JPH061351B2 - Photographic material - Google Patents

Description

The present invention relates to a photographic light-sensitive material, and more particularly to a photographic light-sensitive material using a support having a film cured by electron beam irradiation. The present invention can be suitably used, for example, as a photographic printing paper.

[Prior Art and Problems Thereof] Conventionally, this type of material, for example, a photosensitive material for photographic printing paper in which the support base material is paper includes a material in which the surface of the paper base material is coated with a polyolefin resin. However, this has been widely used in recent years in order to cope with speeding up of photographic processing.

The polyolefin resin contains an inorganic white pigment such as titanium oxide or calcium carbonate in order to enhance the whiteness and hiding power of the support, the resolution after coating the photographic emulsion, and the sharpness.

By the way, when forming a coating of a polyolefin resin, it is necessary to melt the resin at a high temperature of approximately 280 to 340 ° C. A large amount of the above-mentioned inorganic white pigment cannot be added to the polyolefin resin melted at high temperature, and the dispersibility is poor under such conditions. For this reason, a sufficiently satisfactory sharpness of the photographic image cannot be obtained.

Under such circumstances, attempts have been made to disperse a large amount of inorganic pigments in a polyolefin resin by using a dispersant.

For example, JP-A-51-6531 and JP-A-52-35625.
No. 55-108658, No. 55-113039.
No. 55-113040 and the like disclose techniques for coating the surface of titanium oxide particles with various compounds. However, in these techniques, when the polyolefin resin is melted at a high temperature, the tie outlet end of the extruder is contaminated by these additives, and a concave line stripe is formed on the surface of the molten film. There is a problem that it becomes a groove on the surface and uneven coating of the emulsion occurs.

Further, JP-A-57-151942 proposes that an alkyl titanate is used in place of the above-mentioned additive (which functions as one kind of dispersant). Be improved.

However, in this case, the pigment treated with the alkyl titanate is insufficient in sharpness because it contains only about 10 to 20 wt% in the molten polyolefin resin, and free alkyl titanate that is not bound to the pigment is not obtained. It is liable to occur, and when it melts, it causes thermal decomposition and smoke in the coating, and it adheres to the cooling rolls to make it impossible to obtain a smooth film surface.

As described above, when a conventional polyolefin resin coating contains a pigment, sufficient sharpness has not yet been obtained.

In order to solve the above problems, JP-A-57-27257 has been proposed.
No. 57-49946 proposes a photographic support having a coating layer obtained by applying a composition curable by electron beam irradiation onto a paper base material and irradiating the composition with an electron beam to cure the composition. .

When such a support is used, the content of the inorganic white pigment is
It can be increased up to 20-70wt%, and as a result, the sharpness is significantly improved compared with the polyolefin resin coating.

However, a photographic light-sensitive material obtained by coating a photosensitive layer on a coating layer cured by electron beam irradiation increases fog when it is developed after a normal storage time, which is not negligible as a product. It turned out that there is a case.

As a method for improving this, JP-A-59-124336 discloses that
Techniques have been proposed in which a barrier layer is provided between the support substrate paper and the electron beam curable lacquer layer. However, the effect of suppressing fogging is still insufficient, and a process for providing a blocking layer is required in addition to the conventional manufacturing process, which is disadvantageous in manufacturing cost.

Although the cause of fogging is not clear, the above-mentioned JP-A-5
It is presumed that one of the causes is a curable or uncured low molecular weight monomer contained in the lacquer layer in the specification of 9-124336, page 10, lines 4-12.
In order to put a photographic light-sensitive material using a support having an electron beam curing coating layer into practical use, it is desired to solve the above fog.

In addition, Japanese Patent Application No. 59-251261 discloses that the electron beam absorption
A method of reducing fogging by curing at a low dose of 0.1 Mrad or more and less than 2.0 Mrad is disclosed. However, in this technique, it is necessary to contain a certain amount or more of terminal reactive groups capable of causing a curing reaction in the electron beam curable resin composition in order not to impair the adhesiveness.
However, in order to obtain this condition, it has been necessary to use a large amount of an electron beam-curable compound containing a relatively expensive terminal reactive group in the molecule.

[Object of the Invention]

An object of the present invention is to coat an electron beam-curable composition on at least one side of a support base material, and to provide a photographic support obtained by curing with an electron beam, by coating a photosensitive layer on the cured coating layer. When a photographic light-sensitive material is formed by using a photographic light-sensitive material, there is little increase in fogging during storage, and a photographic light-sensitive material excellent in the sharpness of photographic images, the smoothness of the support surface, and the adhesion between the base material and the coating layer is provided. To do.

