JPH0685063B2 - Method for producing photographic light-sensitive material - Google Patents

Description

The present invention relates to a method for producing a photographic light-sensitive material, more specifically, an electron beam curable resin composition layer is provided on a substrate, and this layer is irradiated with an electron beam. The present invention relates to a method for producing a photographic light-sensitive material in which a photographic light-sensitive layer is provided on the support by curing it by curing.

[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, etc. 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 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, a photographic light-sensitive material obtained by applying photosensitivity to a coating layer cured by electron beam irradiation increases fog when developed after a normal storage time, and this becomes a non-negligible product. It turns out that there are cases.

As a method for improving this, JP-A-59-124336 proposes a technique of providing a blocking layer between the support base 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-59
It is presumed that one of the causes is a curable or uncured low molecular weight monomer contained in 9-124336, page 10, lines 4-12. In order to put into practical use a photographic light-sensitive material using a support having an electron beam curable coating layer, it is required to solve the above fog.

On the other hand, JP-A-57-30830, JP-A-59-177543, JP-A-59-
No. 178450, JP-A-60-17446, a technique for producing a photographic support having a coating layer by electron beam irradiation curing, which has irregularities on the surface, is proposed,
In all of these techniques, the photographic light-sensitive material in which the photographic light-sensitive layer is provided on the support has a rapid increase in fogging during storage.

[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, to cure the same with an electron beam, and to obtain a photographic support having irregularities or irregularities on the surface. When a photosensitive layer is formed on the cured coating layer to form a photographic light-sensitive material, there is little increase in fogging during storage, and the sharpness of photographic images and the adhesion between the base material and the coating layer are improved. An object of the present invention is to provide a manufacturing method capable of obtaining an excellent photographic light-sensitive material.

[Structure of Invention]

And to achieve the above-mentioned objects, the present inventors have conducted various studies, and as a result, rather than irradiating with an electron beam sufficiently so that a low-molecular monomer does not remain during curing of the electron beam-curable resin composition, rather than irradiating with an electron beam. Through the electron beam semi-transparent film that absorbs the energy of the electron beam during the curing of the electron beam curable resin composition, that is, the electron beam semi-transparent film, which sometimes absorbs 50% or more of the energy. It has been found that the fogging is significantly reduced when the electron beam curable resin composition layer is irradiated and cured, which is totally unexpected. In this case, the contact surface of the electron beam semi-transmissive film is provided with regular or irregular asperity, so that the surface has regular or irregular asperity, and the photographic light-sensitive layer is formed on the surface. It was possible to obtain a photographic support free from the problems of the prior art even when the layers were formed.

That is, the above-mentioned problems of the prior art are that the electron beam is irradiated from the electron beam curable resin composition layer side, and this electron beam irradiation is performed through an electron beam semi-permeable film that absorbs the energy of the irradiated electron beam. The electron beam semi-transmissive film absorbs 50% or more of the irradiation energy, and the surface of the electron beam semi-transmissive film has regular or irregular unevenness, and the uneven surface is It is solved by a method characterized in that it is in close contact with the electron beam curable resin composition layer during electron beam irradiation.

It may have irregularities on one side or both sides,
It is sufficient that at least the irregularities are in close contact with the electron beam curing composition layer.

When the product was manufactured by the method of the present invention, the sharpness of the photographic image, the surface smoothness, and the adhesiveness between the substrate and the coating layer were not impaired.

Incidentally, it is disclosed in JP-A-47-30730 that an electron beam permeable film is adhered on the electron beam cured resin composition layer during electron beam curing.
JP-A-51-77800, JP-A-57-30576, JP-A-57-2
Although disclosed in 1965, JP-A-57-22204, JP-A-59-68240, etc., they all have the effect of significantly reducing fogging when irradiated with an electron beam under the conditions of the present invention. That's not expected at all.

The constitution, materials used, etc. of the present invention will be further described below.

In the method for producing a photographic light-sensitive material of the present invention, an electron beam curable resin composition consisting essentially of an electron beam curable compound and a pigment is applied to at least one side of a substrate to obtain an electron beam curable resin composition layer. When irradiating this layer with an electron beam, the electron beam is irradiated onto the electron beam-curable resin composition layer through an electron beam semitransparent film that absorbs the energy of the electron beam to be cured, and in this case, the electron beam is irradiated. The surface of the semitransparent film has regular or irregular irregularities, and the irregularities are adhered to the electron beam curable composition layer at the time of electron beam irradiation to prepare a support, and the support is photographed. Providing a photosensitive layer.

