JPH02230236A - Photographic sensitive material - Google Patents

Abstract

PURPOSE:To provided the photosensitive material which has the adaptability to embossing and less uneven colors and has the good adhesive property of silver halide emulsion layers and a substrate by having a laminated polyolefin resin layer on the surface of a thermoplastic resin and providing the photosensitive silver halide emulsion layers thereon. CONSTITUTION:The silver halide emulsion layers are applied on a substrate obtd. by extrusion/lamination of the polyolefin resin on at least one surface of the thermoplastic resin, i.e., on the side where the silver halide emulsions are applied. The polyolefin resin to be used is particularly preferably polyethylene. Polyvinyl chloride, polypropylene, polystyrene, etc., are usable as the thermoplastic resin. The lower limit of the thickness of the polyolefin resin is regulated from the adhesive strength of the silver halide emulsion layers and the upper limit is regulated from the adaptability to embossing. The photosensitive material which has the adaptability to embossing, the excellent sharpness of the images and the decreased uneven colors is obtd. in this way and the adhesive strength of the substrate and the silver halide emulsion layers is improved.

Description

DETAILED DESCRIPTION OF THE INVENTION (Industrial Application Field) The present invention relates to silver halide photographic materials and photographic prints, particularly! Concerning photo prints useful for D cards, cash cards, telephone cards, etc. (Prior art) Conventional supports for silver halide photographic light-sensitive materials include, for example, transparent plastic films such as cellulose triacetate, polyethylene terephthalate, and vinyl resin for transmission types, and baryta paper and synthetic materials for reflective types. Paper, polyethylene-laminated paper, plastic sheets impregnated with white pigment, glass plates, and metal plates (for example, aluminum plates with anodized surfaces) are known. However, silver halide photographic materials using these supports were not suitable for use in D cards, cash cards, telephone cards, etc. as they were not suitable for embossing numbers and letters by thermal processing. As a material suitable for embossing, a silver halide color photographic material using a vinyl chloride resin containing a white pigment as a support is disclosed in European Patent Application Publication No. 270,078! Plan I has been proposed. (Problem B to be solved by the invention) Although color photographic materials using a vinyl chloride resin containing white pigment as a support are excellent in terms of image sharpness, the white pigment dispersed in the vinyl chloride resin It was found that color unevenness tends to occur, which is thought to be caused by uneven pigment dispersion and yellowing of the white pigment that occurs during the manufacturing process (thermal processing). As a result of various studies, the present inventors have discovered that color unevenness can be eliminated by incorporating a white pigment into a polyolefin resin layer laminated on a thermoplastic resin, leading to the present invention.

It has also been found that in photosensitive materials in which a silver halide emulsion layer is coated on a thermoplastic resin, the silver halide emulsion layer tends to peel off from the support, particularly after development, impairing image quality.

The present inventors devised a method for laminating a polyolefin resin layer on a thermoplastic resin and were able to solve the problem of poor adhesion. Therefore, an object of the present invention is to provide a silver halide photographic material that is suitable for embossing, has excellent image sharpness, has less color unevenness, and has good adhesion between the silver halide emulsion layer and the support. It's about doing.

Another object of the present invention is to provide a silver halide color photographic material further containing a color coupler.

Still another object is to provide a color print obtained by subjecting such a color photographic material to a color development process.

(Means for Solving the Problems) As a result of extensive research, the present invention has achieved the above object by extruding and laminating a polyolefin resin on at least one surface of a thermoplastic resin, that is, on the side to which a silver halide emulsion is applied. It has been found that this can be effectively achieved by using a photographic material in which a halogenated emulsion is coated on a support obtained by this process. The present invention will be explained in detail below. The lower limit of the thickness of the polyolefin resin used in the present invention is determined by the adhesion of the silver halide emulsion, and the upper limit is determined by the suitability for embossing. From the above viewpoint, the thickness is preferably 5 to 35 μm, more preferably 10 to 20 pm.

The temperature during extrusion lamination of the polyolefin resin used in the present invention is closely related to improving adhesion;
C to 350 C is preferred. If the temperature exceeds 350°C, thermal decomposition of the polyolefin resin tends to occur, which is undesirable. Moreover, if the temperature is less than 300°C, the effect of improving adhesion will be poor and undesirable.

In addition, the polyolefin resin used in the present invention has whiteness determined from two points: uneven dispersion of the white pigment that occurs in the thermoplastic resin, concealment of color unevenness caused by thermal decomposition, and thickness of the polyolefin resin defined by adhesion. In order to control and obtain a good reflective halogenated photosensitive material, white R
It is preferable to contain 6 to 15 parts by weight of the ingredients. 10 more
-12 parts by weight is more preferred.

In addition, the polyolefin resin used in the present invention includes:
Polyethylene and polystyrene are preferred, and polyethylene is particularly preferred.