[Structure of Invention]

As a result of various studies by the present inventors, when curing the electron beam curable composition, the electron beam curable resin composition contains a polymerization inhibitor, the content of which is 30 with respect to the electron beam curable compound.
The inventors have found that when the content is 0 ppm or less, a cured coating layer with a small increase in fogging can be obtained without impairing the adhesiveness with a support substrate, and completed the present invention.

Since the electron beam curable resin composition of the present invention contains a polymerization inhibitor, it has good storage stability. If the polymerization inhibitor is not contained, it will polymerize and harden unless it is stored under extremely strict storage conditions, and cannot be used. In the composition of the present invention, the content of the polymerization inhibitor is 300 ppm or less based on the total amount of the electron beam curable compound, so that the adhesiveness can be improved.

That is, in the electron beam curing, since the energy level of the electron beam to be irradiated is high, it can be cured in a very short time as compared with the conventional curing by UV light irradiation and curing by heating. Therefore, it is considered that the content of the polymerization inhibitor has almost no influence on various properties after curing. However, as a result of various studies by the present inventor, the amount of the polymerization inhibitor has a great influence on the characteristics of the photographic light-sensitive material according to the constitution of the present invention, particularly the adhesiveness, and particularly when the irradiation intensity is relatively small. It was also found that when the content of the polymerization inhibitor is 300 ppm or less of the total amount of the electron beam curable compound, the adhesiveness is remarkably improved.

From the viewpoint of improving the adhesiveness, the smaller the content of the polymerization inhibitor, the better. But considering the preservation,
The content of the polymerization inhibitor is 20 ppm or more, preferably 30 ppm or more,
More preferably, it is 50 ppm or more. Also, preferably 200
It should be below ppm.

The materials that can constitute the electron beam curable composition used for obtaining the silver halide photosensitive material of the present invention will be described below.

In the present invention, as the electron beam curable compound for forming the coating layer on the support, any compound can be used as long as it is a compound curable by irradiation with an electron beam.

The compound curable by an electron beam that can be used in the present invention includes, for example, two or more unsaturated double bonds in its molecular chain, such as radicals are generated by electron beam irradiation to polymerize or crosslink to cure. A compound can be mentioned. Further, for example, cationically polymerizable compounds (in this case, combined with an initiator) shown in JP-A-59-147018, JP-A-59-32237 and the like can be mentioned.

As described above, the compound that is cured by an electron beam is not particularly limited, but acrylate compounds (including acrylate compounds having a urethane bond in the molecule and acrylate compounds having an epoxy bond in the molecule) and esters (similar to (Including those having a bond) and the like.
Further, particularly when a paper base material is used as the support base material,
If the added amount of the inorganic white pigment is increased, the cured coating amount may be easily embrittled. Therefore, it is preferable to select one that does not impair the flexibility peculiar to paper. The following examples can be preferably used.

1) Acrylic compounds such as acrylic polymers 1) -1 Aromatic acrylates such as aromatic monoacrylates and aromatic diacrylates (such as those used in the examples).

Aliphatic acrylates such as aliphatic monoacrylate, aliphatic diacrylate, and aliphatic triacrylate (such as those used in the examples).

1) -2 Polyester acrylate ACJ van Dostahort &
A Fan Near Boss (ACJVan Dosterhout and
A. van Neerbos), Polyester described in Double Liajson-Chim Peint. 27 (295), 135 (1980).

1) -3 Acrylate oligomer 1) -4 Epoxy acrylate Compounds disclosed in JP-A-47-13023 and JP-A-57-162713.

That is, an epoxy acrylate obtained by adding acrylic acid or other α, β unsaturated carboxylic acid to a polyfunctional epoxy compound.

Trade name: EA800, EPM
There is 800 (Shin Nakamura Chemical Co., Ltd.).

1) -5 Silicon acrylate A condensate of hydroxyethyl methacrylate with a hydroxyl group- or methoxy group-containing silicone disclosed in JP-B-48-22172 and JP-A-48-39594.

1) -6 Urethane acrylate Aromatic urethane acrylate (such as those used in the examples)
Such.

U.S. Pat. Nos. 3,864,133, 3,891,523 and 3,
912516, Japanese Examined Patent Publication No. 48-22172, JP-A No. 4-4
8-39594, JP-A-49-26337, JP-B-49-35346, JP-A-49-96043, JP-B-52-31239, JP-A-54-80394, JP-A-54-129034. JP-A-54-127994
Urethane acrylates disclosed in No.

Specifically, a urethane acrylate obtained by adding hydroxyethyl methacrylate to a polyfunctional isocyanate compound, a polyoxyalkylene bisphenol A derivative, and a urethane acrylate obtained by reacting a polyisocyanate and a hydroxyl group-containing acrylate. Examples thereof include amide urethane acrylate obtained by reacting an amide-containing compound having a group, polyisocyanate, and a hydroxyl-containing acrylate compound.

