emulsions are described by Cugnac and Chateau, "Development of Morphology of Silver Bromide Crystals During Physical Aging (Evolution of the Morphology of Silver Promide Crystals).・ During / Physical / Liping) Science
E-Industrie Photography, Volume 33, No.
(1962) pp.121-125, Duffin
"Photographic emulsion Chemistry", Focal Press, New York, 1966, p.
66-P. 72, A, P. H. Tribelli,
W. F. Smith Photographic Journal
(Potographic Journal) 80, 285 (1940)
(Japanese Patent Publication No. 58-127,92).
1, JP-A-58-113, 927, JP-A-58-11
It can be easily prepared by referring to the method described in US Pat. No. 3,928, U.S. Pat. No. 4,439,520. The projected area diameter of the tabular emulsion contained in the light-sensitive material used in the present invention is 0.3 to
It is preferably 2.0 μm, particularly preferably 0.5 to 1.2 μm. The distance between parallel planes (particle thickness) is 0.
It is preferably from 05 μm to 0.3 μm, particularly from 0.1 to 0.25 μm, and the aspect ratio is preferably 3 or more and less than 20, particularly preferably 4 or more and less than 8. In the tabular silver halide emulsion of the present invention, silver halide grains having an aspect ratio of 2 or more are present in an amount of 50% (projected area) or more, particularly 70% or more of all grains, and the average aspect ratio of the tabular grains is It is preferably 3 or more, and particularly preferably 4 to 8. Among the tabular silver halide grains, monodisperse hexagonal tabular grains are particularly useful grains. The details of the structure and manufacturing method of the monodisperse hexagonal tabular grain according to the present invention are described in JP-A-63-151618. A substantially non-photosensitive emulsion (eg, internally fogged fine grain emulsion) may be mixed with these photosensitive emulsions. Of course, they may be applied in separate layers.

Further, even if the crystal structure of the silver halide grains is uniform to the inside, it has a layered structure in which the inside and the outside are different, British Patent 635,841 and US Pat. It may be a so-called conversion type as described in No. 622,318. When forming the silver halide grains, as a silver halide solvent for controlling the growth of the grains, for example, ammonia, rodancali, rodanammon, and a thioether compound (for example, US Pat. Nos. 3,271,157 and 3,574,
No. 628, No. 3,704, 130, No. 4, 29
7,439, 4,276,374, etc.) thione compounds (for example, JP-A-53-144319, JP-A-5-144319).
No. 3-82408, No. 55-77737, etc.), amine compounds (for example, JP-A-54-100717, etc.)
Etc. can be used. In addition to the silver halide solvent, a compound that is adsorbed on the grain surface to control the crystal habit, such as a cyanine dye, a tetrazaindene compound, or a mercapto compound, can be used during grain formation. The silver halide emulsion used in the present invention may be monodisperse or polydisperse, but monodispersion is preferred. Two or more kinds of monodisperse emulsions having different grain sizes may be mixed and used. The emulsion of the present invention may be either a negative type or an autopositive type (internal latent image type using a nucleating agent).

The silver halide emulsion of the light-sensitive material of the present invention may contain metal ions such as iridium ions. For example, in order to contain iridium ions, it is common to add a water-soluble iridium compound (for example, hexachloroiridium (IV) salt) in the form of an aqueous solution when preparing a silver halide emulsion. It may be added in the form of the same aqueous solution as the halide for grain formation, may be added before grain formation, during grain formation, or after grain formation until chemical sensitization, but is particularly preferable. Is addition at the time of grain formation.