Further, as the thermoplastic resin, polyvinyl chloride, polypropylene, polystyrene, polyethylene vinyl acetate copolymer resin, polyethylene-acrylic acid copolymer resin, polyethylene-ethyl acrylate copolymer resin, etc. can be used. As the white pigment, zinc oxide, calcium carbonate, calcium sulfate, etc. can be used, and these pigments are preferably sufficiently kneaded with the polyolefin in the presence of a surfactant. Further, it is preferable to use pigment particles whose surfaces have been treated with a dihydric to tetrahydric alcohol. The occupied area ratio (%) of white pigment fine particles per defined unit area is most typically calculated by dividing the observed area into 6-×6- adjacent unit areas and projecting them onto that unit area. It can be determined by measuring the area ratio (%) (R+) occupied by the fine particles. The coefficient of variation of the occupied area ratio (%) is R. The ratio s of the standard deviation S of R1 to the average value (R) of
/R. The number of target unit areas (n) is preferably 6 or more. Therefore, the coefficient of variation S/
π can be found by In the present invention, the coefficient of variation of the occupied area ratio (%) of pigment fine particles is preferably 0.15 or less, particularly preferably 0.12 or less. If it is less than OS, the particle's 11k property can be said to be "uniform". The color photographic optical material of the present invention includes a blue malignant silver halide emulsion layer on a support,
It can be constructed by coating at least one green-sensitive silver halide emulsion layer and one red-sensitive silver halide emulsion layer. For a single shell of color photographic paper, the layers are usually coated on the support in the order listed above, but a different order may be used. Further, an infrared illuminating silver halide emulsion layer can be used in place of at least one of the above-mentioned emulsion layers. These photosensitive emulsion layers contain a halogenated emulsion that has a brightness in each wavelength range, and dyes that are complementary colors to the intense light, namely yellow for blue, magenta for green, and cyan for red. By incorporating so-called color couplers that form, subtractive color reproduction can be performed. However, the coloring hues of the photosensitive layer and the coupler may not have the above-mentioned correspondence {j11 composition. As the silver halide emulsion used in the present invention, those consisting of chlorobromide radicals or silver chloride that do not substantially contain silver iodide can be preferably used. Here, "substantially free of silver iodide" means that the silver iodide content is 1 mol% or less, preferably 0.2 mol% or less. The halogen composition of the emulsion may be different or the same among the grains, but if an emulsion is used that has the same halogen composition among the grains, it is easy to make the properties of each grain homogeneous. In addition, regarding the halogen composition distribution inside silver halide emulsion grains, there are grains with a so-called uniform structure in which the composition is the same in every part of the silver halide grain, and grains with a so-called uniform structure that have the same composition in every part of the silver halide grain, as well as grains with a core inside the halide root grain and surrounding grains. Shell (B) [single layer or multiple layers]
Particles with a so-called layered structure in which the halogen composition differs between the grains, or structures having parts with different halogen compositions in a non-layered manner inside or on the surface of the grain (if they are on the surface of the grain, parts with different compositions on the edges, corners, or surfaces of the grain) Particles with a bonded structure) can be selected and used as appropriate.
In order to obtain a high degree of turbulence, it is more advantageous to use one of the latter than particles with a uniform structure, and it is also preferable from the viewpoint of pressure resistance. When silver halide grains have the above-mentioned structure, even if the boundaries between parts with different halogen compositions are clear boundaries, the boundaries may be unclear due to the formation of mixed crystals due to compositional differences. It is also possible to have continuous structural changes. Regarding the halogen composition of these silver chlorobromide emulsions, any silver bromide/silver chloride ratio can be used. Although this ratio can vary widely depending on the purpose, a silver chloride ratio of 2% or more is preferably used. Furthermore, so-called high-silver chloride emulsions with a high silver chloride content are preferably used for optical materials suitable for rapid processing. The silver chloride content of these high silver chloride emulsions is preferably 90 mol% or more,
More preferably 95 mol% or more. In such high silver chloride emulsions, the silver bromide localized layer may have the layered structure as described above.
It is preferable to have a non-layered structure inside and/or on the surface of silver halide grains. The halogen composition of the localized phase preferably has a silver bromide content of at least 10 mol%, more preferably more than 20 mol%. These localized layers can be located inside the particle, or on the edge, corner, or surface of the particle surface, but one preferred example is a layer that has grown epitaxially on a part of the corner of the particle. ．． On the other hand, in order to suppress as much as possible the decrease in intensity when a photosensitive material is subjected to pressure, even in high silver chloride emulsions with a silver chloride content of 90 mol% or more, grains with a uniform structure with a small distribution of halogen composition within the grains are used. It is also preferable to use It is also effective to further increase the silver chloride content of the silver halide emulsion for the purpose of reducing the amount of replenishment of the processing solution.
In such cases, the silver chloride content is 98 mol% to 10
Emulsions of nearly pure silver chloride, such as 0 mol %, are also preferably used. Average grain size of the silver halide grains contained in the silver halide emulsion used in the present invention (the grain size is defined as the diameter of a circle equivalent to the projected area of the grain, and the number average thereof is taken)
is preferably 0.1-2n, and their particle size distribution has a coefficient of variation (I! standard deviation of particle size divided by average particle size) of 20% or less, preferably 15% or less. I prefer the one that loses. At this time, in order to obtain a wide latitude, it is preferable to blend the above-mentioned monodispersed emulsions in the same layer or to apply multilayer coating. The shape of silver halide grains contained in photographic emulsions is regular (cubic, tetradecahedral, or octahedral).
lar) those with crystal shapes, those with irregular crystal shapes such as spherical, plate-like, etc.
Alternatively, a combination of these can be used. Furthermore, it may be composed of a mixture of crystals having various crystal forms. In the present invention, it is preferable that the particles having the above-mentioned regular crystal form be contained in an amount of 50% or more, preferably 70% or more, and more preferably 90% or more. In addition to these, emulsions in which tabular grains with an average aspect ratio (circular diameter/thickness) of 5 or more, preferably 8 or more, account for more than 50% of the total grains as a projected area can also be preferably used. The silver chlorobromide emulsion used in the present invention is P. Chisie by Glafkides
et Physique PhoLographjq
ue (published by f'aul Monte 1, 1967)
,G. F. PhoLo-8rapl by Duffin
+ic Emulsion Che+sisLry (
Focal Press, 1966), V.
L. Making a by Zemekman at at
ndCoating Photographic Es
uldion (published by Focal Press, 196
4). In other words, any of the acidic method, neutral method, ammonia method, etc. may be used, and the method for reacting the soluble silver salt and the 7-soluble halogen salt may be any method such as one-sided mixing method, simultaneous mixing method, or a combination thereof. You may also use A method in which particles are formed in an atmosphere containing excess silver ions (so-called back-mixing method) can also be used. As one type of simultaneous mixing method, a method in which pjlg in the liquid phase in which silver halide is produced can be kept constant, that is, a so-called controlled 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. Various polyvalent metal ion impurities can be introduced into the silver halide emulsion used in the present invention during the process of emulsion grain formation or physical ripening. Examples of compounds to be used include salts of cadmium, zinc, lead, thallium, etc., or salts of Group I elements such as iron, ruthenium, rhodium, palladium, osmigem, iridium, platinum, etc. be able to. In particular, the above Group Ⅰ elements can be preferably used. The amount of these compounds added varies over a wide range depending on the purpose, but is preferably 10-' to 10' t mol based on the silver halide.The silver halide emulsion used in the present invention usually contains chemical and spectral enhancement. Regarding chemical enhancement methods, sulfur enhancement typified by the addition of unstable sulfur compounds, noble metal sensitization typified by gold sensitization, or reduction enhancement can be used alone or in combination. Compounds used for chemical sensitization can be found in the lower right column of page 18 of JP-A-62-215272.
The method described in the upper right column of page 22 is preferably used. Spectral amplification is carried out for the purpose of imparting spectral intensity in a desired light wavelength range to the emulsion of each layer in the optical material of the present invention. In the present invention, it is preferable to add a spectral brightening dye that absorbs light in a wavelength range corresponding to the desired spectral brightness. Spectral sensitizing dyes used at this time include, for example, F, M. He by llarmer
terocyclic compoundsCyanl
ne dies and related c
compounds (John11i1ey & S
ons (New York+London),
(1964). Examples of specific compounds are described in the above-mentioned Japanese Patent Application Laid-Open No. 62-215.
Those described in the upper right column of page 22 to page 38 of the specification of No. 272 are preferably used. The silver halide emulsion used in the present invention has the following properties:
Alternatively, various compounds or their precursors can be added for the purpose of stabilizing photographic performance. These are generally called photographic stabilizers. As specific examples of these compounds, those described on pages 39 to 72 of the specification of JP-A-62-215272 mentioned above are preferably used. The emulsion used in the present invention is either a so-called surface latent image type emulsion in which a latent image is formed mainly on the grain surface, or a so-called internal latent image type emulsion in which a latent image is mainly formed inside the grain. Also good. When the present invention is applied to a color photosensitive material, the color photosensitive material includes a yellow coupler, a magenta coupler, and a magenta coupler, which each produce yellow, magenta, and cyan colors by coupling with an oxidized product of an aromatic amine color developer. Cyan coupler is usually used. Cyan couplers, magenta couplers and yellow couplers preferably used in the present invention have the following one-shell formulas (1), (It), (III), (IV) and (V).
This is shown in .