Commercially available products include Ubisan 783 and Ubisan 793 (Toray Thiokol Co., Ltd.).

2) Unsaturated polyester Japanese Patent Publication No. 48-23654, Japanese Patent Publication No. 49-23293
No. 4, Japanese Patent Publication No. 49-47103, Japanese Patent Publication No. 49-4457
2, compounds disclosed in JP-A-54-7473. Commercially available products include trade names M8030 and M8060 (both are Toagosei Chemical Industry Co., Ltd.).

3) Modified Unsaturated Polyester Urethane Modified Unsaturated Polyester In particular, the compound disclosed in JP-B-48-14667.

Acrylic Urethane Modified Unsaturated Polyester In particular, the compounds disclosed in Japanese Patent Publication No. 48-14790.

Liquid unsaturated polyester having an acrylic group at the terminal, especially US Pat. No. 3,455,802, US Pat.
The compounds disclosed in No. 2.

4) Acrylates of ester oligomers such as oligoester monoacrylate, oligoester diacrylate, oligoester triacrylate, etc. As this compound, the following can be preferably exemplified.

Maronix M-102, M-150, M-152, M
-5400, M-5500, M-5700, XM-10
1, XM-111, XM-113, XM-117, X2
15A (all are trade names, Toagosei Chemical Industry Co., Ltd.
Made).

5) Butadiene-based polymer Urethaned 1,2-polybutadiene disclosed in JP-A-50-123187 and JP-A-54-14809
Examples thereof include modified polybutadiene obtained by adding a monoester compound to epoxidized polybutadiene disclosed in No. 4 and further adding an aliphatic lower carboxylic acid.

In addition, it contains hydrogenated or non-added polybutadiene in the molecular chain, electron beam reactive group (vinyl group, epoxy group, isocyanate group, etc.) or non-reactive group (hydroxyl group, alkyl group,
A compound containing a carboxyl group, a COOR group (where R is an alkyl group, etc.) can be used. Examples of such compounds include NISSO PB B series, G series, C series, BI series, GI series, CI series resins, TE resin, maleated PB resin, and BF.
Resin (Nippon Soda Co., Ltd.), Poly bd series, HTP-
4, HTP-9, HTP-5MLD, HTP-9PA,
R-45HT, R-45M, R-45MA, R-45E
Commercially available products such as PT, R-45EPI, R-45ACR (Idemitsu Petrochemical Co., Ltd.) are also available.

6) Electron beam curable polymer containing carbon ring or heterocyclic bond in the molecular chain Such a polymer has a terminal reactive group capable of undergoing a curing reaction by two or more electron beams in the molecule and has a molecular chain. An electron beam curable compound containing a carbon ring or a heterocyclic bond can be used. Preferable examples of the ring structure of this compound include a phenylene ring, a spirane ring and a triazolone ring. Also a cycloalkylene ring,
Bicycloalkylene ring, naphthalene ring, furan or condensed furan ring, thiophene or condensed thiophene ring, pyrrole or condensed pyrrole ring, pyran or pyrone ring, pyridine ring, quinoline or isoquinoline ring, azole ring and azine ring are also preferable.

These compounds are, for example, NK ester EA-800, EP
M-800, A-BPE-4, BPE-200 (Shin-Nakamura Chemical Co., Ltd.), Photomer 4028 (DiamondShamroc
k), M210 (Toagosei Chemical Industry Co., Ltd.), R-60
Commercial products such as 4 (Nippon Kayaku Co., Ltd.), M315, M325 (Toagosei Chemical Industry Co., Ltd.) are also available.

The above compounds may be used alone or in combination of two or more.

The number average molecular weight is preferably about 500 to 20000,
More preferably, it is about 1000 to 10000.

In addition, for the purpose of adjusting the viscosity of the composition, the curing characteristics, the physical properties of the cured layer and the like, in particular, for the purpose of imparting flexibility, it is possible to use a monomer having an unsaturated bond mixed with the above compound. preferable.

The mixing ratio with the monomer is arbitrary, for example, 5/95 to 90 /
It can be used in a wide range of 10 weight ratio range.

Any of these monomers may be mixed as long as they are copolymerizable reactive compounds, but acrylate and methacrylate monomers are particularly preferable.

The following are typical examples of the monomers to be mixed and used.

A) Polyester acrylate, polyester methacrylate Toagosei Chemical Industry Co., Ltd., trade name Aronix M610
0, Aronix M6200, Aronix M625
0, Aronix M6300, Aronix M650
0, Aronix M7100, Aronix M810
0.

San Nopco Ltd., trade name Huotomer 5007, Huotomer 5018, and Huotomer 4149.

Nippon Kayaku Co., Ltd., trade name Kayamer MANDA; Kayarat HX220, Kayarat HX620.

