JPH0685061B2 - Silver halide photographic light-sensitive material - Google Patents

Description

TECHNICAL FIELD The present invention relates to a silver halide photographic light-sensitive material, and more particularly to a silver halide photographic light-sensitive material having a cured coating layer formed by electron beam irradiation. This kind of material is used, for example, as a photosensitive material for photographic printing paper.

[Conventional technology and its problems]

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, which accelerates photographic processing. In recent years, it has been widely used in order to cope with the above.

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, the 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, JP-A-52-35625, and JP-A-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 is thermally decomposed and smokes in the coating, and it adheres to the cooling roll to cause a problem that a smooth film surface cannot be obtained.

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 and 57-499
No. 46 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 it 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, the above technique also has a problem in terms of flexibility.
That is, a photographic light-sensitive material using a support having an electron beam-cured coating layer has reduced flexibility and is easily broken,
It turns out that this can be a non-negligible photographic product.

As a method for improving this, it has been proposed to mix a monomer or polymer having flexibility with the electron beam curable composition, but the effect may not always be sufficient.

Moreover, if the flexibility is improved, there is a problem that fogging, especially fogging with time, becomes large.

In order to put the support having an electron beam curing coating layer into practical use,
There is a demand for solving the above-mentioned flexibility and the problem of fogging that is compatible with this and is difficult.

[Object of the Invention]

An object of the present invention is to provide a coating layer formed on a support with excellent flexibility, and further to significantly reduce the occurrence of fogging (especially fogging over time). Another object of the present invention is to provide a silver halide photographic light-sensitive material having a hardened coating layer.

[Structure and Action of Invention]

As a result of earnest studies, the inventors of the present invention have shown that at least one surface of a support base material of a silver halide photographic light-sensitive material is coated with an electron beam-curable composition, and the composition is cured by irradiation with an electron beam. With the formation of the electron-curable composition, the electron-curable composition contains an electron beam-curable compound containing polybutadiene in the molecular chain in an amount of 5 to 65% by weight based on the total curable compound.
The electron beam curable compound is represented by any one of the following general formulas (1) to (3).
The above objectives have been achieved.

(1) (AX) (2) (AY) n (3) (A'Y) n In the formula, (A) is polybutadiene having a hydrogenation of less than 70%,
(A ') is polyptadiene with 70% or more hydrogenation, (X)
Is an electron beam non-reactive group, (Y) is an electron beam curable functional group, n
Is an integer of 1 or more. Further, the average molecular weight of (A) and (A ') is preferably in the range of 300 to 4000. Further, (Y) is preferably an electron beam curable functional group such as a vinyl group, an epoxy group or an isocyanate group. (A)
Examples of the (X) bonded to the polybutadiene include a hydroxyl group, an alkyl group, a carboxyl group, a -COOR group (R: alkyl group), and the (A) polybutadiene has a structure to which an acid such as maleic acid is added. But it's okay.

Next, specific compound examples that can be preferably used in the present invention are shown.

These compounds are, for example, NISSO PB B series, G series, C
Series, BI series, GI series, CI series resins,
TE resin, maleated PB resin, BF resin (Nippon Soda Co., Ltd.) Poly bd series, HTP-4, HTP-9, HTP-5MLD, HTP-9PA, R
Commercial products such as -45HT, R-45M, R-45MA, R-45EPT, R-45EPI, R45ACR (Idemitsu Petrochemical Co., Ltd.) are also available. These electron beam curable compounds may be used alone or in combination of two or more.

Further, for the purpose of lowering the viscosity of the electron beam curable compound to improve the coating workability and improve the curing reactivity, another electron beam curable compound such as a monomer having an unsaturated bond (monomer) It is necessary to mix.

In the electron beam curable composition of the present invention, the electron beam curable compound containing polybutadiene in the molecular chain is 5 to 5% of all curable compounds.
It is contained in an amount of 65% by weight, preferably 10 to 60% by weight. If it is less than 5% by weight, the desired flexibility cannot be obtained, which is not preferable as a photographic support. If it exceeds 65% by weight, a large amount of energy is required to cure it, which is not preferable in practice. The mixing ratio with the monomer is arbitrary, and for example, it can be used in a wide range of 5/95 to 65/35 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 M6100,
Aronix M6200, Aronix M6250, Aronix M6
300, Aronix M6500, Aronix M7100, Aronix M8100 San Nopco Ltd., trade name Huotomer 5007, Phutomer 5018, Phutomer 4149 Nippon Kayaku Co., Ltd., trade name Kayamer MANDA: Kayarad HX
220, Kayarad HX620 B) Polyurethane acrylate, polyurethane methacrylate Acrylic Organic Chemicals Co., Ltd., trade name Bismart 829 Toagosei Chemical Industry Co., Ltd., trade name Aronix M1200,
Aronix M1100 Nippon Yupica Co., Ltd., trade name AC5801 Shin Nakamura Chemical Co., Ltd., trade name NK Ester U-108A, NK Ester U4HA Toray Thiokol Co., Ltd., trade name Ubisan 893 San Nopco Co., Ltd., trade name Huotomer 5007, Huotomer 6008 C) Epoxy Acrylate, Epoxy Methacrylate Osaka Organic Chemical Co., Ltd., trade name Viscoat 60 San Nopco Ltd., trade name Fuotomer 3016, Phutomer 3082 Nippon Yupica Co., Ltd., trade name AC5301, AC5701, AC5702: EX9
004, 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 trimethacrylate, 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 Nitrocellulose, cellulose acetate butyrate,
Ethyl cellulose, butyl cellulose, etc.