General formula (1) 0H General formula (II3 0H General formula (V) yg General formula (I[I) R, -shell formula (IV) Moon [However, in general formulas (1) and (n), R,, h
and R, represents a disubstituted or unsubstituted aliphatic, aromatic, or heterocyclic group; R, R, and 1 represent a hydrogen atom, a halogen atom, an aliphatic group, an aromatic group, or an acylamino group; , is R! May also represent a group of nonmetallic atoms forming a nitrogen-containing 5- or 6-membered ring with Yl, Y
! represents a hydrogen atom or a group that can be separated during a coupling reaction with an oxidized form of a developing agent. ] R in formula (II) 1a is preferably an aliphatic group, such as a methyl group, an ethyl group, a propylene group,
Examples include a Kano group, a butyl group, a pentadecyl group, a Lert-butyl group, a cyclohexyl group, a cyclohexylmethyl group, a phenylthiomethyl group, a dodecyloxyphenylthiomethyl group, a butanamidomethyl group, a methoxymethyl group, and the like. Preferred examples of the cyan coupler represented by formula (1) or (It) are as follows. -a In formula (1), preferred R is an aryl group,
It is a cyclic group such as a halogen atom, an alkyl group, an alkoxy group, an aryloxy group, an acylamino group, an acyl group,
Carbamoyl group, sulfonamide group, sulfamoyl group, sulfonyl group, sulfamide group, oxycarbonyl group, cyano group, W. It is even more preferable that the aryl toxin is a substituted aryl toxin. In general formula (1), when R and R do not form a ring, R is preferably a substituted or unsubstituted alkyl group or aryl group, particularly preferably a substituted aryloxy-substituted alkyl group, and R , is preferably a hydrogen atom. -a In formula (lm), R4 is preferably a substituted or unsubstituted alkyl group or aryl group, particularly preferably a substituted aryloxy W-substituted alkyl group. In the general formula (II), R preferably has 2 to 15 carbon atoms.
It is a methyl group having an alkyl group and a substituent having one or more carbon atoms, and the substituent is preferably an arylthio group, an alkylthio group, an acylamino group, an aryloxy group, or an alkyloxy group. In the one-shell formula (It), R is more preferably an alkyl group having 2 to 15 carbon atoms, particularly preferably an alkyl group having 2 to 4 carbon atoms. -a In formula (It), R & is preferably a hydrogen atom or a halogen atom, with chlorine and fluorine atoms being particularly preferred. Preferred Y and Y in general formulas (1) and (II) are respectively a hydrogen atom, a halogen atom,
These are alkoxy groups, aryloxy groups, acyloxy groups, and sulfonamide groups. In the 1C formula (I[[), R
, and R represent an aryl group; represents a hydrogen atom, an aliphatic or aromatic acyl group, an aliphatic or aromatic sulfonyl group, and Y represents a hydrogen atom or a leaving group. The substituent to be taken is the it substituent 1? , and two or more z t
When au is present, they may be the same or different. R.
is preferably a hydrogen atom, an aliphatic acyl group or a sulfonyl group, and particularly preferably a hydrogen atom. Preferred V is of the type that leaves off with either sulfur, oxygen or nitrogen atoms, such as those described in U.S. Pat. No. 4,351,
Particularly preferred are sulfur atom dissociative types such as those described in No. 897 and International Publication No. WO 88/04795. In formula 1a (IV), R1. represents a hydrogen atom or a substituent. Y4 represents a hydrogen atom or a leaving group, and particularly preferably a halogen atom or a arylthio group. Za, Zb
and Zc is methine, IttA methine, .N1 or -N
ll-, one of the Za-Zb bond and the Zb-Zc bond is a double bond, and the other is a single bond, Zb
The case where the -Zc bond is a carbon-carbon double bond includes the case where it is part of an aromatic ring. l? 1. Or, when Y4 forms a dimer or more multi-I body, or when Za, Zb or Zc is a substituted methine, this includes the case where a dimer or more multimer is formed with the iWIA methine. Type 1a (
Among the birazoloazole couplers represented by IV), the imidazo(1,g-b)pyrazoles described in U.S. Pat. is preferred, and U.S. Pat.
, 540,654, pyrazolo (1,5-b) (
1,2.4) Triazoles are particularly preferred. In addition, a branched alkyl group as described in JP-A-61-65245 is directly connected to the 2, 3, or 6-position of the birazolotriazole ring to create a birazolotriazole coupler, which is described in JP-A-61-65246. birazoloazole couplers containing a sulfonamide group in the molecule, alkoxyphenyl sulfonamide ballast group omotubirazoroazole couplers as described in JP-A-61-147254, and European Patent Publication No. 226. It is preferable to use a birazolotriazole coupler having an alkoxy group or an aryloxy group at the 6-position as described in , No. 849 and No. 294.785. In general formula (V), Rl+ represents a halogen atom or an alkoxy group, and RI! represents a hydrogen atom, a halogen atom, or an alkoxy group. A is -NHCOR l 3, (
C- 1 ”) -N}ISOt-Js, -SOtNHR+3, -COO
R+s, -So! Represents N-RI3RI4. However, Rlj and R+a each represent an alkyl group. Y, represents a leaving group e Rl! and Rl3, R
The substituent for +s is the same as the substituent allowed for R1, and the leaving Mys is preferably of the type that leaves with either an oxygen atom or a nitrogen atom, and the nitrogen atom #deforming is particularly preferable. Specific examples of couplers represented by -In formulas (+) to (V) are listed below. (C-4) (C-5) (C-9) (C-6) C! +1 5 (C-7) CJs (C-13) (C-14) (C-15) (C-20) (C-21) (C-22) +13 (C-17) (C-18 ) (C-19) II Shil (M-1) (M-2) (M-3) Ct C! Shil Shil (M-4) (M-6) CI CHS (M-7) (M-13) Clls Shi! (Y-3) Ul+ (Y-4) (Y-1) (Y-2) (Y-5) (Y-6) (Y-7) (Y-8) The above general formulas (1) to (V ) is contained in the silver halide emulsion layer constituting the photosensitive layer, usually 0.1 to 1.0 mol, preferably 0.1 to 1.0 mol per 1 mol of halide.
It is contained in an amount of 1 to 0.5 mole. In the present invention, various known techniques can be applied to add the coupler to the photosensitive layer. Usually, it can be added by the oil-in-water dispersion method known as the oil protection method, in which it is dissolved in a solvent and then emulsified and dispersed in an aqueous gelatin solution containing a surfactant. Alternatively, water or an aqueous gelatin solution may be added to a coupler solution containing a surfactant to form an oil-in-water dispersion through phase inversion. Alkali-soluble couplers can also be dispersed by the so-called Fischer dispersion method. The low-boiling organic solvent may be removed from the coupler dispersion by distillation, noodle washing, ultrafiltration, or the like, and then mixed with the photographic emulsion. As a dissolution medium for such a coupler, a high boiling point organic solvent and/or a water-insoluble polymer compound having a dielectric constant (25°C) of 2 to 20 and a refractive index (25°C) of 1.5 to 1.7 is used. It is preferable to use As the high boiling point organic solvent, preferably the following general formula (A) ~
A high boiling point solvent represented by (E) is used. General formula (A) Edge. θ General formula (B) W + -Coo H, General formula (E) Ka + O 'f4x (In the formula, 1, 6 and - are each substituted or unsubstituted alkyl group, cycloalkyl group, alkenyl group, aryl group or represents a heterocyclic group, W. represents Ka., 0 Ka. or S-1, n is an integer from E to 5,
1 when n is 2 or more. may be the same or different, and in formula (E), 1 and h may form a fused ring). The high boiling point organic solvent that can be used in the present invention also has a melting point of 100'C or less and a boiling point of 140'
Compounds that are immiscible with water above °C and can be used as long as they are good solvents for couplers. The melting point of the high-boiling organic solvent is preferably 80°C or lower. High boiling point 1! The boiling point of the solvent is preferably 160°C or higher, more preferably 170°C or higher.
A grade of C or higher. For details of these high boiling point organic solvents, see JP-A-62-215272, No. 137.
It is written in the lower right column of the page to the upper right column of page 144. Additionally, these couplers can be combined with loadable latex polymers (
For example, it can be emulsified and dispersed in an aqueous hydrophilic colloid solution by impregnating it with a polymer (for example, US Pat. No. 4,203,716) or by dissolving it in a water-insoluble but organic solvent-soluble polymer. Homopolymers or copolymers described on pages 12 to 30 of International Publication No. WO 88/00723 are preferably used, and acrylamide-based polymers are particularly preferred from the viewpoint of color image stabilization. The bright light material produced using the present invention may contain a hydroquinone derivative, an aminophenol derivative, a gallic acid derivative, an ascorbic acid ms form, etc. as a color antifogging agent. Various anti-fading agents can be used in the photosensitive material of the present invention. That is, hydroquinone is frequently used as an organic anti-fade agent for cyan, magenta and/or yellow images.
-Hydroxychromans, 5-hydroxycoumarans,
Spirochromans, P-alkoxyphenols, hindered phenols centered on bisphenols, gallic acid derivatives, methylenedioxybenzenes, aminophenols, hindered amines, and silylation and alkylation of the phenolic hydroxyl groups of these compounds. Typical examples include ether or ester derivatives. Further, metal complexes such as (bissalicylaldoximato)nickel complex and (bis-N.N-dialkyldithiocarbamato)nickel complex can also be used. Specific examples of anti-fading agents are disclosed in the following patents:
It is stated in i. Hydroquinones are U.S. Patent No. 2.360.290,
Same No. 2,418.613, Same No. 2.700,453, Same No. 2.701,197, Same No. 2,728.659
No. 2,732,300, No. 2.735,76
No. 5, No. 3.982.944, No. 4,430.4
25, British Patent No. 1,363,921, U.S. Patent No. 2,710,801, U.S. Patent No. 2.816.028, etc. U.S. Patent No. 3.432.30
No. 0, No. 3,573.050, No. 3.574,6
No. 27, No. 3,698,909, No. 3.764.
No. 337, JP-A-52-152225, etc., and spiroindanes are described in U.S. Pat. No. 4,360,589, p-
Alkoxyphenols are U.S. Patent No. 2,735,76
No. 5, British Patent No. 2,066,975, Japanese Unexamined Patent Publication No. 1983-
No. 10539, Japanese Patent Publication No. 57-19765, etc., and hindered phenols are disclosed in U.S. Pat.
Gallic acid derivatives, methylenedioxybenzenes, and aminophenols are disclosed in U.S. Pat. No. 3,457.079, U.S. Pat. No. 21144, hindered amines are disclosed in U.S. Pat. No. 3,336. 1
No. 35, No. 4,268,593, British Patent No. 1.3
No. 2,889, No. 1,354.313, No. 1
．． Metal complexes are described in US Pat.
No. 050,938, British Patent No. 4,241,155, British Patent No. 2,027,731 (A), etc., respectively. The purpose of these compounds can be achieved by co-emulsifying them with the respective color couplers in an amount of usually 5 to 100% by weight and adding them to the photosensitive layer. In order to prevent the cyan dye image from deteriorating due to heat and especially light, it is more effective to introduce an ultraviolet absorber into the cyan coloring layer and the layers on both sides adjacent to it. As ultraviolet absorbers, penzotriazole compounds substituted with aryl groups (for example, U.S. Pat. No. 3,533,7
94), 4-thiazolidone compounds (e.g., U.S. Pat. No. 3,314,794, U.S. Pat. No. 3,352,
681), benzophenone compounds (e.g., those described in JP-A-46-2784), cinnamic acid ester compounds (e.g., U.S. Pat. No. 3,705,8)
No. 05, No. 3,707,395), bucdiene compounds (as described in U.S. Pat. No. 4,045,229), or benzoxide compounds (e.g., U.S. Pat. No. 3,700,455). ) can be used. UV-absorbing couplers (e.g. α
- Naphthol-based cyan dye-forming couplers) or ultraviolet-absorbing polymers may also be used. These ultraviolet absorbers may be mordanted in a specific layer. Among these, the above-mentioned aryl-substituted penzotriazole compounds are preferred. In addition, it is particularly preferable to use the following compounds together with the above-mentioned couplers. It is particularly preferred to use it in combination with virazoloazole coupler. In other words, a compound (F
) and/or a compound (G
) is preferably used simultaneously or singly in order to prevent the generation of stains and other side effects due to the reaction between the color developing agent or its oxidized product remaining in the film during storage after processing, or the coupler, to form a coloring dye. A preferred compound (F) has a second-order reaction rate constant kt (in trioctyl phosphate at 80°C) with p-anisidine of 1. Of/mol-sec~1×10