The negative emulsion used in the present invention is a chemical sensitizing method which is usually used, for example, sulfur sensitization (US Pat. Nos. 1,574,944 and 2,278,947;
No. 3,021,215, No. 3,635,717, etc.), reduction sensitization (US Pat. No. 2,518,698,
Research Disclosure
Vol. 176 (1978.12) 17643, item 3, etc., and sensitization with thioether compounds (for example, US Pat. Nos. 2,521,926 and 3,021,215).
No. 3,046,133, No. 3,165,55
No. 2, No. 3,625,697, No. 3,635,7
No. 17, No. 4,198,240, etc.) or various sensitizing methods combined therewith. More specific chemical sensitizers include sulfur sensitizers such as sodium thiosulfate, allyl thiocarbamide, thiourea, thiosulfate, thioether and cystine;
Examples include reduction sensitizers such as tin chloride, phenylhydrazine and reductone, and sensitization with selenium compounds and tellurium compounds. The negative type silver halide emulsion used in the present invention has a silver halide adsorptivity of 0.5 mmol or more per mol of silver halide during chemical sensitization during the emulsion preparation process as described in JP-A-2-68539. It is preferred to have the substance present. This silver halide adsorptive substance is
It may be added at any time during grain formation, immediately after grain formation, before or after the start of post-ripening, but before addition of a chemical sensitizer (for example, gold or sulfur sensitizer), or chemical sensitizer. It is preferable to be added at the same time, and it is necessary to be present at least in the process of progress of chemical sensitization. As a condition for adding the silver halide adsorbing substance, the temperature is 30 ° C. to 8 °
Any temperature of 0 ° C may be used, but for the purpose of enhancing the adsorptivity,
The range of 50 ° C to 80 ° C is preferable. pH and pAg may be arbitrary, but at the time of chemical sensitization, pH 5 to 10,
It is preferably pAg7-9.

In the present invention, the silver halide adsorbing material means a sensitizing dye or a class of photographic performance stabilizers. That is, azoles {eg benzothiazolium salts, benzimidazolium salts, imidazoles, benzimidazoles, titroindazoles, triazoles, benzotriazoles, tetrazoles, triazines, etc.); mercapto compounds {eg mercaptothiazoles, Mercaptobenzothiazoles, mercaptoimidazoles, mercaptobenzimidazoles, mercaptobenzoxazoles, mercaptothiadiazoles, mercaptooxadiazoles, mercaptotetrazoles, mercaptotriazoles, mercaptopyrimidines, mercaptotriazines and the like}; for example, oxadrine Thioketo compounds such as thione; azaindenes {eg triazaindenes, tetraazaindenes (especially 4-hydroxy) Substituted (1,3,3a, 7) tetraazaindenes), pentaazaindenes such like);
Many compounds known as antifoggants or stabilizers such as can be mentioned as the silver halide adsorbing material. Further, purines or nucleic acids, or polymer compounds described in JP-B-61-36213, JP-A-59-90844, etc. are also adsorbable substances that can be used. Of these, azaindenes, purines, and nucleic acids are particularly preferable and can be used in the present invention. The addition amount of these compounds is 10 to 500 per mol of silver halide.
mg, preferably 20-300 mg.

As the silver halide-adsorptive substance of the present invention,
Sensitizing dyes can achieve favorable effects. As the sensitizing dye, cyanine dye, merocyanine dye, complex cyanine dye, complex merocyanine dye, holoholer cyanine dye, styryl dye, hemicyanine dye, oxonol dye, hemioxonol dye and the like can be used. Useful sensitizing dyes used in the present invention are, for example, U.S. Pat. Nos. 3,522,052 and 3,619,
No. 197, No. 3,713,828, No. 3,615,6
No. 43, No. 3,615, 632, No. 3,617, 29
No. 3, No. 3,628,964, No. 3,703,377
Issue No. 3,666,480 Issue 3,667,960
Nos. 3,679,428 and 3,672,897
Issue No. 3,769,026 Issue No. 3,556,800
Issue No. 3,615,613 Issue No. 3,615,638
Nos. 3,615,635 and 3,705,809
No. 3,632,349, No. 3,677,765
No. 3,370,449, No. 3,770,440
No. 3, ibid. 3,769,025, ibid. 3,745,014
Issue 3, Issue 3,713,828, Issue 3,567,458
Nos. 3,625,698, 2,526,632
No. 2,503,776, JP-A-48-76525.
And Belgian Patent No. 691,807. Addition amount of sensitizing dye is 1 per mol of silver halide
00 mg or more and less than 2000 mg, preferably 200 mg or more 1
Less than 000mg is good. Specific examples of the sensitizing dye effective in the present invention are shown below.