B) Polyurethane acrylate, polyurethane methacrylate Osaka Organic Chemical Co., Ltd., trade name Bismart 829.

Toagosei Chemical Industry Co., Ltd., trade name Aronix M12
00, Aronix M1100 Nippon Yupica Co., Ltd., trade name AC5801 Shin-Nakamura Chemical Co., Ltd., trade name NK Ester U-108
A, NK Ester U4HA Toray Thiokol Co., Ltd., trade name Ubisan 893 San Nopcoco Co., Ltd., trade name Phutomer 5007, Photomer 6008.

C) Epoxy acrylate, epoxy methacrylate Acrylic Organic Chemicals Co., Ltd., trade name Viscoat 60 San Nopco Co., trade name Phutomer 3016, Photomer 3082 Nippon Yupica Co., trade name AC5301, AC570
1, AC5702; EX9004, EX9006.

D) Silicone acrylate Compounds disclosed in JP-B-48-22172 and JP-A-48-39594.

E) Monofunctional monomer Methyl acrylate, ethyl acrylate, butyl acrylate, 2-ethylhexyl methacrylate, 2-
Hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, glycidyl methacrylate, n-
Hexyl acrylate, lauryl acrylate, etc.

The product name Photom is commercially available.
er4039 (Diamond Shamrock), etc.

F) Bifunctional monomer 1,6-hexanediol diacrylate, 1,6-hexanediol dimethacrylate, neopentyl glycol, 1,4-butanediol diacrylate, ethylene glycol diacrylate, polyethylene glycol diacrylate, pentaerythritol diacrylate , Divinylbenzene, etc.

G) Trifunctional or higher functional monomers trimethylolpropane triacrylate, trimethylolpropane methacrylate, pentaerythritol triacrylate, dipentaerythritol hexaacrylate, acrylic acid amide of ethylenediamine, and the like.

Further, for the purpose of improving flexibility and adhesiveness of the support base material, a thermoplastic resin represented by the following may be mixed and used.

(1) Cellulose derivative Nitrocellulase, Cellulose acetate dodecylate,
Ethyl cellulose, butyl cellulose, etc.

(2) Polyvinyl alcohol resin Polyvinyl alcohol, polyvinyl butyral, polyvinyl acetal and the like.

(3) Vinyl chloride-based copolymer Vinyl chloride-vinyl acetate copolymer, vinyl chloride-vinyl acetate-maleic acid copolymer and the like.

(4) Polyurethane resin (5) Unsaturated and saturated polyester resin (6) Polyamide resin (7) Low molecular weight polyolefin, low molecular weight polybutadiene, etc.

These thermoplastic resins may or may not have an acrylic modified double bond introduced therein.

These thermoplastic resins can be used, for example, in an amount of 50 wt% or less with respect to the total amount of the electron beam curable compound of the present invention and the electron beam curable monomer.

However, as described above, the amount of the polymerization inhibitor contained in the electron beam curable resin composition, relative to the total electron beam curable compound.
It should be 300 ppm or less, preferably 200 ppm or less. If it is more than 300 ppm, a large amount of electron beam irradiation is required for curing, the adhesion to the support is deteriorated, and fogging is increased, which is not preferable. Here, the polymerization inhibitor generally includes all compounds added to suppress the polymerization reaction during the synthesis of the electron beam curable compound or during the storage after the synthesis. Osamu Shimamura et al .: Free radical reaction (above), Tokyo Kagaku Dojin (1969), Chapter 1, Kimura Furuyuki: Chemistry monograph 15, Chemistry of polymer synthesis, Kagaku Doujin (1)
973) 102 pages, J Brand Wrap, E. H. Imaget: "Polymer Handbook", published by John Willie & Sons (J. Brandrup, E.
H. Immergut: Polymer Handbook) (1974), II-53 and the like, which are polymerization inhibitors (inhibitors), polymerization inhibitors (retarders), polymerization terminators (terminators) and the like.
Specifically, diphenylpicrylhydrazyl, galvinoxyl, ferdazyl, sulfur, benzoquinone derivative,
Nitro compounds, diferylamine, hydroquinone, third
Butyl catechol and the like. These may be used alone or in combination of two or more.

The polymerization inhibitor is quantified by gas chromatography analysis, high performance liquid chromatography analysis, or the like. Specifically, edited by The Japan Society for Analytical Science: Polymer Handbook, published by Asakura Shoten (1985), Chapter I-3, Vuice: "Determination of Organic Compound Method and Proceedure", John Willie・ Published by And Sons (Weiss: Determination of Organic Co
mpoundand Procedures, John Wiley and Sons) (1970),
Quantify using the method described in Chapter 21, etc.

Further, the composition for coating a cured coating layer in the present invention,
A solvent can be added if necessary.

The solvent to be used is not particularly limited and is appropriately selected in consideration of the solubility and compatibility with the electron beam curing composition.