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

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

(4) Polyurethane resin (5) Unsaturated and saturated polyester resin (6) Polyamide resin and the like.

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.

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 ether, glycol ethers such as dioxane Benzene, aromatic hydrocarbons such as toluene and xylene, hexane, aliphatic hydrocarbons such as heptane, and mixtures thereof.

The support according to the present invention uses a white pigment in order to increase reflectance for use as a reflective support, and the following inorganic white pigments are typically mentioned. That is, titanium oxide (anatase type, rutile type), barium sulfate, calcium carbonate, aluminum oxide, magnesium oxide and the like can all be used. Preferred are titanium oxide, barium sulfate, and calcium carbonate. It is also possible to improve the dispersibility of titanium oxide by treating the surface thereof with a hydrous metal oxide such as a metal oxide such as hydrous alumina and 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 diameter of the pigment is preferably 0.05 to 10 μm, more preferably 0.1 to 3 μm.

By irradiating the composition obtained by mixing the above monomers and the like with an electron beam, the elastic modulus of the coating layer is 180 kg / mm ²
The following are preferable, and such a light-sensitive material has sufficient flexibility and exhibits good performance as a photographic material. When the elastic modulus is further reduced to obtain a coating layer having an elastic modulus of 120 kg / mm ² or less, better flexibility can be obtained.

As the support base material used in the present invention, commercially available medium-quality paper,
In addition to high-quality paper, paper bases 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 basis weight of the paper substrate is 60 to 250 g / m ² , and more preferably 8
It is preferably 0 to 200 g / m ² , and the surface thereof may be smooth or rough.

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 charged into the kneading machine at the same time or individually. Various kneading machines may 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 750 KV, more preferably 100 to 300 KV so that the absorbed dose is 0.1 to 20 Mrad.

It should be noted that the electron beam irradiation is preferably performed 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 the 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 of the yellow, magenta and cyan couplers used may be used if desired.

Preferred yellow couplers include benzoyl acetanilide couplers and bivaloyl acetanilide 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 contained in a silver halide emulsion layer in an amount of 0.05 to 0.05 per mol of silver halide.
It is preferably contained in an amount of about 1 mol.

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 acid 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 derivative, partially hydrolyzed polyvinyl acetate, polyacrylamide, polyvinyl alcohol, polyvinylpyrrolidone, and copolymers of these vinyl compounds 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, etc.), selenium sensitization with selenium compounds, or reduction sensitization under stannous salts, polyamines and low PAg conditions. Chemical sensitization 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.
939,201, 2,072,908, 2,739,149, 2,213,995
, 2,493,748, 2,519,001, West German Patent 929,080
Cyanine dyes, merocyanine dyes or complex cyanine dyes described in Japanese Patent No. 505,979 and the like can be used alone or in combination of two or more. Such various optical sensitizers have a purpose different from their original purpose,
For example, it can be used for the purpose of preventing fogging, preventing deterioration of photographic performance due to storage of color photographic light-sensitive materials, and controlling development (for example, gradation control).

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, dialkoxybenzene compounds, etc.),
Anti-staining agents (eg hydroquinone derivatives), surfactants (eg sodium alkylnaphthalene sulfonate, sodium alkylbenzene sulfonate, sodium alkyl succinate sulfonate and polyalkylene compounds), water-soluble anti-irradiation dyes (eg , Azo compounds, styryl compounds, oxonol compounds, and triphenylmethane compounds), hardeners (for example, halogen-substituted S-triazine compounds, active vinyl compounds, ethyleneimino compounds, epoxy compounds and Water-soluble aluminum salt, etc., film physical property improving agent (eg, glycerin, polyalkylene glycols, polymer aqueous dispersion [latex])
And solid or liquid paraffin, etc.) 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 if each process is independent,
In some cases, two or more steps may be completed once by using a processing solution having those functions. Further, in each of the steps, the treatment can be performed twice or more as needed. During the treatment process, in addition to the above,
If necessary, various steps such as a pre-hardening bath, a neutralizing bath, a first development (black and white development), an image stabilizing bath, and a water washing 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 the phenyl group may or may not be substituted. Among them, particularly useful compounds include 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-methanesulfonamide ethyl-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-
Examples thereof include methylaniline-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, 4-
Amino-3-methyl-N, N-diethylaniline hydrochloride,
And 4-amino-N- (β-methoxyethyl) -N-
Examples include ethyl-3-methylaniline-p-toluenesulfonate and N, N-diethyl-4-amino-3- (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, thioethers, 1-aryl-3-pyrazolidones, N-methyl-p-aminophenol, Development accelerator such as polyalkylene glycol, organic solvent such as benzyl alcohol, ethylene glycol, diethylene glycol, methanol and acetone, development inhibitor such as potassium bromide and nitrobenzimidazole, sulfite, hydroxylamine, glucose, alkanolamines And preservatives such as polyphosphoric acid compounds and water softeners such as nitrilotriacetic acid.