[0051]

[Chemical 14]

[0052]

[Chemical 15]

The spectral sensitizer used in the present invention includes
Examples include infrared, panchromatic, ortho, and regular. In the present invention, as the infrared spectral sensitizer, for example, at least one of a tricarbocyanine dye and / or a 4-quinoline nucleus-containing dicarbocyanine dye described in JP-A-63-89838 can be used. it can. In addition, JP-A-59-192242 and JP-A-59
The thing described in -191032 is used. As the panchromatic sensitizing dye, those described in JP-B-43-4933 and JP-B-60-45414 are used. The above-mentioned spectral sensitizing dye used in the present invention is contained in the silver halide photographic emulsion in a ratio of 10 ^-7 to 10 ^-2 mol, preferably 10 ^-6 to 10 ^-3 mol per mol of silver halide. .. The method described in U.S. Pat. Nos. 2,912,343, 3,342,605, 2,996,287, and 3,429,835 can be used for addition to the emulsion. .. The above-mentioned spectral sensitizing dye may be uniformly dispersed in a silver halide emulsion before being coated on a suitable support.
As described above, it can be dispersed at any stage of preparation in the silver halide emulsion. Furthermore, other sensitizing dyes can be used in the present invention. For example, US Pat. Nos. 3,703,377 and 2,688,545.
No. 3, ibid. 3,397,060, ibid. 3,615, 63
5, No. 3,628,964, British Patent Nos. 1,24
No. 2,588, No. 1,293,862, Japanese Patent Publication No. 43
-4936, 44-14030, 43-107.
73, U.S. Pat. No. 3,416,927, Japanese Patent Publication No. 43
-4930, US Pat. Nos. 3,615,613, 3,615,632, 3,617,295, and 3,635,721. Alternatively, the above infrared sensitizing dye and these spectral sensitizing dyes may be used in combination.

In the present invention, the compounds described in JP-A-63-89838 can be used together with the above-mentioned sensitizing dye for the purpose of further enhancing the supersensitizing effect. Furthermore, together with the above-mentioned sensitizing dye, JP-A-63-89838
A combination of storability improvers as described in US Pat. No. 4,096,839 may be used in an amount of about 0.01 to 5 g per mol of silver halide in the emulsion.

The photographic light-sensitive material of the present invention has a manufacturing process,
Various compounds can be added in order to prevent sensitivity deterioration and fog generation during storage or processing. These compounds include nitrobenzene imidazole, ammonium chloroplatinate, 4-hydroxy-6-methyl-
1,3,3a, 7-tetrazaindene, 1-phenyl-
An extremely large number of compounds such as 5-mercaptotetrazole, many heterocyclic compounds, mercury-containing compounds, mercapto compounds and metal salts have long been known. One example of a compound that can be used is C.I. E. K. "The Thoery" by Mees
of the Photographic Process "(3rd edition, 1966
(Year) pp. 344-349 with reference to the original literature.
For example, US Patent Nos. 2,131,038 and 2,6
94,716 and other thiazolium salts; US Pat. Nos. 2,886,437 and 2,444,60.
5, Azaindenes described in US Pat. No. 3,287,135, etc. Urazols described in US Pat. No. 3,287,135, Sulfacatechols described in US Pat. No. 3,236,652, UK; Patent No. 623,448
Oximes described in US Pat. No. 2,4
No. 03,927, No. 3,266,897, No. 3,
397,987 and other mercaptotetrazoles, nitrones, nitroindazoles; US Pat. No. 2,839,405 and other polyvalent metal salts; US Pat.
No. 0,839 and other thiuronium salts (Thi
uronium salts); palladium, platinum and gold salts described in US Pat. Nos. 2,566,263 and 2,597,915.

The silver halide emulsion used in the present invention is
(100) face / (111) face ratio is 1 or more, preferably 2
50 or more, more preferably 4 or more silver halide grains.
The content is preferably at least wt%, more preferably at least 60 wt%, and particularly preferably at least 80 wt%.