-'41! /mol・sec. Note that the second-order reaction rate constant is based on JP-A-63-1585.
It can be measured by the method described in No. 45. ? If ■ is larger than this range, the compound itself becomes unstable and may react with gelatin or water and decompose. On the other hand, if k8 is smaller than this range, the reaction with the remaining aromatic amine developing agent will be slow, and as a result, side effects of the remaining aromatic amine developing agent may not be prevented. A more preferable compound (F) can be represented by the following general formula (FT) or (Fn). Single shell type (Fl) R. -(^), -X General formula (F■) R*-Cguy Y B In the formula, R1 and R8 each represent an aliphatic group, an aromatic group, or a heterocyclic group. n represents 1 or 0. A represents a group that reacts with the aromatic amine developer to form a chemical bond, and X represents a group that reacts with the aromatic amine developer and leaves. B represents a hydrogen atom, an aliphatic group, an aromatic group, a heterocyclic group, an acyl group, or a sulfonyl group, and Y represents an aromatic amine developing agent added to the compound of FII. Represents a promoting group. Here R1 and X, Y
and R or B may be bonded to each other to form a cyclic structure. Among the methods of chemical combination with residual aromatic amine developing agents, the typical ones are substitution reactions and addition reactions. -a Regarding specific examples of compounds represented by formulas (F1) and (FII), see JP-A No. 63-158545, in the same formula No. 62, R represents an aliphatic group, an aromatic group, or a heterocyclic group. Represent. Z represents a nucleophilic group or a group that decomposes in the photosensitive material to release a nucleophilic group. In the compound represented by the general formula (G!), Z has Pearson's nucleophilicity "Clsl value (R
．． G. Pearson, et al. , J.
Am. CheeI. Soc. ．． 9jl. 319
(196B)) is preferably 5 or more, or a group derived therefrom. For specific examples of compounds represented by the 1C formula (G!), see European Patent Publication No. 255722;
Japanese Patent Application Laid-open Nos. 143048/1980, 229145/1982, and 136724/1980, preferably. On the other hand, a more preferable compound (G) that chemically bonds with the oxidized aromatic amine developing agent remaining after color development processing to produce a chemically inert and colorless compound is the following one-shell formula ( Gl). General formula (Gl) R-Z Details of the combination of the above compound (G) and compound (F) are described in European Patent Publication No. 277589. The photosensitive material produced according to the present invention may contain a water-soluble dye in the hydrophilic colloid layer as a filter dye or for the purpose of preventing irradiation or other purposes. Such dyes include oxonol dyes, hemioxonol dyes, styryl dyes, merocyanine dyes, cyanine dyes 14 and azo dyes. Among them, oxonol dye, hemioxonol dye and merocyanine dye 4 are used for 1f. As the binder or protective colloid that can be used in the emulsion layer of the light-sensitive material of the present invention, it is convenient to use gelatin, but other hydrophilic colloids can be used alone or together with gelatin. In the present invention, the gelatin may be either lime-treated or acid-treated. Details of the method for producing gelatin can be found in Arthur Vuis, The Macromolecule Chemistry of Gelatin (Academic Press, 1964). This is an alkaline aqueous solution whose main component is a class amine color developing agent.
Aminophenol compounds are also useful as color developing agents, but p-phenyl diamine compounds are preferably used, and a typical example is 3-methyl-4-
Amino-N,N-diethylaniline, 3-methyl-4-
Amino-N-ethyl-N-β-hydroxyethylaniline, 3-methyl-4-amino-N-ethyl-N-β-methanesulfonamidoethylaniline, 3-methyl-4-
Examples include amino-N-ethyl-N-β-methoxyethylaniline and their sulfates, hydrochlorides, and <p-}luenesulfonates. These compounds are used depending on the purpose2
More than one species can be used together. The color developer is a pl such as alkali metal carbonate, borate or phosphate.
It is common to include development inhibitors or antifoggants such as additives, bromide salts, iodide salts, penzimidazoles, penzothiazoles or mercapto compounds. If necessary, hydroxylamine, diethylhydroxylamine, sulfite hydrazines, phenyl semicarbazides, triethanolamine, catechol sulfonic acids, triethylenediamine (1,4-diazabicyclo[2,2.2]octane), etc. Various preservatives, solvents such as ethylene glycol, diethylene glycol, development accelerators such as benzyl alcohol, polyethylene glycol, quaternary ammonium salts, amines, dye-forming couplers, competitive couplers, sodium boron hydride, etc. Fogging agents, auxiliary developing agents such as 1-phenyl-3-virazolidone, viscosity-imparting agents, various chelating agents such as aminobolycarboxylic acids, aminobolyphosphonic acids, alkylphosphonic acids, and phosphonocarboxylic acids, e.g. , ethylenediaminetetraacetic acid,
Nitrilotriacetic acid, diethylenetriaminepentaacetic acid, cyclohexanediaminetetraacetic acid, hydroxyethyliminodiacetic acid, 1-hydroxyethylidene-1,1-diphosphonic acid, nitriloN,N,N-}rimethylenephosphonic acid, ethylenediamine-N,N, Representative examples include N'N'-tetramethylenephosphonic acid, ethylene diamine di(0-hydroxyphenylacetic acid), and salts thereof. Also, when performing reversal processing, black and white development is usually performed first, followed by color development. This black and white developer contains dihydroxybenzenes such as hydroquinone! - 3-Vyrazolidone such as phenyl-3-pyrazolidone or N
Known black and white developing agents such as aminophenols such as -methyl-p-aminophenol can be used alone or in combination. The pl+ of these color developing solutions and black and white developing solutions is 9 to 12.
It is common that The amount of replenishment of these developing solutions depends on the color photographic light-sensitive material to be processed, but is generally 3 liters or less per square meter of light-sensitive material, and by reducing the bromide ion concentration in the replenisher,
It can also be less than 0*ffi. ! When reducing the filling amount, it is preferable to prevent liquid evaporation and air oxidation by reducing the area of contact with the air in the processing tank. In addition, the amount of replenishment can be reduced by using means to suppress the accumulation of ionized ions in the developer. After color development, the photographic emulsion layer is usually bleached. Bleaching treatment may be performed simultaneously with fixing treatment (bleach-fixing treatment),
May be done individually. Furthermore, in order to speed up the processing, a processing method may be used in which bleaching is followed by bleach-fixing. Furthermore, processing in two consecutive clean-fix baths, fixing before bleach-fixing, or bleaching after bleach-fixing can be carried out as desired, depending on the purpose. Examples of bleaching agents include compounds of polyvalent metals such as iron (■), cobal} (nl), chromium (Vl), and w4 (II);
Peracids, quinones, nitro compounds, etc. are used. Typical bleaching agents include ferricyanide; dichromate; organic complex salts of iron ([[) or cobalt (I[l), such as ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, cyclohexanediaminetetraacetic acid, and methyliminonitriacetate]. Acetic acid, 1. Aminobolycarboxylic acids such as 3-diaminopropanetetraacetic acid and glycol ether diaminetetraacetic acid, or complex salts of citric acid, tartaric acid, and malic acid;
Persulfates; bromates; permanganates; nitrobenzenes, etc. can be used. Among these, aminobolycarboxylic acid iron (Ill) #f salts including ethylenediaminetetraacetic acid iron (III) complex salts and persulfates are preferred from the viewpoint of rapid processing and prevention of environmental pollution. Furthermore, aminobocarboxylic acid iron(III) complexes are particularly useful in both bleach and bleach-fix solutions. The pif of the bleach or bleach-fix solution using these aminoboricarboxylic acid iron (IIIHs salts) is usually 5.5 to 8, but it can be processed at an even lower po for faster processing. Bleach accelerators can optionally be used in the bleach, bleach-fix and prebaths thereof. Specific examples of useful bleach accelerators are found in the following specification: US Pat. Patent No. 3,893,858, West German Patent No. 1,290,81
No. 2, JP-A No. 53-95630, Research Disclosure T Hong 17.129 (July 1978), and other compounds having a mercabuto or disulfide bond; thiazolidine described in JP-A No. 50-140129 Derivatives; thiourea derivatives described in US Pat. No. 3,706,561; iodide salts described in JP-A-58-16235; polyoxyethylene compounds described in West German Patent No. 2,748,430; Polyamine compounds described in Japanese Patent Publication No. 45-8836; bromide ions, etc. can be used. Among these, compounds having a mercabuto group or a disulfide group are preferred from the viewpoint of a large promoting effect, and are particularly preferred, as described in US Pat. No. 3,893.858 and West German Patent No. 1,290.
, No. 812 and JP-A-53-95630 are preferred. Further preferred are the compounds described in US Pat. No. 4,552,834. These bleach accelerators may be added to light-sensitive materials. These bleaching and whitening accelerators are effective when bleaching and fixing color light-sensitive materials for photographic printing. Examples of fixing agents include thiosulfates, thiocyanates, thioether compounds, thioureas, and large amounts of iodide salts, but thiosulfates are commonly used, with ammonium thiosulfate being the most widely used. It can be used for As a preservative for the bleach-fix solution, sulfites, bisulfites, or carbonyl bisulfite adducts are preferred. The silver halide color photographic material of the present invention is generally subjected to a water washing and/or stabilization process after desilvering treatment.
The amount of water used in the washing process depends on the characteristics of the photosensitive material (for example, depending on the material used, such as a coupler), the application, the temperature of the washing water, the number of washing tanks (number of stages), the replenishment method such as countercurrent or forward flow, and various other conditions. Can be set over a wide range. Among these, the relationship between the number of washing tanks and the amount of water in the multistage countercurrent method is
Urnalof the Society or Mo
tion Picture and Televisi
on Engineers No. 64 SSL 248 ~2
53 (May 1955 issue). According to the multistage countercurrent method described in the above literature,
Although the amount of water used for washing can be significantly reduced, the increased residence time of water in the tank causes problems such as bacteria propagation and the resulting floating matter adhering to photosensitive materials. In the processing of the color light-sensitive material of the present invention, as a solution to such problems, the method for reducing calcium ions and magnesium ions described in JP-A-62-288838 can be used very effectively. Also, JP-A-5
Isothiazolone compounds and cyabendazoles described in No. 7-8542, chlorinated carbonicides such as chlorinated sodium isocyanurate, and other penzotriazole, Hiroshi Horiguchi, "Chemistry of antibacterial and antifungal J (1986) Sankyo Publishing, Hygiene Technology Society, ed., “Microbial sterilization, sterilization, and anti-mold technology,”
(1982) and the Japan Society of Antibacterial and Antifungal Agents (1986). The ρI1 of the washing water in the processing of the photosensitive material of the present invention is 4 to 9, preferably 5 to 8. The washing water temperature and washing time can be set variously depending on the characteristics of the photosensitive material, its use, etc.;
The temperature is preferably 30 seconds to 5 minutes at 25 to 40°C. Furthermore, the photosensitive material of the present invention can also be processed directly with a stabilizing solution instead of washing with water. In such stabilization treatment, Japanese Patent Application Laid-Open No. 57-8543
No. 58-14834, No. 60-220345
All known methods described in this issue can be used. Further, following the water washing treatment, a further stabilization treatment may be carried out; an example of this is a stabilizing bath containing formalin and a surfactant, which is used as a final bath for a color irradiation material for shadowing. Can be done. Various chelating agents and antifungal agents can also be added to this stabilizing bath.