Solvents that can be preferably used in adjusting the composition include methanol, ethanol, isopropanol, alcohols such as butanol Acetone, methyl ethyl ketone, methyl isobutyl ketone, ketones such as cyclohexanone Methyl acetate, ethyl acetate, butyl acetate, ethyl butyrate, etc. Esters Ethylene glycol dimethyl ether, ethylene glycol monoethyl ethyl, glycol ethers such as dioxane Benzene, aromatic hydrocarbons such as toluene and xylene hexane, aliphatic hydrocarbons such as heptane, and mixtures thereof.

As the inorganic white pigment in the present invention, any of titanium oxide (anatase type, rutile type), barium sulfate, calcium carbonate, aluminum oxide, magnesium oxide and the like can be used, but titanium oxide, barium sulfate and calcium carbonate are preferable. . It is also possible to improve the dispersibility by treating the surface of titanium oxide with a hydrous metal oxide, for example, a metal oxide such as hydrous alumina or hydrous ferrite.

The amount of the inorganic white pigment is preferably 25 to 250 parts by weight with respect to 100 parts by weight of the electron beam curable composition. More preferably, it is 30 to 150 parts by weight. The average particle size of the pigment is preferably 0.05 to 10 μm, more preferably
It is 0.1 to 3 μm.

In addition to the above, a blue pigment, an antistatic agent, a fluorescent whitening agent and the like may be added to the electron beam curable resin composition, if necessary.

As the support base material used in the present invention, commercially available medium-quality paper,
In addition to fine paper, a paper base made of natural pulp, synthetic pulp or a mixture thereof and various photographic base papers can be used.

Alternatively, a film in which an inorganic white pigment is dispersed in a base of polyesters or polyolefins, if necessary, may be used.

The thickness of the paper base is 80-250 μm, and the basis weight is 60-250 g.
/ M ² , more preferably 80 to 200 g / m ² , and the surface may be smooth or rough. If necessary, the surface may be subjected to various surface treatments such as corona discharge.

The electron beam curable composition for coating in the present invention is prepared, for example, as follows.

That is, the above-mentioned respective components to form the composition are all introduced into the kneader at the same time or individually. Various kneading machines can be used for kneading and dispersing the coating composition in this case, and examples of usable kneading machines include a two-roll mill, a three-roll mill, a pepper mill, a ball mill, a sand grinder, a high speed stone mill, and a high speed. There are impact mills, kneaders, homogenizers, etc.

As a coating method, for example, air doctor coating, blade coating, squeeze coating, air knife coating, reverse roll coating, transfer roll coating, cast coating, or the like is used.

The coating thickness is 1 to 100 μm, more preferably 5 to 5 μm.
The thickness is preferably 0 μm.

The coating layer of the present invention can be subjected to a smoothing treatment so as to have a mirror-finished surface, and can be provided with a mold if necessary.

In order to perform mirror finishing, the surface to be treated can be brought into contact with a mirror roll and irradiated with an electron beam from the rear surface of the roll to be cured to give a mirror finish. In addition, after pre-irradiating in advance to partially harden the surface, contact the mirror roll and peel it off.
A method of performing secondary irradiation and completely curing may be used.

Further, when applying a pattern, a desired pattern, such as a silk pattern and a fine grain surface, can be formed by using the patterning roll instead of the mirror surface roll.

The electron beam accelerator used may be, for example, an electro curtain system, a van de Graaff type scanning, a double scanning system, or the like.

Further, as the electron beam characteristics, from the viewpoint of penetrating power, preferably
It is preferable to use an electron beam accelerator of 50 to 75 KV, more preferably 100 to 300 KV so that the absorbed dose is 0.1 to 20 Mrad.

It is preferable to irradiate the electron beam in an atmosphere of an inert gas such as N ₂ , He or CO ₂ .

Further, the coating layer may be subjected to a surface treatment such as corona discharge treatment, or an undercoat layer may be separately provided on the surface of the coating layer for the purpose of improving the adhesiveness to the photographic constituent layer.

The photographic emulsion layer and the photographic light-sensitive material provided on such a coating layer may have any layer structure. Monochrome and color emulsion layers can be provided as the photographic emulsion layer. A color photographic emulsion layer can be preferably provided in the cured coating layer of the light-sensitive material of the present invention.

When applied to a color photographic light-sensitive material, the photographic light-sensitive material according to the present invention usually has three kinds of light-sensitive silver halide emulsion layers having different spectral sensitivities, and each emulsion layer includes a yellow coupler, a magenta coupler, And cyan couplers, one of each of the three couplers.