Example of Invention

 Next, the present invention will be described more specifically by way of examples.

Example 1 30 g / m ² of the following mixture on one side of a photographic base paper weighing about 160 g / m ^2.
2 was coated and then cured using an electron beam with an energy dose of 10 J / g. The composition of the mixture is as follows.

Exemplified Compound (7) 10 parts by weight Hexanediol diacrylate 45 parts by weight Trimethylolpropane triacrylate 45 parts by weight Titanium dioxide (rutile type, average particle size 0.2 μm) 50 parts by weight Example 2 Using a mixture having the following composition The same operation as in Example 1 was performed to prepare a support.

Exemplified Compound (7) 40 parts by weight Hexanediol diacrylate 30 parts by weight Trimethylolpropane triacrylate 30 parts by weight Titanium dioxide (rutile type average particle size 0.2 μm) 50 parts by weight Example 3 Implemented using a mixture having the following composition The same operation as in Example 1 was performed to prepare a support.

Exemplified Compound (7) 64 parts by weight Hexanediol diacrylate 18 parts by weight Trimethylolpropane triacrylate 18 parts by weight Titanium dioxide (rutile type average particle size 0.2 μm) 50 parts by weight Example 4 Implementation using a mixture having the following composition The same operation as in Example 1 was performed to prepare a support.

Exemplified compound (11) 40 parts by weight Hexanediol diacrylate 30 parts by weight Trimethylolpropane triacrylate 30 parts by weight Titanium dioxide (rutile type average particle size 0.2 μm) 50 parts by weight Example 5 Exemplified compound (12) 40 parts by weight hexanediol Diacrylate 30 parts by weight Trimethylolpropane triacrylate 30 parts by weight Titanium dioxide (rutile type average particle size 0.2 μm) 50 parts by weight Example 6 Exemplified compound (13) 40 parts by weight Hexanediol diacrylate 30 parts by weight Trimethylolpropane triacrylate 30 parts by weight Titanium dioxide (rutile type average particle size 0.2 μm) 50 parts by weight Example 7 Example compound (15) 40 parts by weight Hexanediol diacrylate 30 parts by weight Trimethylolpropane triacrylate 30 parts by weight Titanium dioxide (rutile type average particle size) Diameter 0.2 μm) 50 parts by weight Comparative Example 1 The mixture was prepared support The same procedure as in Example 1 by using made.

Exemplified compound (7) 4 parts by weight Hexanediol diacrylate 48 parts by weight Trimethylolpropane triacrylate 48 parts by weight Titanium dioxide (rutile type average particle size 0.2 μm) 50 parts by weight Comparative Example 2 Using a mixture having the following composition A support was prepared in the same manner as in Example 1.

Exemplified Compound (7) 80 parts by weight Hexanediol diacrylate 10 parts by weight Trimethylolpropane triacrylate 10 parts by weight Titanium dioxide (rutile type average particle size 0.2 μm) 50 parts by weight Comparative Example 3 Implemented using a mixture having the following composition A support was prepared in the same manner as in Example 1.

Fatty acid polyurethane acrylate 40 parts by weight Trimethylolpropane triacrylate 30 parts by weight Diethylene glycol diacrylate 30 parts by weight Titanium dioxide (rutile type average particle size 0.2 μm) 50 parts by weight Comparative Example 4 A mixture of Example 1 and Example 1 was used. A similar operation was performed to prepare a support.

Exemplified Compound (11) 70 parts by weight (average molecular weight 1000 TEA-1000 manufactured by Nippon Soda Co., Ltd.) 20 parts by weight of hexanediol diacrylate 10 parts by weight of trimethylolpropane triacrylate 50 parts by weight of titanium dioxide (rutile type average particle size 0.2 μm) When the comparative example was prepared under the above-mentioned conditions, curing was insufficient and cracking occurred. Therefore, JP-A-60-66247, JP-A-60-67939,
A support prepared by performing the same operation as the irradiation condition disclosed in JP-A-60-70445 was used as a comparative example.