The overflow liquid from water washing and/or stabilizing liquid replenishment can be reused in other processes such as the wL silver process. The silver halide color light-sensitive material of the present invention may contain a color developing agent for the purpose of simplifying and speeding up processing. In order to incorporate the color developing agent, it is preferable to use various precursors of the color developing agent. For example, U.S. Patent No. 3,342.59
Indoaniline compounds described in No. 7, No. 3,342.
No. 599, Research Disclosure 14,850
and the Schiff base-type compounds described in No. 15,159, No. 13. Aldol compounds described in No. 924, metal complexes described in U.S. Pat. No. 3,719,492, JP-A-53-1
The urethane compound described in No. 35628 can be woven with splashed patterns. The halogenated limited color light-sensitive material of the present invention may optionally contain various 1-phenyl-3
- Typical compounds that may contain virazolidones include JP-A-56-64339, JP-A-57-144547;
and No. 58-115438. The various processing solutions used in the present invention are used at 10°C to 50°C. Normally, the standard temperature is 33°C to 38°C, but higher temperatures can be used to accelerate processing and shorten processing time, or lower temperatures can be used to improve image quality and stability of the processing solution. It can be achieved. Furthermore, in order to reduce the silver content of the oxidizing material, a treatment using cobalt fortification or hydrogen peroxide fortification as described in West German Patent No. 2,226.770 or U.S. Pat. No. 3,674,499 may be carried out. ．． 4 hours? Example 1 A hard vinyl chloride resin (containing 12 parts by weight of TiO, a vinyl chloride monomer component of at least 50 mol% of the total monomer components, and a copolymer consisting of vinylidene chloride and methyl methacrylate) with a thickness of 160 μm and in the visible range After laminating polyethylene as shown in Tables 1 and 2 on a support with an average reflectance of 85% or more, and applying an undercoat (gelatin N), a multilayer color photographic paper with the following layer composition was created. did. The coating solution was prepared as follows.