In such a case, as the combination of the photosensitive silver halide emulsion layer and the coupler, a cyan coupler is usually used in the red photosensitive silver halide emulsion layer, and a magenta coupler is further used in the green photosensitive silver halide emulsion layer. A yellow coupler is associated with each blue-sensitive silver halide emulsion layer. There is no particular limitation on the order of laminating each emulsion layer.

Any yellow, magenta and cyan couplers may be used as desired.

Preferred yellow couplers include benzoylacetanilide couplers and bivaloylacetanilide couplers. Preferred magenta couplers include 1-phenyl-3-anilino-5-pyrazolone couplers and pyrazolotriazole couplers. Preferable cyan couplers include phenol couplers. Each of these couplers is preferably contained in the silver halide emulsion layer in an amount of about 0.05 to 1 mol per mol of silver halide.

In the color photographic light-sensitive material using the present invention, in addition to the silver halide emulsion layer described above, a non-light-sensitive material such as a protective layer, an intermediate layer, a filter layer and a scavenger layer having an appropriate layer order and number of layers on the support. A conductive layer can be provided.

The silver halide contained in the silver halide emulsion layer used is any of silver iodobromide, silver chlorobromide, silver bromide, silver chloroiodobromide, silver chloride and silver chloroiodide. May be
It may be a mixture of these. These silver halides may be produced by any of the ammonia method, the neutral method, the acidic method, etc., and may be prepared by the simultaneous mixing method, the forward mixing method, the back mixing method, the conversion method or the like. Those produced may be used, and those with or without boundaries having different halogen compositions inside the silver halide grains may be effectively used.

As the binder that can be used in the constituent layers of the color photographic light-sensitive material of the present invention, gelatin such as alkali-processed gelatin or acid-processed gelatin is the most common, and a part of this gelatin and phthalated gelatin and phenylcarbamoyl gelatin are used. Derivatives such as gelatin, albumin, agar, gum arabic, alginic acid, partially hydrolyzed cellulose derivatives, partially hydrolyzed polyvinyl acetate, polyacrylamide, polyvinyl alcohol, polyvinylpyrrolidone, and copolymers of these vinyl compounds are used in combination. You can also

The silver halide emulsion used is a precious metal salt of a noble metal such as ruthenium, rhodium, palladium, iridium, platinum and gold (for example, ammonium chloroparadate, potassium chloroplatinate, potassium chloroparadide and potassium chloroaurate). Sensitization, active gelatin, sulfur sensitization with unstable sulfur compounds (eg, sodium thiosulfate), selenium sensitization with selenium compounds,
Alternatively, chemical sensitization such as reduction sensitization under the conditions of stannous salt, polyamine, etc. and low PAg can be performed.

Further, these silver halide emulsions can be optically sensitized by using various sensitizing dyes in order to impart photosensitivity in a desired light-sensitive wavelength region. Preferred sensitizing dyes that can be used at this time include, for example, US Pat.
No. 39201, No. 2072908, No. 2739149.
No. 2213995, No. 2493748, No. 25
19001, West German Patent 929080, British Patent 50
The cyanine dyes, merocyanine dyes, or complex cyanine dyes described in JP-A-5979, etc. can be used alone or in combination of two or more. Such various optical sensitizers are used for purposes other than their original purpose, such as prevention of fogging, prevention of deterioration of photographic performance due to storage of color photographic light-sensitive materials, and development adjustment (for example, gradation control). It can also be used for purposes.

Further, in the constituent layers of the color photographic light-sensitive material using the present invention, various photographic additives such as an ultraviolet absorber (for example, a benzophenone compound and a benzotriazole compound), a dye image stabilizer (for example, a phenol compound, Bisphenol compounds, hydroxychroman compounds, bisspirochroman compounds, hydantoin compounds and dialkoxybenzene compounds, etc.), stain inhibitors (for example, hydroquinone derivatives), surfactants (for example, sodium alkylnaphthalene sulfonate, Alkylbenzene sulfonic acid soda, alkyl succinic acid ester sodium sulfonate, polyalkylene compound, etc.), water-soluble anti-irradiation dye (for example, azo compound, styryl compound, oxonol compound,
And triphenylmethane compounds, etc.), hardeners (eg halogen-substituted S-triazine compounds, active vinyl compounds, ethyleneimino compounds, epoxy compounds, water-soluble aluminum salts, etc.), film physical property improvers (eg , Glycerin, polyalkylene glycols, polymer aqueous dispersion [latex] and solid or liquid paraffin) can be added.