Next, the materials that can constitute the electron beam curable resin composition used for obtaining the silver halide photographic light-sensitive material of the present invention will be described.

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, JP-A-59-147018, Japanese Patent Application No. 59-32237.
And the like (in this case, combined with an initiator).

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 addition amount of the inorganic white pigment is increased, the cured coating layer may be easily embrittled. Therefore, it is preferable to select a material 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 monoacrylate and aromatic diacrylate (those used in Examples) Aliphatic monoacrylate, aliphatic diacrylate, aliphatic triacrylate Aliphatic acrylates (such as those used in the examples) 1) -2 Polyester acrylate ACJ van Dostahort &
A Fan Near Boss (ACJVan Dosterhout and
A. van Neerbos), Double Liajson-Chim Peint. 27 (295), 135 (198)
The polyesters described in 0).

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

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

Commercially available products include trade names EA800 and EPM800 (Shin Nakamura Chemical Co., Ltd.).

1) -5 Silicon Acrylate Condensates of hydroxyethyl methacrylate and hydroxyl group- or methoxy group-containing silicones 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. 3864133, 3891523, 3912516, JP-B-48-22172, JP-A-48-39594, JP-A-49-26337, JP-B-49-35346, JP-A-49-96043, Japanese Patent Publication Sho 52-31239
JP-A-54-80394, JP-A-54-129034, JP-A-54-
Urethane acrylate disclosed in 127994.

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 trade names Ubisan 783 and Ubisan 793 (Toray Thiokol Co., Ltd.).

2) Unsaturated polyester Japanese Patent Publication No. 48-23654, Japanese Patent Publication No. 49-23293, Japanese Patent Publication No. 49-47103
Compounds disclosed in JP-B-49-44572 and 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 compound disclosed in Japanese Examined Patent Publication No. 48-14790.

Liquid unsaturated polyesters having an acrylic group at the end, especially compounds disclosed in US Pat. No. 3,455,802 and US Pat. No. 3,485,732.

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

MARONIX M-102, M-150, M-152, M-5400, M-5500, M
-5700, XM-101, XM-111, XM-113, XM-117, X215A (all are trade names, manufactured by Toagosei Chemical Industry Co., Ltd.).

5) Butadiene-based polymer A monoester compound is added to the elethanated 1,2-polybutadiene disclosed in JP-A-50-123187 or the epoxidized polybutadiene disclosed in JP-A-54-148094, and further Examples thereof include modified porbutadiene to which an aliphatic lower carboxylic acid is added.

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,
Carboxyl group, COOR group (where R is alkyl group, etc.)
Compounds including 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, BF resin (Nippon Soda Co., Ltd.), Poly by series, HTP-4, HTP-9, HTP-5MLD, HTP
-9PA, R-45HT, R-45M, R-45MA, R-45EPT, R-45EPI, R45ACR
Commercial products such as (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. The ring structure of this compound is preferably a phenylene ring, a spirane ring or 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, EPM-800, A-BPE
-4, BPE-200 (Shin-Nakamura Chemical Co., Ltd.), Photomer4028 (Diam
ond Shamrock), M210 (Toagosei Chemical Industry Co., Ltd.), R-
Commercial products such as 604 (Nippon Kayaku Co., Ltd.) and 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, a monomer having an unsaturated bond (monomer) is used by mixing with the above compound. Is preferred.

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

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 M630
0, Aronix M6500, Aronix M7100, Aronix
M8100 San Nopco Ltd., trade name Huotomer 5007, Huotomer 5
018, Photomar 4149.

Nippon Kayaku Co., Ltd., trade name Kayamar MANDA; Kayarad HX22
0, Kayarad HX620.

B) Polyurethane Acrylate, Polyurethane Methacrylate Osaka Organic Chemical 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 names NK Ester U-108A, NK Ester U4HA Toray Thiokol Co., Ltd., trade names Ubisan 893 San Nopco Ltd., trade name Huotomer 5007, Huotomer 6
008.

C) Epoxy Acrylate, Epoxy Methacrylate Osaka Organic Chemicals Co., Ltd., trade name Viscoat 60 San Nopco Co., Ltd., trade name Photomer 3016, Photomer 3
082 Nippon Yupika Co., Ltd., trade name AC5301, AC5701, AC5702; EA900
4, 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.

Commercially available products have the trade name Phorom
er4039 (Diamond Shamrock), etc.

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

G) Trifunctional or higher functional monomers trimellityl propane triacrylate, trimethylol propane 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 (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.

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 alcohols such as methanol, ethanol, isopropanol, butanol, acetone, methyl ethyl ketone, methyl isobutyl ketone, ketones such as cyclohexanone, methyl acetate, ethyl acetate, butyl acetate, ethyl acetate, 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.