First layer coating solution preparation Yellow coupler (ExY) 19.1 g, color image stabilizer (Cpd-1) 4.4 g and (Cpd-7) 1
．． 8 g to 27.2 cc of ethyl acetate and solvent (So1
Add and dissolve 4.1 g each of v-3) and (Solv-6),
This solution was emulsified and dispersed in 185 cc of gelatin aqueous solution containing 8 cc of 10% sodium dodecylbenzenesulfonate. On the other hand, silver chlorobromide emulsion (1180.0 mol% bromide, cubic: average grain size 0.85 μm, coefficient of variation 0
．． 08 and silver bromide 80.0%, cubic: average grain size 0.62 μm, coefficient of variation 0.07, 1 =
The following blue-sensitive sensitizing dye was added to the sulfuric acid sensitized product (mixed at a ratio of 3 (Ag molar ratio)). 5. per mole. O
A sample containing XIO-' moles was prepared. The above emulsified dispersion and this emulsion were mixed and dissolved to prepare a first layer coating solution having the composition shown below. The coating solutions for the second to seventh layers were prepared in the same manner as the first layer coating solution. As the gelatin hardening agent for each layer, 1-oxy-3,5-dichloros-}riazine sodium salt was used. The following spectral sensitizing dyes were used in each layer.

Blue emulsion layer (5.OX10-' mole per halogenated 111 monole) and (4.OX10-' mole per halogenated 111 monole) and (halogenated!Il per monole?) .O x 10-'
mol) Red-sensitive emulsion layer (halogen {0.9 x 10-' monole per IJ monole) To the red-sensitive emulsion layer, the following compound was added in an amount of 2.6 x 10-1 mol per mole of halogen If. In addition, for the blue-sensitive emulsion layer, green-sensitive emulsion layer, and red-sensitive emulsion layer,
1-(5-methylureidophenyl)=5-mercaptotetrazole per mole of each halogenated compound
．． OX10-' monore, 3. OX10-'mol, 1. O
X10-' moles of 2-methyl-5-octylhydroquinone per mole of silver halide, respectively.
0-' monole, 2 x 10-' monole, 2 x 10-t mole added. In addition, for the blue-sensitive emulsion layer and the green-sensitive emulsion layer, 4-hydroxy-6-methyl-1.3.3a,7-tetrazaindene was added at a rate of 1.2
0-"mol, 1.IX10-"mol was added. The following dyes were added to the emulsion layer to prevent irradiation. and (layer horizontal formation) The composition of each layer is shown below. The number is the coating amount (g/rrf)
represents. Silver halide emulsions represent coating amounts in terms of silver. Support polyethylene laminate JLB-tv, $147!
1 [The polyethylene on the first layer side contains a white pigment (white pigment (h) and a blue dye (ulmarine blue)] First layer (blue-sensitive layer) The above-mentioned silver chlorobromide emulsion (AgBr; 80 mol%) 0
．． 26 gelatin 1.83
Yellow Cabler (EXY) 0.
83 color image stabilizer (Cpd-1)
0.19 color image stabilizer (Cpd-7)
0.08 solvent (Solv-3)
0. 18 solvent (Solv-6)
0.18 Second layer (color mixing prevention layer) Gelatin 0.99 Color mixing prevention agent (Cpd-6) 0.08 Solvent (Solv-1) 0.
16 solvent (Solv-4)
0.08 Third layer (green layer) Silver chlorobromide emulsion (AgBr 90 mol%, cubic, average grain size 0.474, coefficient of variation 0.12, Ag
Br 90 mol%, cubic, average particle size 0.36μ
, and those with a coefficient of variation of 0.09 are mixed at a ratio of tri (Ag molar ratio)) 0. 16 gelatin
1.79 color image stabilizer (Cpd
-8) Color image stabilizer (Cpd-4) Color image stabilizer (Cpd-9) Solvent (Solv-2) Fourth i (ultraviolet absorption N) Gelatin 0.03 0.01 0.04 0.65 1. 58 Ultraviolet absorber (UV-1) 0.4
7 Color mixing prevention agent (Cpd-5) 0
．． 05 Solvent (Solv-5)
0.24 Fifth layer (red sensitive layer) Silver chlorobromide emulsion (AgBr 70 mol%, cubic, average grain size 0.49 m, coefficient of variation 0.08, Ag
Br 70 mol%, cubic, average particle size 0.34 m
, and those with a coefficient of variation of 0.10 are mixed at a ratio of }l (Ag molar ratio) 0. 23 gelatin
1.34 cyan coupler (EX
C) 0.30 color image stabilizer (Cp
d-6) 0. 17 color image stabilizer (Cpd-7) 0.40 solvent (
Solv-6) 0.20 Sixth layer (ultraviolet absorption layer) Gelatin 0.53 Ultraviolet absorber (UV-1) 0.16 Color mixture prevention agent (Cpd-5) 0.02
Solvent (SOIV-5) 0.
08 Seventh N (retention layer) Gelatin polyvinyl alcohol scum (denaturation degree 17%) Liquid paraffin (Cpd-1) Color image stabilizer 1.33 Lyle modified copolymer 0.17 0.03 (Cpd-2) Color image stabilizer (Cpd-4) Color image stabilizer (Cpd-9) Color image stabilizer CZ ([IV-1) Ultraviolet absorber (Cpd-5) Color mixture inhibitor 0■ (Cρd-6) Color image stabilizer 2:4 mixture (weight ratio) of the agent (Cpd-7) Color image stabilizer -FCIlt-CH}t-CONHCnll*(t) 4:2;4 mixture (weight ratio) with an average molecular weight of 80,000 ( Solv-1)f@ Solv-2) 2:1 mixture of solvents (weight ratio) (Solv-3) Solvent (Solv-4) Solvent (Solv-5) Solvent COOCJ+t (CHt) @ COOCtH+q (Solv-6 )solvent? sHth C}ICH (CI+■), COOC. I＋■＼
/ (ExY) Yellow Cabler C! II S CExC) Cyan coupler 1: mixture (mole ratio) (ExM) Magenta coupler 1: 1 mixture (mole ratio) Below +. b First, a sensitometer (manufactured by Fuji Photo Film Co., Ltd.,
A FWH model (light source color temperature 3200°K) was used to provide gradation exposure of a three-color separation filter for sensitometry. The exposure at this time was carried out so that the exposure time was 0.1 seconds and the light amount was 250 CMS. The exposed sample was processed using an automatic processor using the following processing steps and processing solution composition. LILTJl Star 11 1 Ship 11 ■Color development 37°C 3 minutes 30 seconds bleach fixing 3
3°C 1 minute 30 seconds water washing 24-3
Dry for 3 minutes at 4℃ 70-80
°C for 1 minute The composition of each treatment solution is as follows. Sadate Niri l water discharge 800
ddiethylenetriaminepentaacetic acid 1.0 g
Nitrilotriacetic acid 2.0 g Benzyl alcohol 15 m Diethylene glycol 10 d Sodium sulfite
2.0g potassium bromide
1.0 g potassium carbonate
30 g N-ethyl-N-(β-methanesulfonamidoethyl)-3-methyl-4-aminoaniline sulfate 4.5 g hydroxylamine sulfate 3.0 g optical brightener (W)
IITRX 4B, manufactured by Sumitomo Chemical) Add 1.0g water and make 1000II1p}I (2
5℃) 10.251 feet of water sprinkling 400
dAmmonium thiosulfate (70%) 150
trl sodium sulfite 18 g
Iron ethylenediaminetetraacetate (I[l) Ammonium 55 g Disodium ethylenediaminetetraacetate 5g Add water
1000 agpl+ (25
゜C) 6.70 As mentioned above, the adhesion between the emulsion layer and the support was tested before and after the color development process, and it was found that the thickness of the polyethylene was 5μ to 35μ and the lamination temperature was 300μ. Adhesion improved when the temperature was above °C. (Table 1, Table 2) Table 1 Comparison of adhesion *・・・Good adhesion, but poor suitability for embossing Table 2 Comparison of adhesion **・・・Polyethylene decomposition It happens. In the adhesion test, the sample was scratched with a needle and then rubbed with rubber, and a sensory test was performed to see how well the film peeled off. × indicates poor, Δ indicates slightly poor, and O indicates good.