Various additives and the like used in the photographic light-sensitive material of the present invention are not particularly limited in addition to the above, and for example, those described in the following relevant parts can be used. Item This section 1) Silver halide emulsion and JP-A-2-68539, page 8, lower right column, lower column, 6 from its production line to the same, page 10, upper right column, 12th column, 3-245 37 Gazette, page 2, lower right column, line 10 to page 6, upper right column, line 1; page 10, upper left column, line 16 to page 11, lower left column, line 19; Japanese Patent Application No. 2-225637. 2) Chemical sensitization method JP-A-2-68539, page 10, upper right column, line 13 to upper left column, line 16; Japanese Patent Application No. 3-105035. 3) Antifoggants and Stabilizers JP-A-2-68539, page 10, lower left column, line 17 to page 11, upper left column, line 7 and page 3, lower left column, line 2 to page 4, lower left column .. 4) Color improver JP-A-62-276539, page 2, lower left column, line 7 to page 10, lower left column, line 20; JP-A-3-94 249, page 6, lower left column, line 15 to Page 11, right upper column, line 19 5) Spectral sensitizing dye JP-A-2-68539, page 4, lower right column, line 4 to page 8, lower right column. 6) Surfactant JP-A-2-68539, page 11, upper left column, line 14 Antistatic agent to page 12, upper left column, line 9 7) Matting agent, slipping agent JP-A-2-68539, page 12, upper left column, line 10 Plasticizer to the same upper right column, line 10; page 14, lower left column, line 10 to right lower column, line 1

8) Hydrophilic Colloid JP-A-2-68539, page 12, upper right column, line 11 to lower left column, line 16 9) Hardener JP-A-2-68539, page 12, lower left column, line 17 to page 13, upper right column, line 6 10) Supports JP-A-2-68539, page 13, upper right column, lines 7 to 20. 11) Crossover JP-A-2-264944, page 4, upper right column, line 20 From cut method, page 14 upper right column. 12) Dyes and mordants JP-A-2-68539, page 13, lower left column, line 1 to page 14, lower left column, line 9 No. 3-24537, page 14, lower left column to page 16, lower right column. 13) Polyhydroxy JP-A-3-39948, page 11, upper left column to the same benzenes, page 12, lower left column, EP Patent No. 452772A. 14) Layer structure JP-A-3-198041. 15) Development processing method JP-A-2-103037, page 16, upper right column, line 7 to page 19, left lower column, line 15 and JP-A-2-115837, page 3, lower right column, line 5 Page 6, upper right column, line 10 The present invention will be further described below with reference to examples. In addition,
"Parts" and "%" are based on weight.

[0059]

【Example】

 Example 1 (Preparation of coating solution for reversible thermosensitive layer) Behenic acid 8 parts Stearyl stearate 2 parts Di (2-ethylhexyl) phthalate 3 parts Vinyl chloride-vinyl acetate copolymer (UCY VYHH) 28 parts Tetrahydrofuran 200 Department

(Formation of Reversible Heat Sensitive Layer) The above coating solution was coated on a 75 μm thick undercoated PET film support with a wire bar and dried by heating to form a heat sensitive layer. The thickness of the heat sensitive layer was 15 μm. A solution consisting of 10 parts of polyamide resin (CM8000 manufactured by Toray Industries, Inc.) and 90 parts of methyl alcohol was applied thereto by a wire bar, and dried by heating to 1
A μm thick intermediate layer was provided. Furthermore, a butyl acetate solution of urethane acrylate-based UV curable resin (Unidick 17-824-9, manufactured by Dainippon Ink and Chemicals, Inc.) is applied with a wire bar, and after heating and drying, UV rays are applied with an 80 W / cm UV lamp. It was irradiated for 5 seconds to form an overcoat layer having a thickness of 5 μm. Then, the support having a transparent reversible thermosensitive layer was prepared by reheating to 65 ° C.