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 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.

If necessary, a blue pigment, an antistatic agent, a fluorescent whitening agent, etc. may be added to the electron beam curable resin composition.

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 thickness of the paper base is 80-250 μm, and the basis weight is 60-250 g /
It is preferably m ² , more preferably 80 to 200 g / m ² , and the surface thereof 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 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 side 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 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 70 to 750 KV, more preferably 100 to 300 KV, and to set the absorbed dose to 0.1 to 10 Mrad.

When it is 70 KV or less, the uniformity of the electron beam in the width direction of the base material is poor at the time of electron beam irradiation, and it is difficult to obtain a uniform curing and a coating film.

In the present invention, the electron beam curable resin composition is cured by irradiating the electron beam through the electron beam semi-permeable film. The electron beam semi-transparent film may be anything as long as it absorbs the energy of the irradiated electron beam. A flexible film-like sheet material can be preferably used. Specifically, steel plates, aluminum plates, metal plates such as copper plates, polyester films, acetic acid fiber films, fluorohydrocarbon (so-called Teflon) films, polyamide films, polycarbonate films, polyolefin films, polyolefin-vinyl acetate copolymer films, Examples include synthetic resin films such as polyimide films, paper sheets, and synthetic paper sheets. A metal plate is more preferable in terms of resistance to electron beams and shielding properties.

In the present invention, the electron beam semi-permeable film is brought into close contact with the electron beam curable resin composition layer. The surface of the electron beam semi-transmissive film that is in close contact is provided with regular or irregular irregularities in advance. Specifically, the electron beam semi-permeable film surface is made uneven by matting, etching, engraving, or pressing the electron beam semi-permeable film itself so as to have predetermined unevenness. The unevenness may be provided by any other means. There are no particular restrictions on this unevenness,
Any kind of material may be used, but for example, the unevenness conventionally provided on a photographic support is disclosed in JP-A-51-3222 and JP-A-55-2650.
No. 7, JP-B-55-5103, JP-B-56-4902, JP-B-57-53
The electron beam semi-transmissive film can be previously provided with the irregularities described in No. 941, RD18717, RD19745 and the like.

The thickness of the electron beam semi-transmissive film cannot be specified unconditionally because the applied voltage at the time of electron beam irradiation and the shielding performance of the electron beam semi-transmissive film differ greatly depending on the material, but it is not less than the film thickness obtained according to the following formula. Something is preferable.

H = (V-60) / D where H is the electron beam semi-permeable film thickness (μm), V is the electron beam applied voltage (KV), and D is the electron beam semi-permeable film density (g / cm ³ ). Most of the irradiation electron beam energy is absorbed by the electron beam semi-permeable film. The amount of absorbed electron beam energy can be confirmed by the method described below.

An electron beam sensitive film whose color density changes depending on the amount of electron beam irradiation energy on the market, such as FWT Radiochromic Film Detector sold by Toyo Medic Co., Ltd. or CAT film manufactured by Fuji Photo Film Co., Ltd. Then, the amount of electron beam irradiation energy with and without passing the electron beam semi-permeable film is determined. The electron beam semi-permeable film used in the present invention has an electron beam energy absorption amount thus determined of 50% or more of irradiation energy.

Incidentally, when the electron beam is irradiated, an inert gas such as N ₂ , He,
Irradiation in a gas atmosphere such as CO ₂ is desirable.

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 a combination of the light-sensitive silver halide emulsion layer and the coupler, a cyan coupler is usually used in the red light-sensitive silver halide emulsion layer, and a magenta coupler is further added in the edge light-sensitive 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 pyrazoloazole couplers such as 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 to which the present invention is applied, in addition to the above-described silver halide emulsion layer, a non-adhesive layer such as a protective layer, an intermediate layer, a filter layer, a scavenger layer having an appropriate layer order and number of layers is formed on the support. A photosensitive 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 to which the present invention is applied, gelatin such as alkali-treated gelatin or acid-treated gelatin is the most common, but a part of this gelatin and phthalated gelatin or phenylcarbamoyl gelatin. Derivatives such as gelatin, albimine, agar, gum arabic, alginic acid, partially hydrolyzed cellulose derivatives, partially hydrolyzed polyvinyl acetate, polyacrylamide, polyvinyl alcohol, polyvinyl pyrrolidone, and copolymers of these vinyl compounds in combination It can also be used.