Example 2 A multilayer color photographic paper was prepared using the support shown in Example 1 and having the layer structure shown below.

The coating solution was prepared as follows.

First layer coating liquid preparation Yellow coupler (ExY) 19. 1 and color image stabilizer (Cpd-1) 4.4 and color image stabilizer (Cpd-7
) 0.7 g, 27.2 cc of ethyl acetate and solvent (S
olv-3) 8.2 g was added and dissolved, and this solution was
The mixture was emulsified and dispersed in 18.5 cc of a 10% aqueous gelatin solution containing 8 cc of sodium dodecylbenzenesulfonate.

On the other hand, silver chlorobromide emulsion (cubic, average grain size 0.88μ
A 3:7 mixture of m and 0.70 μm (silver molar ratio). The coefficient of variation of particle size distribution is 0.08 and 0.10.
, each emulsion contains 0.2 mol% of silver cobromide locally on the grain surface)
The following blue-sensitive sensitizing dyes were added at 2.0% per mole of silver for large-sized emulsions, respectively. Add 10-' mol of OX,
For small size emulsions, 2.5X10-
A sample was prepared in which sulfur sensitization was carried out after adding 'mol. The above emulsified dispersion and this emulsion were mixed and dissolved to prepare a first coating solution having the composition shown below. The coating solutions for the second to seventh layers were prepared in the same manner as the first layer coating solution. As the gelatin hardening agent for each layer, l-oxy-3,5-dichloro-s-}riazine sodium salt was used. The following spectral brightening dyes were used in each layer. Blue-sensitive emulsion layer Green-sensitive emulsion layer (per mole of halogenated 11, 4.OX10-' mole for large size emulsions, 5.OX10-' mole for small size emulsions)
．． 6 X 10-' mol) and (2.OX 10-' mol each for large-sized emulsions and 2.5 X 10-' mol each for small-sized emulsions per mole of silver halide) ( per mole of silver halide, for large size emulsions ?.OX10-' mole and for small size emulsions 1.OX10-' mole) Red-sensitive emulsion layer: 8.5xlO- per mole of silver 'Mole, 7.7XI
O-' moles, 2.5X10-' moles were added. The following dyes were added to the emulsion layer to prevent irradiation. (per mole of halogenated If, 0.9X10-' mole for large emulsions and 1 mole for small emulsions)
．． IX10-' moles) For the red emulsion layer, the following compounds were halogenated 1
1 2.6 x 10-' moles were added per mole.
Also, 1-(5-methylureidophenyl)-5-mercabutotetrazole is added to each of the blue-sensitive emulsion layer, green-sensitive emulsion layer, and red-sensitive emulsion layer (layer structure) The composition of each layer is shown below. ．． The number is the coating amount (g/+rf)
represents. The silver halide emulsion represents the coated amount in terms of silver.