For coating each constituent layer of the color photographic light-sensitive material on the support of the light-sensitive material of the present invention, a generally known coating method,
For example, it is applied by a method such as dip coating, roller coating, bead coating, curtain flow coating, and then dried. In order to obtain a dye image with a color photographic light-sensitive material, after imagewise exposure, color development processing is carried out if necessary. The processing step basically comprises steps of color development and bleach-fixing. In this case, even when each process is independent, two or more processes among them may be completed once by using a processing solution having those functions. Also,
If necessary, each step may be performed twice or more. During the processing step, in addition to the above, if necessary, a pre-hardening bath, a neutralizing bath, a first development (black and white development),
Various processes such as image stabilizing bath and washing with water are combined. The processing temperature is set within a preferable range depending on the light-sensitive material and processing recipe. The temperature is generally 20 to 60 ° C, but the color photographic light-sensitive material described above is particularly suitable for processing at 30 ° C or higher.

Color developing agents used for color development include various ones widely used in various color photographic processes. Particularly useful color developing agents are N, N
It is a -dialkyl-p-phenylenediamine compound and the alkyl group and phenyl group may be substituted or may not be substituted. Among them, particularly useful compounds are N, N-diethyl-p-phenylenediamine hydrochloride, N-methyl-p-phenylenediamine hydrochloride, N, N-dimethyl-p-phenylenediamine hydrochloride, 2-amino- 5-(-N-ethyl-N-dodecylamino) -toluene, N-ethyl-N-β-methanesulfonamidoethyl-3-methyl-4-aminoaniline sulfate, N-ethyl-N-β-hydroxyethyl Aminoaniline sulfate, 4-amino-3-methyl-N, N
-Diethylaniline sulfate, N-ethyl-N-β-hydroxyethyl-3-methyl-4-aminoaniline sulfate, 4-amino-N- (β-methoxyethyl) -N-ethyl-3-methylaniline- Examples thereof include p-toluenesulfonate, N, N-diethyl-4-amino-3- (β-methanesulfonamidoethyl) aniline sulfate, and the like. Of these exemplified compounds, more preferably used are N-ethyl-N-β-methanesulfonamidoethyl-3-methyl-4-aminoaniline sulfate and 4-amino-3-methyl-N, N-. Diethylaniline hydrochloride, and 4-amino-N- (β-methoxyethyl) -N-ethyl-3-methylaniline-p-toluenesulfonate, N, N-diethyl-4-amino-3.
Examples include-(β-methanesulfonamidoethyl) aniline sulfate.

Various additives can be added to the color developing solution as needed. For example, alkali metal hydroxides and carbonates, alkaline agents such as tertiary phosphate, buffering agents such as boric acid and acetic acid, thioether, 1-aryl-3-pyrazolidone, N-methyl-p-aminophenol, Development accelerator such as polyalkylene glycol, benzyl alcohol,
Organic solvents such as ethylene glycol, diethylene glycol, methanol and acetone, development inhibitors such as potassium bromide and nitrobenzimidazoles, preservatives such as sulfite, hydroxylamine, glucose, alkanolamines, polyphosphoric acid compounds, nitrilotriacetic acid There are water softeners such as.

Example of Invention

Examples of the present invention will be described below. It should be understood that the present invention is not limited to the examples below.

The materials were blended as shown in the following compositions 1 to 7 and comparative compositions 1 and 2, and kneaded with a pole mill for 20 minutes and uniformly dispersed to obtain 7 kinds of compositions and 2 kinds of comparative compositions. .

(Composition 1) (Composition 2) Composition 1 except that the content of hydroquinone is 200 ppm
Blended in the same manner as above and kneaded to obtain.

(Composition 3) Composition 1 except that the content of hydroquinone is 300 ppm
Blended in the same manner as above and kneaded to obtain.

(Composition 4) Methoxyhydroquinone was used in place of 10
A product obtained by blending and kneading in the same manner as in Composition 1 except that 0 ppm was blended.

(Composition 5) Formulated in the same manner as in Composition 1 except that 100 ppm of tert-butoxyhydroquinone was blended in place of hydroquinone,
The one obtained by kneading.

(Composition 6) Hydroquinone 100 ppm and tert-butoxyhydroquinone
A compound obtained by blending and kneading in the same manner as in Composition 1 except that 50 ppm was used.

(Composition 7) (Comparative composition 1) Composition 1 except that the content of hydroquinone was 400 ppm
Blended in the same manner as above and kneaded to obtain.

(Comparative composition 2) Epoxy acrylate, aliphatic acrylate, and trimethylolpropane triacrylate were used as unrefined products, and methoxyhydroquinone was used instead of hydroquinone at 780p.
It was obtained by blending and kneading in the same manner as in Composition 1 except that pm was blended.

Then, each of Compositions 1 to 7 and Comparative Compositions 1 and 2 was applied on one side of a paper of about 160 g / m ² with a reverse coater to give a film pressure of 25
A coating layer was formed by coating so as to have a thickness of μm.