(Preparation of silver halide emulsion A) 40 g of gelatin was dissolved in 1 liter of water, and 3 g of potassium bromide and the following compound [I] were placed in a container heated at 55 ° C.

[0062]

[Chemical 16]

After adding 60 mg of the above, an aqueous solution 1 containing 200 g of silver nitrate while maintaining the pAg value in the reaction vessel at 7.0
2,000 ml and 1080 g of an aqueous solution of 140 g of potassium bromide containing potassium hexachloroiridium (III) in a molar ratio of 10 ^-7 to silver were added by the double jet method to give an average particle size (projected area diameter) of 0.35 μm. Cubic monodisperse silver bromide grains (variation coefficient of projected area diameter 11%)
Was prepared. After desalting this emulsion, gelatin 77.5
g, 1.75 g of phenoxyethanol were added, and the pH was adjusted to 6.
5, pAg 8.5.

Thereafter, the temperature was raised to 65 ° C., 3 mg of sodium thiosulfate was added, and 2 minutes after that, 4 mg of chloroauric acid was added,
After 80 minutes 4-hydroxy-6-methyl-1,3,3
After adding 200 mg of a, 7-tetrazaindene, it was rapidly cooled and solidified to obtain Emulsion A.

(Preparation of Emulsion Coating Solution) The following chemicals were added to Emulsion A per mol of silver halide to prepare an emulsion coating solution. I. Spectral sensitizing dye Exemplified Compound I-1 138 mg b. Spectral sensitizing dye Exemplified compound I-2 42.5 mg c. Polyacrylamide (molecular weight 40,000) 8.54 g d. Trimethylolpropane 1.2 g e. Sodium polystyrene sulfonate (average molecular weight 600,000) 0.46 g f. Latex of poly (ethyl acrylate / methacrylic acid) 32.8 g. 1,2-bis (vinylsulfonylacetamide) ethane 2 g

(Preparation of Coating Solution for Surface Protecting Layer of Emulsion Layer) The container was heated to 40 ° C., and the following chemicals were added to prepare a coating solution. I. Gelatin 100 g b. Polyacrylamide (molecular weight 40,000) 12.3 g c. Sodium polystyrene sulfonate (molecular weight 600,000) 0.6 g d. Polymethylmethacrylate fine particles (average particle size 2.5 μm) 2.7 g e. Sodium polyacrylate 3.7 g f. Sodium t-octylphenoxyethoxyethane sulfonate 1.5 g. C ₁₆ H ₃₃ O- (CH ₂ CH ₂ O) ₁₀ -H 3.3 g h. C ₈ F ₁₇ SO ₃ K 84 mg Re. _{C 8 F 17 SO 2 N (} C 3 H 7) (CH 2 CH 2 O) 4 (CH 2) 4 -SO 3 Na 84mg j. 0.2 g of NaOH. Methanol 78cc. Adjusted to be 2.3% by weight based on the amount of 1,2-bis (vinylsulfonylacetate emulsion layer and surface protection layer total ziramide) ethane.

(Preparation of Back Layer (B Side) Coating Solution) The container was heated to 40 ° C. and the following chemicals were added to prepare a back layer coating solution. I. Gelatin 100 g b. Dye D 2.39g

[0068]

[Chemical 17]

D. Sodium polystyrene sulfonate (molecular weight 600,000) 1.1 g e. Phosphoric acid 0.55 g f. Poly (ethyl acrylate / methacrylic acid) latex 2.9 g (Preparation of coating solution for surface protection layer of B side) A container was heated to 40 ° C., and the following chemicals were added to prepare a coating solution. I. Gelatin 100 g b. Sodium polystyrene sulfonate (molecular weight 600,000) 0.3 g c. Polymethylmethacrylate fine particles (average particle size 3.5 μm) 4.3 g d. Sodium t-octylphenoxyethoxyethane sulfonate 1.8 g e. Sodium polyacrylate 1.7 g f. C ₁₆ H ₃₃ O- (CH ₂ CH ₂ O) ₁₀ -H 3.6 g g. C ₈ F ₁₇ SO ₃ K 268 mg Chi. C ₈ F ₁₇ SO ₂ N (C ₃ H ₇ ) (CH ₂ CH ₂ O) ₄ (CH ₂ ) _4- SO ₃ Na 45 mg. NaOH 0.3 g Nu. 131 ml of methanol 1,2-Bis (vinylsulfonylacetate back layer and surface protection layer) Adjusted to 2.2% by weight based on the amount of ethanelatin.