Support polyethylene laminate paper [The polyethylene on the first layer side contains a white pigment (Tidy) and a bluish dye (ulmarine)] First layer (Seidaku 71) Said silver chlorobromide emulsion 0.30 Gelatin 1.86 Yellow Coupler (ExY) 0.82 Color image stabilizer (Cpd-1) 0.19 Solvent (Solv-3) 0.35
Color image stabilizer (Cpd-7) 0.
06 Second IW (color mixing prevention layer) Gelatin 0.99 Color mixing prevention agent (Cpd-5) 0.08 Solvent (Solv-1) 0.1
6-medium (Solv-4)
0.08 tertiary N (green sensitive layer) Silver chlorobromide emulsion (cubic, 1:3 mixture of one with an average grain size of 0.55 μm and one with an average grain size of 0.39 μm (Ag molar ratio). Grain size distribution The coefficient of variation is 0.10 and 0.08,
Each emulsion contained 0.8 mol% of 8gBr locally on the grain surface) 0. 12 gelatin
1,24 Magenta Kabra ([!
xM) 0.20 Color image stabilizer (Cpd-3) Color image stabilizer (Cpd-4) 0.15 0.02 Fourth layer (ultraviolet absorption IW) Gelatin 1.58 Ultraviolet absorber (UV-1) 0 .47 Color mixing prevention agent (Cpd-5) 0.05
Solvent (S01ν-5) 0.
24 No. 551 (Red Sensation Jl) Silver chlorobromide emulsion (cubic, 1=4 mixture (8 g molar ratio) of one with an average grain size of 0.58n and one with an average grain size of 0.45n. Variation in grain size distribution The coefficients are 0.09 and 0.11,
Each emulsion contains AgBrO. (6 mol% was locally contained on a part of the particle surface) 0.23 gelatin
1.34 cyan coupler (ExC
) 0.32 color image stabilizer (Cpd
-6) 0. 17 color image stabilizers (
Cpd-8) 0.04 color image stabilizer (Cpd-7) Solvent (Solv-6) Sixth N (ultraviolet absorption FJ) Gelatin ultraviolet absorber (UV-1) Color mixing inhibitor (Cpd-5) Solvent (Solv -5) Seventh layer (protective layer) Gelatin polyvinyl alcohol scum (denaturation degree 17%) Liquid paraffin 0.40 0.15 0.53 0. l6 0.02 0.08 1.33 1:1 mixture (molar ratio) with Lyle-modified copolymer 0.17 0.03 (EXM) Magenta coupler (ExY) 1:1 mixture (molar ratio) of yellow coupler (EχC) Cyan coupler R””CtHs and C4H! A 2:4:4 mixture (by weight) of Ce and 0■ (Cpd-1> Color image stabilizer (Cpd-6) 2:4:4 mixture (weight ratio) of Ce and 0) (Cpd-3) Color image stabilizer (Cpd-5) Color mixture prevention agent 0■ (Cpd-4) Color image stabilizer (Cpd-2) Color image stabilizer (Cpd-7) Color image stabilizer {CHz-Cll?=; CON} ICJw (n) Average molecular weight 60,000 (Cpd-8) Color image stabilizer +114 0H (Cpd-9) Color image stabilizer (IJV-1) Ultraviolet absorber: 2:4 mixture cap 1 ratio) (Solν-01 2:1 mixture (volume ratio) (Solv-3) t8 Solvent (Solv-4) Solvent (Solv-5) Solvent COOCJ+q ?CHg)s 蕃COOCIII■ ? First, each sample was exposed to light according to the method described in Example 1. Samples that had been exposed to n-light were subjected to continuous processing (running test) using a paper processing machine until twice the capacity of the color development tank was replenished in the next processing step. Toro Yueit Ikki Tomo ■Fork standing゜LヱL 1 color development
35℃ 45 seconds 161d l? ffi bleach fixing 30-35"C 45 seconds 215d l7
N rinse ■ 30~35°C 20 seconds - 10
1 Rinse 0 30-35℃ 20 seconds ■ 20
f Rinse■ 30-35℃ 20 seconds 350d
10 ffi drying 70 to 80°C for 60 seconds The amount of replenishment was per photosensitive material (3 tank countercurrent method from rinse ■ to ■ was used.) The composition of each processing solution was as follows. Left standing 21 statue hill LヱL hill and L standing water
800 m 800
ml ethylenediamine-N,N,N,N-tetramethylenephosphonic acid 1.5 g 2.0 g
Triethanolamine Sodium chloride Potassium carbonate N-Ethyl-N-(β-methanesulfonamidoethyl)-13-methyl-4-A-minoaniline sulfate N,N-bis(carboxymethyl)hydrazine Optical brightener (WIIITll' X 4B, 8.0 g 1.4 g 25 g 5. (} g 5.5 g Add water to 1000 mtρH (25
℃) 10.05tE1 pair! tjfL
C tank solution and refill solution are the same) Ammonium hydrothiosulfate (70%) Sodium sulfite Iron ethylenediaminetetraacetate (1) Ammonium ethylenediaminetetraacetic acid disodium 12.0 g 25 g 7, Og 7.0 g iooom 10.45 Ammonium Add water to 1000 PH
(25℃) 6.0 14 tank (tank liquid and replenisher are the same) Ion exchange water (calcium and magnesium are each 3pp
m1 or less) As mentioned above, when the adhesion between the emulsion layer and the support was tested before and after the color development process, it was found that the thickness of the polyethylene was 5 μm to 35 μm, and the lamination temperature was 300 μm.
``Adhesion improved when the temperature was C or higher. (Table 3, Table 4
) Table 3 Comparison of adhesion of polyethylene 2 μ 5 μ 10 μ
30μ 45μ 50μ Thickness 400 d 100 d lT g *・・・Good adhesion, but poor embossing suitability 55 g 5 g Table 4 Comparison of adhesion laminates 200°C 250°C
300 °C 350 °C 400 Temperature °C Procedural amendment (voluntary) **・・・Polyethylene decomposition occurs. Similar results were obtained when using polypropylene, boestyrene, polyethylene-vinyl acetate copolymer resin, polyethylene-acrylic acid copolymer resin, or polyethylene-ethyl acrylate copolymer resin instead of polyvinyl chloride as the support (thermoplastic resin). is obtained.

(Effects of the Invention) The present invention provides a photographic material that has embossing suitability, excellent image sharpness, little color unevenness, and improved adhesion between the support and the silver halide emulsion layer. ．． Patent applicant: Fuji Photo Film Co., Ltd. 1. 2. 3.

Claims (5)

[Claims] (1) A photographic material characterized by having a polyolefin resin layer laminated on at least one surface of a thermoplastic resin, and further having a photosensitive silver halide emulsion layer thereon. (2) The photographic light-sensitive material according to claim (1), wherein the polyolefin resin layer has a thickness of 5 to 35 μm and is extrusion laminated at a temperature of 300° C. or higher. (3) The photographic material according to claim (2), wherein the polyolefin resin layer contains 6 to 15 parts by weight of titanium oxide. (4) The photographic material according to claim (1), (2) or (3), wherein the thermoplastic resin is a vinyl chloride resin. (5) The photosensitive silver halide emulsion layer contains a color coupler that forms a dye by coupling with an oxidized product of an aromatic primary amine color developer. The photographic material according to any one of (4).