(Coating layer elastic modulus test) In order to measure the elastic modulus of each obtained coating layer, each sample was tested.
Humidity is controlled for 10 minutes at 23 ℃ and relative humidity 55%, and the sample length is 10 × 100 (m
It was cut to a size of m ² ) and measured using Tensilon UTM-III (manufactured by Toyo Baldwin Co., Ltd.) in a range of 1 kg of full scale at a pulling speed of 100 mm / min. The results are shown in Table-1.

(Folding endurance test of support) In order to measure the folding endurance of each obtained support, each sample was tested.
The sample length is adjusted to 15 x 200 (m
It was cut to a size of m ² ) and measured with a load of 1.0 kg using a MIT folding endurance tester (manufactured by Uesima). The results are shown in Table-1.
Shown in.

(Fog Test of Photographic Layer) In order to measure the effect of each obtained support on fog, the following layers were sequentially coated on the cured coating layer to prepare five kinds of color photographic paper samples (addition amount). Represents per 1 m ² unless otherwise specified, and silver halide emulsions are shown in terms of silver).

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

Layer 2: Dissolved 1.2 g gelatin, and 0.05 g HQ-1
First intermediate layer containing 0.2 g of dioctyl phthalate.

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. Green-sensitive silver chlorobromide emulsion layer containing 0.36 g of dioctyl phthalate.

Layer 4: Second interlayer containing 1.9 g gelatin, and 0.5 g dioctyl phthalate with 0.02 g HQ-1 and 0.7 g UV absorber (UV-1) 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 A red light sensitive emulsion layer containing 0.35 g of dioctyl phthalate with UV-1 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 by 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 process (33 ℃) Color development 3 minutes 30 seconds Drift fixing 1 minute 30 seconds Water wash 3 minutes Dry 60-80 ℃ [Color developer] Pure water 800ml Ethylene glycol 15ml Benzyl alcohol 15ml Whitex BBcone 1g (Sumitomo Chemical Co., Ltd.) Fluorescent bleach) Hydroxylamine sulfate 3g 3-Methyl-4-amino-N-ethyl-N- (β-methanesulfonamidoethyl) aniline sulfate 4.5g Potassium carbonate (anhydrous) 30g Potassium sulfite (anhydrous) 2.0g Potassium bromide 0.65g 1-Hydroxyethylidene-1,1-diphosphonic acid (60%
Aqueous solution) Add 2 ml water to make 1 and add pH with sulfuric acid or potassium hydroxide.
Adjust to 10.1.

[Bleaching fixer]

Pure water 600 ml Ethylenediaminetetraacetic acid-2-sodium 2H ₂ O2
5g Ammonium sulfite (40% aqueous solution) 35ml Ammonium thiosulfate (70% aqueous solution) 150ml Ethylenediaminetetraacetic acid iron (III) ammonium 9
5g Ammonia water (28%) 25ml Add water to make 1 and pH with ammonia water or glacial acetic acid.
Adjust to 6.9.

The fogging density of the developed sample was measured using a Sakura color densitometer PPA-60 type (manufactured by Konishi Roku Photo Industry Co., Ltd.). The results are shown in Table-2.

As is apparent from the above table, the sample obtained by coating on the support using the electron beam-curable compound according to the present invention has a significantly improved strength against bending, and has a fog in the emulsion layer. It can be seen that it is significantly reduced.

Further, the sharpness of the image, the smoothness of the support, the heat resistance, the weather resistance and the adhesiveness between the paper and the cured coating layer were sufficiently satisfactory.

〔The invention's effect〕

As described above, in the silver halide photographic light-sensitive material of the present invention, the covering layer of the support is excellent in flexibility, and in the past, it was difficult to achieve compatibility with flexibility. The present invention solves the problems of the conventional light-sensitive material having an electron beam-curable coating layer, which has good photographic performance such that it can be reduced while improving it.

Claims (1)

[Claims] 1. A silver halide photographic light-sensitive material in which at least one silver halide emulsion layer is provided on a support, wherein the support has an electron beam curable composition on at least one side of a support base material. A cured coating layer is formed by coating the composition and irradiating it with an electron beam to cure the composition. The electron beam curable composition comprises an electron beam curable compound containing polybutadiene in its molecular chain. A silver halide photographic light-sensitive material containing 5 to 65% by weight of a curable compound, and the electron beam curable compound is represented by any one of the following general formulas (1) to (3). material. (1) (AY) (2) (AX) n (3) (A'Y) n In the formula, (A) is polybutadiene having a hydrogenation of less than 70%,
(A ') is polyptadiene with 70% or more hydrogenation, (X)
Is an electron beam non-reactive group, (Y) is an electron beam curable functional group, n
Is an integer of 1 or more.