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 to which the present invention is applied, various photographic additives such as ultraviolet absorbers (for example, benzophenone compounds and benzotriazole compounds), dye image stabilizers (for example, phenol compounds). , Bisphenol compounds, hydroxychroman compounds, bisspirochroman compounds, hydantoin compounds and 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.

In the present invention, in order to coat each constituent layer such as a color photographic light-sensitive material on the support of the light-sensitive material, various coating methods can be used, for example, dip coating, roller coating,
A method such as bead coating or curtain flow coating can be adopted. Following application, drying is performed. 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. Further, in each of the steps, the treatment can be performed twice or more as needed. In addition,
In the processing step, in addition to the above, 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 in addition to the above. The processing temperature is set within a preferable range depending on the light-sensitive material and processing recipe. In general
The temperature is 20 to 60 ° C.
Suitable for processing above ℃.

Color developing agents used in color development include the 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-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-p-toluenesulfonate, N, N-
Examples thereof include diethyl-4-amino-3- (β-methanesulfonamidoethyl) aniline sulfate.

Among 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)-
Examples thereof include N-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 accelerators such as polyalkylene glycols, organic solvents such as benzyl alcohol, ethylene glycol, diethylene glycol, methanol and acetone, development inhibitors such as potassium bromide and nitrobenzimidazoles, sulfites, hydroxylamines, glucoses, alkanolamines And preservatives such as polyphosphoric acid compounds and water softeners such as nitrilotriacetic acid.

Example of Invention

Hereinafter, examples of the present invention will be described in more detail. As a matter of course, the present invention is not limited to the examples below.

The materials were blended as shown in the following compositions 1 and 2, and kneaded for 20 minutes with a pole mill and uniformly dispersed to obtain two kinds of compositions. Then, Compositions 1 and 2 were applied to one side of a paper having a basis weight of about 160 g / m ^{2 by} a reverse coater so that the thick film was 25 μm to form an electron beam curable resin composition layer.

(Composition 1) Toagosei Kagaku Kogyo Co., Ltd. Aronix M8060 10 parts by weight Nippon Soda Co., Ltd. polybutadiene TEA1000 25 parts by weight Nippon Yupica Co., Ltd. UPICA Coat AC5701 20 parts by weight Titanium dioxide (anatase type, average particle size 0.20 45 parts by weight Osaka Organic Chemicals Co., Ltd. Viscoat 700 30 parts by weight Izumi Petrochemical Co., Ltd. Polybutadiene R45ACR 15 parts by weight Shin Nakamura Chemicals Co., Ltd. NK ester AHD 15 parts by weight Titanium dioxide (rutile type, average particle size) Diameter 0.25 μm 40 parts by weight Next, while conveying the paper at a line speed of 10 m / min,
280kV 8mA, 200kV 10mA, 200kV from the side of the applied composition layer
The electron beam was irradiated with an intensity of 1 mA to cure the electron beam curable composition layer. Prior to electron beam irradiation, the electron beam curable composition layer is surface-matted to 30 μm, 40 μm and 50 μm
The stainless steel plate of was adhered, cured by electron beam irradiation, and then peeled off. As a result, the composition was cured and unevenness was formed on the cured layer. Next, an electron beam curable layer was provided on the opposite surface of the paper by the same operation. For comparison, a comparative sample was prepared by the same operation without adhering the electron beam semi-permeable film.

FIG. 1 schematically shows a state in which the electron beam irradiation device irradiates the electron beam curable resin composition layer provided on the paper with an electron beam in this case. In the figure, 1 is a paper as a base material, 2 is an electron beam curable resin layer, 3 is an electron beam irradiation device, 4 is an accelerator, 5 is an electron beam irradiation window, and 6 is an electron beam semitransparent film.

As shown enlarged and exaggerated, the electron beam semi-transmissive film 6
Has irregularities, which are in close contact with the resin layer 2.

Corona discharge treatment was applied to one side of each support thus obtained at a strength of 20 W / m ² min, and the photographic constituent layers described below were sequentially applied and dried to prepare 10 kinds of color photographic paper samples. (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: 1.2 g gelatin, and 0.05 g HQ-1 0.2 dissolved
A first intermediate layer containing g of dioctyl phthalate.

Layer 3: 1.9 g of gelatin, 0.040 g of edge-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. An edge-sensitive 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 gelatin, 0.027 g red-sensitive silver chlorobromide emulsion (50 mol% silver chloride), and 0.4 g cyan coupler (C-1) below, 0.01 g HQ-1 and 0.3 g 0.35 with UV-1 dissolved
Red light sensitive emulsion layer containing g dioctyl phthalate.

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.) Company's 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.