(Preparation of coating sample) On the side of the support provided with the reversible thermosensitive layer described above, on the side provided with the reversible thermosensitive layer, the above-mentioned back layer coating solution was added together with the surface protective layer coating solution of the back layer and gelatin of the back layer the coating amount is 2.69 g / m ^2, a gelatin coating amount of the surface protective layer layer of the back layer was coated to a 1.13 g / m ^2. Subsequently, the emulsion coating liquid and the surface protective layer coating liquid described above were applied to the opposite side (A side) of the support, and the coating Ag amount of the emulsion coating liquid was 2.3 g / m ² and the gelatin for the surface protective layer was coated. A sample (a) was prepared so that the amount was 1.2 g / m ² . Next, as a comparative example, a sample (b) was prepared in the same manner except that the reversible thermosensitive layer coating solution was not applied to the support of Example 1.

(Formation of Image) The above-mentioned coated sample (a),
(B) was exposed for image by a He-Ne laser printer of FCR AC-1 system manufactured by Fuji Photo Film Co., Ltd., and was automatically developed by an automatic processor directly connected. In each of the coated samples (a) and (b), a black image of silver halide was formed on a transparent support.

Then, when the samples (a) and (b) were heated to 65 ° C., the sample (a) became cloudy and opaque, and the sample (b) did not change at all. The silver halide light-sensitive material of the present invention is
Since the reversible thermosensitive layer is provided, it is possible to select a transmission image or a reflection image as required. Next, when the sample (a) was heated again to 65 ° C., it became transparent.

Example 2 Infrared absorbing dye compound in the reversible thermosensitive layer of Example 1
Samples (c) and (d) were prepared by performing the same operation except that 0.14 g / m ^{2 of} 1 and -2 was contained. Next, the same FC as in Example 1 together with the samples (a) and (b) described above was used.
An image was recorded using a RAC-1 laser printer, and then an automatic development process was performed. Sample (a),
Images (b), (c) and (d) were image-formed on the transparent support. Samples (a)-(d) above were then exposed to a focused 830 nm laser beam on a drum rotating at 180 rpm. The laser light source is a laser model SDL-2420-H2 manufactured by Spectrodiode Labs.
Met. Spot diameter 50μm, exposure time 5msec,
The output is 86mW and the exposure energy is 44μW / mm at maximum.
^{Was 2} . The exposure energy was applied to the image area and not to the non-image area. Only the supports in the image areas of samples (c) and (d) became cloudy and opaque, and the non-image areas remained transparent. No changes were observed in the samples (a) and (b).

[0074]

[Chemical 18]

Example 3 A coated sample (e) was prepared by the same procedure except that the support of Example 2 was replaced with a support in which a blue pigment was dispersed. Next, the same image recording and automatic development processing as in Example 2 were performed, and then the same procedure as in Example 2 was performed using the infrared laser exposure machine of Example 2. The non-image area was formed on a blue background and the image area was formed on a white background.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁵ Identification code Office reference number FI technical display location G03C 1/825

Claims (3)

[Claims] 1. A silver halide photographic light-sensitive material having at least one photosensitive silver halide emulsion layer and at least one heat-sensitive layer on a support, wherein the heat-sensitive layer is a resin base material and this resin base material. A silver halide photographic light-sensitive material comprising an organic low-molecular substance dispersed in a material, the transparency of which reversibly changes with temperature. 2. The silver halide photographic light-sensitive material according to claim 1, wherein the heat-sensitive layer is a reversible heat-sensitive recording layer due to heat induced by laser light. 3. The silver halide photographic light-sensitive material according to claim 1, which contains an infrared absorbing substance.