Then, each layer made of Compositions 1 to 7 and each layer made of Comparative Compositions 1 and 2 were irradiated with an electron beam at an acceleration voltage of 150 KV so as to have an absorbed dose of 1.5 Mrad to be electron beam cured. Note that the thickness
An acceleration voltage of 150 KV was applied to each layer of the 25 μm comparative compositions 1 and 2.
Also, a sample was prepared by irradiating with an electron beam so as to have an absorbed dose of 4 Mrad and electron beam curing. An electron beam curable layer was provided on the opposite side of the paper by the same operation as above, and 11 kinds of photographic supports were prepared. One side of the 11 types of supports thus obtained was subjected to corona discharge treatment at a strength of 20 W / m ² · min, and the photographic constituent layers described below were sequentially applied and dried.
Various color photographic paper samples were prepared (the addition amount is shown per 1 m ² unless otherwise specified, and the silver halide emulsion is shown in terms of silver).

Layer 1: 2 g of gelatin, 0.042 g of blue-sensitive silver chlorobromide emulsion (silver chloride 10 mol%), and 0.83 g of the following yellow coupler (Y-1), 0.01 g of HQ-1 dissolved 0.6
A blue-sensitive emulsion layer containing g dioctyl phthalate.

Layer 2: First interlayer containing 1.2 g gelatin and 0.2 g dioctyl phthalate in 0.05 g HQ-1.

Layer 3: 1.9 g of gelatin, 0.040 g of green-sensitive silver chlorobromide emulsion (50 mol% silver chloride), and 0.42 g of the following magenta coupler (M-1), 0.015 g of HQ-1 were dissolved. 0.3
Green light-sensitive emulsion layer containing 6 g of dioctyl phthalate.

Layer 4: 1.9 g gelatin, and 0.02 g HQ-1 and 0.7.
A second intermediate layer containing 0.5 g of dioctyl phthalate in which 1 g of UV absorber (UV-1) is dissolved.

Layer 5: 1.5 g of gelatin, 0.027 g of red-sensitive silver chlorobromide emulsion (50 mol% of silver chloride), and 0.4 g of the following cyan coupler (C-1), 0.01 g of HQ-1 and 0.3 g of UV-
Red sensitive emulsion layer containing 0.35 g of dioctyl phthalate in which 1 is dissolved.

Layer 6: Protective layer containing 1.4 g of gelatin.

Each of the samples thus obtained was stored at 30 ° C. and 60% relative humidity for 3 months, subjected to optical wedge exposure, and then color-developed with the processing steps and processing solutions shown below. In addition, a part of each sample was exposed and developed 10 days after coating and drying to obtain data on the same day.

Processing step (33 ° C) Color development 3 minutes 30 seconds Drift fixing 1 minute 30 seconds Water washing 3 minutes Drying 60-80 ° C [color developing solution] Add water to make the pH 1 and add pH with sulfuric acid or potassium hydroxide.
Adjust to 10.1.

[Bleaching fixer]

Add water to make 1 and p with ammonia water or glacial acetic acid.
Adjust to H = 6.9.

The fogging density of the developed sample was measured using a Sakura color densitometer PDA-60 type (manufactured by Konishi Roku Photo Industry Co., Ltd.).

Next, the following adhesion test was performed.

(Adhesion test) An adhesive tape is attached to the developed sample, and the sample is rapidly peeled off. At that time, it is evaluated whether peeling occurs between the paper and the electron beam cured layer.

(Measurement of Fogging Density) The fogging density of the developed sample was measured using a Sakura color densitometer PDA-60 type (manufactured by Konishi Rokusha Kogyo Co., Ltd.).

The measurement results are shown in the table. As is clear from the table, the polymerization inhibitor according to the present invention is 300 p based on the total amount of the electron beam curable compound.
It was found that the photographic materials obtained by using the compositions 1 to 7 having a pm or less had good adhesiveness and little fog with time.

On the other hand, the comparative composition 1, in which the amount of the polymerization inhibitor is 400 ppm and 780 ppm,
The photographic material obtained by using No. 2 has a small electron beam absorbed dose 1.
Adhesion is poor at 5Mrad, and the electron beam absorbed dose is 4M.
It was found that rad showed a large increase in fog over time and could not be used as a photographic material.

[Effects of the Invention] As described above, according to the present invention, the increase in fog over storage is small, the sharpness of photographic images, the smoothness of the support surface, and the adhesiveness between the substrate and the coating layer are excellent. A photographic light-sensitive material is obtained.

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Claims (1)

[Claims] 1. A photographic light-sensitive material comprising a support and a photographic light-sensitive layer coated on the support, wherein the support has an electron beam-curable compound and a pigment as main components on at least one side of a substrate. To form a coating film by coating the product, having a film obtained by polymerizing and curing the coating film by irradiating an electron beam, and the electron beam curable resin composition contains a polymerization inhibitor,
A photographic light-sensitive material characterized in that the content thereof is 300 ppm or less based on the total amount of the electron beam curable compound.