(Bleach-fixing solution) Pure water 600ml Ethylenediaminetetraacetic acid-2-sodium / 2H ₂ O 25g Ammonium sulfite (40% aqueous solution) 35ml Ammonium thiosulfate (70% aqueous solution) 150ml Ethylenediaminetetraacetic acid iron (III) ammonium 95g Ammonia water (28 %) Add 25 ml water to make 1 and pH with ammonia water or glacial acetic acid.
Adjust to 6.9.

Next, the following adhesion test and measurement of fogging density were 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 Roku Photo Industry Co., Ltd.).

2 and 3 show the results of measuring the electron beam irradiation energy amount of the example by FWT radiochromic film detector sold by Toyo Medic Co., Ltd. The conditions of measurement result-are as follows.

When irradiating with electron beam at 280Kv, 8mA and not passing through electron beam semi-permeable membrane) When irradiating with electron beam at 280Kv, 8mA and passing through 30μm thick side blasted stainless steel plate with matte surface When irradiated with an electron beam at 280Kv, 8mA and passed through a stainless steel plate with a 40μm surface matted 280Kv, when irradiated with an electron beam at 8mA and passed through a stainless steel plate with a 50μm surface 220Kv, Irradiate electron beam at 10mA and do not pass electron beam semi-permeable membrane 220Kv, 1mA electron beam do not pass electron beam semi-permeable membrane 220Kv, 10mA electron beam irradiated, 30μm thick When a stainless steel plate having a matte surface was passed through, the electron beam irradiation energy shielding effect of the electron beam semi-permeable film obtained from this table was as follows.

Shielding effect 65% 〃 85% 〃 94% 〃 87% Next, Table 1 shows the results of the fogging and adhesion test.

The photographic materials of Examples 1 to 7 had matt surfaces with a clean surface.

As is apparent from Table 1, Examples 1, 2, 3 and 4 according to the present invention have significantly improved fogging with time and have no problem in adhesion as compared with Comparative Examples 1 and 2 which are outside the scope of the present invention. Is clear.
Further, in Comparative Example 3, it is clear that in order to reduce the fog, the electron-electron irradiation current can be reduced to cure and the fog can be lowered to some extent, but it is clear that the adhesiveness is poor and the purpose cannot be achieved. Examples 5, 6 and 7 according to the present invention also have significantly improved fogging with time as compared with Comparative Examples 4 and 5, which are outside the scope of the present invention, and even if the content of the electron beam curable composition changes, the present invention Is clearly effective.

[Advantages of the Invention] As described above, according to the present invention, a photograph showing little increase in fogging during storage, sharpness of photographic images, smoothness of the surface, and excellent adhesion to the coating layer of the substrate A photosensitive material can be manufactured.

[Brief description of drawings]

FIG. 1 is a view showing a state in which an electron beam curable resin composition layer provided on paper is irradiated with an electron beam from an electron beam irradiation device, and FIG.
FIG. 3 and FIG. 3 are views showing several examples of the measurement results of the electron energy applied to the electron beam curable resin composition layer provided on the paper. 1 ... Paper, 2 ... Electron beam curable resin layer, 3 ... Electron beam irradiation device, 4 ... Accelerator, 5 ... Electron beam irradiation window, 6 ... Electron beam semitransparent film

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Hanawa No. 1 Sakura-cho, Hino-shi, Tokyo Photo by Konishi Roku Photo Industry Co., Ltd. (56) References JP 57-30830 (JP, A) JP 57-30576 (JP, A) JP 57-21965 (JP, A) JP 47-30730 (JP, A) JP-A-60-53949 (JP, A) JP-A-60-17446 (JP, A) JP-A-59-177543 (JP, A)

Claims (1)

[Claims] 1. An electron beam curable resin composition layer is obtained by coating an electron beam curable resin composition substantially composed of an electron beam curable compound and a pigment on at least one surface of a substrate, and an electron beam curable resin composition layer is formed on this layer. To prepare a support as a cured resin layer, and in the method for producing a photographic photosensitive material in which a photographic photosensitive layer is provided on the support, the electron beam curable resin composition layer is irradiated with an electron beam. When forming a cured resin layer, an electron beam is irradiated from the electron beam curable resin composition layer side, and this electron beam irradiation is performed through an electron beam semi-permeable film that absorbs the energy of the electron beam irradiated, The line semi-transparent film absorbs 50% or more of the irradiation energy, and the surface of the electron beam semi-transparent film has regular or irregular irregularities, and the irregular surface has an electron beam. Adheres to the electron beam curable resin composition layer during irradiation Method for producing a photographic light-sensitive material characterized in and.